* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With sodium In tetrahydrofuran; paraffin oil at 50℃; for 6 h;
In this example, following Example 1, the synthesis of 4,4′-di-tert-butyl-2,2′-bipyridine was investigated. In this example, the synthesis was performed through the reaction of 4-tert-butylpyridine with SD at low concentrations in THF. 4-tert-Butylpyridine (0.5 mmol) was reacted with SD in an amount of molar equivalents with respect to 4-tert-butylpyridine as shown in FIG. 2 in THF. The usage amounts of THF, the reaction temperatures and the reaction times were set as shown in FIG. 2, and the synthesis was performed in the same manner as in Example 1. After the reaction, in the same manner as in Example 1, the production amounts of 4,4′-di-tert-butyl2,2′-bipyridine (Compound 2), which was the target reaction product, and 4-tert-butyl-1,4-dihydropyridine (Compound 1) and 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine (Compound 3), which were the possible reaction by-products, were measured, and their yields were calculated. The recovery rate of the unreacted 4-tert-butylpyridine was calculated in the same manner. The results are summarized in FIG. 2. It is found from these results that when 4-tert-butylpyridine (0.5 mmol) was reacted with SD in an amount of 1 to 2 mol equivalents with respect to the 4-tert-butylpyridine in 2 to 4 ml of THF at 25 to 50° C. for 1 to 24 hours, the 4,4′-di-tert-butyl-2,2′-bipyridine compound was obtained with a high yield in all of the cases. In particular, when 0.5 mmol 4-tert-butylpyridine was reacted with SD in an amount of 1 mol equivalent with respect to the 4-tert-butylpyridine in 2 ml of THF at 50° C. for 1 to 6 hours, the 4,4′-di-tert-butyl-2,2′-bipyridine compound was obtained with a high yield without the generation of reaction by-products. In addition, when 0.5 mmol 4-tert-butylpyridine was reacted with SD in an amount of 1 mol equivalent with respect to the 4-tert-butylpyridine in 4 ml of THF at 25° C. for 6 hours, the 4,4′-di-tert-butyl-2,2′-bipyridine compound was obtained with a high yield without the generation of reaction by-products. It was found that when SD in an amount of 2 mol equivalents was used, the yield decreased compared with the case of 1 mol equivalent, and the material balance also decreased. It was also found from comparison with Example 1 that the lower the concentrations of 4-tert-butylpyridine and SD were with respect to THF, the higher the yield was.
Reference:
[1] Patent: US2018/282278, 2018, A1, . Location in patent: Paragraph 0057; 0127-0130
[2] Helvetica Chimica Acta, 1980, vol. 63, # 6, p. 1675 - 1702
[3] Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999), 2000, # 1, p. 63 - 68
[4] Inorganica Chimica Acta, 2011, vol. 365, # 1, p. 127 - 132
[5] Synthesis (Germany), 2013, vol. 45, # 22, p. 3099 - 3102
[6] Organometallics, 2016, vol. 35, # 14, p. 2348 - 2360
[7] Patent: US4177349, 1979, A,
[8] Patent: US4177349, 1979, A,
2
[ 81167-60-4 ]
[ 72914-19-3 ]
Yield
Reaction Conditions
Operation in experiment
90%
With manganese; nickel(II) bromide trihydrate In N,N-dimethyl-formamide at 20 - 60℃; for 20 h; Inert atmosphere
General procedure: On the benchtop, a 50 mL round-bottomed flask equipped with a inch Teflon coated magnetic stir bar was charged with NiBr2·3H2O(401 mg, 1.47 mmol) and DMF (20.0 mL). The vessel was stopperedwith a rubber septum and heated to 60 °C until a green homogeneoussolution resulted (approx. 20 min). Once homogeneity wasachieved, the vessel was removed from the heat and allowed to coolto r.t. Once at r.t., 4-tert-butyl-2-chloropyridine (2a; 4.99 g, 29.4mmol) and Mn powder (–325 mesh, 3.30 g, 60.0 mmol) were added,and the vessel was resealed with the septum, purged with argon, andheated again to 60 °C for the duration of the reaction. Reactionprogress was monitored by GC analysis of aliquots of the crude reactionmixture. In general, the reaction turns very dark brown orblack in color when complete, and the color change is a reliable indicatorfor the reaction endpoint. Upon completion, the reactionmixture was cooled to r.t., diluted with Et2O (80 mL), and filteredthrough a short pad of Celite (approx. 2 in × 2 in × 2 in) that hadbeen wetted with Et2O to remove metal salts. The reaction vesselwas washed with Et2O (2 × 40 mL) and the washings were thenpassed through the filter. The combined filtrates were transferred toa separatory funnel and washed with aq 1 M NaOH (200 mL). Abrown emulsion formed in the separatory funnel during the workupthat slowly separated. Care was taken to keep the brown emulsion with the organics. Once separated, the aqueous layer was extractedwith additional Et2O (3 × 150 mL). The combined organic extracts and brown emulsion were washed with brine (500 mL). Again carewas taken to keep the brown emulsion with the organics. The organicswere dried with copious amounts of MgSO4. The solid dryingagent was removed by filtration, ground into a fine powder, andwashed with additional Et2O (3 × 150 mL). The filtrate was evaporated to dryness to give 3a (3.57 g) as faintly yellow crystals in 90percentyield. This material was judged analytically pure by NMR and combustion analysis. If necessary the product can be further purified bysublimation (140 °C/300 mtorr).
With sodium In tetrahydrofuran; paraffin oil at 25℃; for 24 h;
In this example, following Example 1, the synthesis of 4,4′-di-tert-butyl-2,2′-bipyridine was investigated. In this example, the synthesis was performed through the reaction of 4-tert-butylpyridine with SD at low concentrations in THF. 4-tert-Butylpyridine (0.5 mmol) was reacted with SD in an amount of molar equivalents with respect to 4-tert-butylpyridine as shown in FIG. 2 in THF. The usage amounts of THF, the reaction temperatures and the reaction times were set as shown in FIG. 2, and the synthesis was performed in the same manner as in Example 1. After the reaction, in the same manner as in Example 1, the production amounts of 4,4′-di-tert-butyl2,2′-bipyridine (Compound 2), which was the target reaction product, and 4-tert-butyl-1,4-dihydropyridine (Compound 1) and 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine (Compound 3), which were the possible reaction by-products, were measured, and their yields were calculated. The recovery rate of the unreacted 4-tert-butylpyridine was calculated in the same manner. The results are summarized in FIG. 2. It is found from these results that when 4-tert-butylpyridine (0.5 mmol) was reacted with SD in an amount of 1 to 2 mol equivalents with respect to the 4-tert-butylpyridine in 2 to 4 ml of THF at 25 to 50° C. for 1 to 24 hours, the 4,4′-di-tert-butyl-2,2′-bipyridine compound was obtained with a high yield in all of the cases. In particular, when 0.5 mmol 4-tert-butylpyridine was reacted with SD in an amount of 1 mol equivalent with respect to the 4-tert-butylpyridine in 2 ml of THF at 50° C. for 1 to 6 hours, the 4,4′-di-tert-butyl-2,2′-bipyridine compound was obtained with a high yield without the generation of reaction by-products. In addition, when 0.5 mmol 4-tert-butylpyridine was reacted with SD in an amount of 1 mol equivalent with respect to the 4-tert-butylpyridine in 4 ml of THF at 25° C. for 6 hours, the 4,4′-di-tert-butyl-2,2′-bipyridine compound was obtained with a high yield without the generation of reaction by-products. It was found that when SD in an amount of 2 mol equivalents was used, the yield decreased compared with the case of 1 mol equivalent, and the material balance also decreased. It was also found from comparison with Example 1 that the lower the concentrations of 4-tert-butylpyridine and SD were with respect to THF, the higher the yield was.
Reference:
[1] Patent: US2018/282278, 2018, A1, . Location in patent: Paragraph 0057; 0127-0130
[2] Chemistry - A European Journal, 2018, vol. 24, # 55, p. 14830 - 14835
4
[ 1187755-05-0 ]
[ 72914-19-3 ]
Reference:
[1] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2010, vol. 65, # 7, p. 861 - 872
[2] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2010, vol. 65, # 7, p. 861 - 872
5
[ 1268488-94-3 ]
[ 72914-19-3 ]
Reference:
[1] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2010, vol. 65, # 7, p. 861 - 872
[2] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2010, vol. 65, # 7, p. 861 - 872
6
[ 1187755-05-0 ]
[ 72914-19-3 ]
Reference:
[1] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2010, vol. 65, # 7, p. 861 - 872
[2] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2010, vol. 65, # 7, p. 861 - 872
7
[ 1268488-94-3 ]
[ 72914-19-3 ]
Reference:
[1] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2010, vol. 65, # 7, p. 861 - 872
[2] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2010, vol. 65, # 7, p. 861 - 872
8
[ 1187755-05-0 ]
[ 72914-19-3 ]
Reference:
[1] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2010, vol. 65, # 7, p. 861 - 872
9
[ 1268488-94-3 ]
[ 72914-19-3 ]
Reference:
[1] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2010, vol. 65, # 7, p. 861 - 872
10
[ 72914-19-3 ]
[ 676525-77-2 ]
Yield
Reaction Conditions
Operation in experiment
77%
Stage #1: at 150℃; for 15 h; Inert atmosphere
A magnetically stirred suspension of 4,4’-di-tert-butyl-2,2’-dipyridyl (118 mg, 0.44 mmol) and tetrakis(2-phenylpyridine-C2,N’)(μ-dichloro)-diiridium (214 mg, 0.2 mmol) in 10 mL of 1,2-ethanediol under nitrogen was heated to 150 °C. The mixture was kept at this temperature for 15h. All the solids dissolved to yield a clear, yellow solution. After cooling the mixture to room temperature, 150 mL of water was added. The excess of bipyridine ligand was removed through three extractions with diethyl ether (50 mL), and the aqueous layer was subsequently heated to 60-70 °C. NH4PF6 (1 g) in 10 mL of water was added, and the PF6 salt of the chromophore immediately precipitated. After cooling the suspension to 5 °C, the yellow solid was separated through filtration, dried, and recrystallized through acetonitrile/ether diffusion. Yield: 280 mg (77percent).
66%
Stage #1: at 150℃; for 15 h; Inert atmosphere
Synthesis of [Ir(ppy)2(dtbbpy)](PF6) was adapted from literature procedures6 for the analogousunsubstituted complex. A stirred suspension of 4,4-di-tert-butyl-2,2-dipyridyl (0.44 g, 0.88mmol) and tetrakis(2-phenylpyridine-C,N)(µ-dichloro)diiridium, A (0.428g, 0.400 mmol) in 20mL of 1,2-ethanediol under nitrogen was heated to 150 °C for 15 h. All the solids dissolved toyield a clear, yellow solution. After cooling the mixture to room temperature, 200 mL of waterwere added. The excess of the bipyridine ligand was removed through three extractions withdiethyl ether (3 × 50 mL), and the aqueous layer was subsequently heated to 70 °C. NH4PF6 (2 g)in 20 mL of water was added, and the PF6 salt of the iridium complex immediately precipitated.After cooling the suspension to 5 °C, the yellow solid was separated through filtration, dried, andrecrystallized through acetonitrile/ether. Yield: 0.50 g (66percent). 1H NMR (acetone-d6, 400 MHz):δ 8.88 (d, J =2.0 Hz, dtb-bpy-H3, 2H), 8.24 (ppy-H6, pyridine, 2H, d, J = 8), 7.99-7.93 ( m,dtb-bpy-H6, 2H, ppy-H5, pyridine, 2H), 7.90 (ppy-H3, phenyl, 2H, dd, J = 7.2, 0.8 Hz), 7.79(ppy-H6, phenyl, 2H, d, J = 6 Hz), 7.71 (dtb-bpy-H5, 2H, dd, J = 6.0, 2.0 Hz), 7.14 (ppy-H4,pyridine, 2H, dt, J = 7.2, 1.6 Hz), 7.04 (ppy-H4, phenyl, 2H, dt, J= 7.6, 0.8 Hz), 6.91 (ppy-H5,phenyl, 2H, dt, J = 6.8, 1.2 Hz), 6.34 (ppy-H3, pyridine, 2H, d, J = 8), 1.42 (18H, s).HRMS (ESI) m/z calculated for C40H40N4Ir+ ([M - PF6]+) 769.2876, found 769.2866.
Reference:
[1] Tetrahedron Letters, 2018, vol. 59, # 21, p. 2046 - 2049
[2] Journal of the American Chemical Society, 2018,
[3] Organic and Biomolecular Chemistry, 2015, vol. 13, # 2, p. 447 - 451
[4] Beilstein Journal of Organic Chemistry, 2016, vol. 12, p. 2636 - 2643
[5] Chemical Communications, 2015, vol. 51, # 89, p. 16033 - 16036
11
[ 17084-13-8 ]
[ 72914-19-3 ]
[ 676525-77-2 ]
Reference:
[1] Organic and Biomolecular Chemistry, 2016, vol. 14, # 38, p. 9088 - 9092
12
[ 870987-64-7 ]
[ 72914-19-3 ]
[ 676525-77-2 ]
Reference:
[1] Chemistry - A European Journal, 2018, vol. 24, # 44, p. 11314 - 11318
13
[ 72914-19-3 ]
[ 676525-77-2 ]
Reference:
[1] Journal of the American Chemical Society, 2004, vol. 126, # 43, p. 14129 - 14135
14
[ 26042-63-7 ]
[ 72914-19-3 ]
[ 676525-77-2 ]
Reference:
[1] Chemistry - A European Journal, 2013, vol. 19, # 20, p. 6340 - 6349
15
[ 26042-63-7 ]
[ 72914-19-3 ]
[ 676525-77-2 ]
Reference:
[1] Journal of Materials Chemistry C, 2018, vol. 6, # 24, p. 6385 - 6397
16
[ 808142-69-0 ]
[ 72914-19-3 ]
[ 808142-80-5 ]
Reference:
[1] Journal of the American Chemical Society, 2004, vol. 126, # 43, p. 14129 - 14135
17
[ 870987-64-7 ]
[ 72914-19-3 ]
[ 870987-63-6 ]
Yield
Reaction Conditions
Operation in experiment
75%
Stage #1: for 15 h; Reflux; Inert atmosphere
Bis-(μ)-chlorotetrakis(2-(4,6-difluoromethylphenyl)-pyridinato-C2,N)diiridium(III) (0.09 mmol, 0.13 g) was heated to reflux with 4,4’-di-tert-butyl-2,2’-dipyridyl (0.20 mmol, 0.054g) in ethylene glycol (6.0 mL) under nitrogen with constant stirring for 15h. Upon cooling to room temperature, the mixture was transferred to a separatory funnel with water (60 mL) and washed with hexanes (3×30 mL). The aqueous layer was heated to 85 °C for 5 min to remove residual hexanes. A 10 mL aqueous ammonium hexafluorophosphate solution (1.0g in 10 mL deionized water) was added to the reaction mixture, producing a yellow-green amorphous powder. This precipitate was filtered, dried, and recrystallized by acetone:pentane vapor diffusion, giving the pure product, [Ir(dF(CF3)ppy)2(dtbbpy)]-(PF6). Yield: 0.15 g (75percent).
121 mg
Stage #1: at 150℃; for 15 h; Inert atmosphere
General procedure: Heteroleptic iridium 4xy were synthesized in a two-step procedure[42,43]. In the first step, chloro-bridged dimer was synthesized by charging a two-necked reaction flask with magnetic stir bar, iridium(III) chloride (1 equiv), ligand (2.26 equiv), and a 2:1 v:v mixture of 2-methoxyethanol/water. The mixture was degased with Ar (via Ar bubbling) and heated under reflux at 120 °C with constant stirring overnight. The reaction mixture cooled to room temperature and filtered. The precipitate was washed with water (3x10 mL), dried in air and taken onto the second step without further purification unless noted. In the second step, the chloro bridging dimer (1 equiv), bipyridyl ligand (2.2 equiv) and ethylene glycol were placed in a two-necked flask and then flushed with Ar. The mixture was heated at 150 °C for 15 h and then cooled. The cooled reaction mixture was washed hexane (3 10 mL) and mixture was heated to 85 °C for 5 min to remove residual hexane. Aqueous ammonium hexafluorophosphate (sat. solution) was added to the reaction mixture causing the iridium-PF6 salt to precipitate,which was filtered, dried and recrystallized (acetone/ether).
Reference:
[1] Journal of Organic Chemistry, 2015, vol. 80, # 15, p. 7642 - 7651
[2] Tetrahedron Letters, 2018, vol. 59, # 21, p. 2046 - 2049
[3] Journal of Organometallic Chemistry, 2015, vol. 776, p. 51 - 59
18
[ 17084-13-8 ]
[ 870987-64-7 ]
[ 72914-19-3 ]
[ 870987-63-6 ]
Reference:
[1] Organic Letters, 2018,
19
[ 387827-64-7 ]
[ 72914-19-3 ]
[ 870987-63-6 ]
Reference:
[1] Chemistry - A European Journal, 2018, vol. 24, # 44, p. 11314 - 11318
With sodium; In tetrahydrofuran; paraffin oil; at 50℃; for 6h;
In this example, following Example 1, the synthesis of 4,4?-di-tert-butyl-2,2?-bipyridine was investigated. In this example, the synthesis was performed through the reaction of 4-tert-butylpyridine with SD at low concentrations in THF. 4-tert-Butylpyridine (0.5 mmol) was reacted with SD in an amount of molar equivalents with respect to 4-tert-butylpyridine as shown in FIG. 2 in THF. The usage amounts of THF, the reaction temperatures and the reaction times were set as shown in FIG. 2, and the synthesis was performed in the same manner as in Example 1. After the reaction, in the same manner as in Example 1, the production amounts of 4,4?-di-tert-butyl2,2?-bipyridine (Compound 2), which was the target reaction product, and 4-tert-butyl-1,4-dihydropyridine (Compound 1) and 4,4?,4?-tri-tert-butyl-2,2?:6?,2?-terpyridine (Compound 3), which were the possible reaction by-products, were measured, and their yields were calculated. The recovery rate of the unreacted 4-tert-butylpyridine was calculated in the same manner. The results are summarized in FIG. 2. It is found from these results that when 4-tert-butylpyridine (0.5 mmol) was reacted with SD in an amount of 1 to 2 mol equivalents with respect to the 4-tert-butylpyridine in 2 to 4 ml of THF at 25 to 50 C. for 1 to 24 hours, the 4,4?-di-tert-butyl-2,2?-bipyridine compound was obtained with a high yield in all of the cases. In particular, when 0.5 mmol 4-tert-butylpyridine was reacted with SD in an amount of 1 mol equivalent with respect to the 4-tert-butylpyridine in 2 ml of THF at 50 C. for 1 to 6 hours, the 4,4?-di-tert-butyl-2,2?-bipyridine compound was obtained with a high yield without the generation of reaction by-products. In addition, when 0.5 mmol 4-tert-butylpyridine was reacted with SD in an amount of 1 mol equivalent with respect to the 4-tert-butylpyridine in 4 ml of THF at 25 C. for 6 hours, the 4,4?-di-tert-butyl-2,2?-bipyridine compound was obtained with a high yield without the generation of reaction by-products. It was found that when SD in an amount of 2 mol equivalents was used, the yield decreased compared with the case of 1 mol equivalent, and the material balance also decreased. It was also found from comparison with Example 1 that the lower the concentrations of 4-tert-butylpyridine and SD were with respect to THF, the higher the yield was.
Yield of 4,4'-di-(t-butyl)-2,2'-bipyridyl, based on 4-t-butylpyridine consumed, was 88.7%. There was no evidence of any 2-amino-4-t-butylpyridine.
With sodium amide;sodium; iron; In ammonia; water;
4,4'-di-(t-butyl)-2,2'-bipyridyl In a one-liter, three-neck flask, equipped with a stirrer and dropping funnel, was prepared one mole of sodamide (23.0 g of sodium and iron catalyst) in 700 cc of liquid ammonia. The ammonia was replaced with 589.7 g (4.37 moles) of 4-t-butylpyridine. The mixture was heated to 135 C. at which time the purple reaction mixture began evolving hydrogen. The reaction was continued for 3.1 hours at 135-149 C. until hydrogen evolution became slow. The reaction mixture was cooled to 100 C. and hydrolyzed with 100 cc of water. The oil layer was separated at 40 C. The aqueous layer was extracted with 50 cc of xylene. The oil layer and xylene extract were charged to a Vigreaux column for distillation. Xylene and about 300 g of unreacted 4-t-butylpyridine were distilled under vacuum. The residue was cooled to room temperature, allowing 4,4'-di-(t-butyl)-2,2'-bipyridyl to crystallize. It was filtered and washed with acetone to give 66.4 g of 4,4'-di-(t-butyl)-2,2'-bipyridyl with a melting point of 159-160 C. The filtrate was then further distilled to give more unreacted 4-t-butylpyridine and 57.7 g additional 2,2'-bipyridyl product (the boiling point of this 4,4'-di-(t-butyl)-2,2'-bipyridyl being about 235 C. at 32 mm Hg). The total 4-t-butylpyridine recovered was 448.7 g (3.32 moles).
Add in 100mL three-necked flaskAnhydrous NiCl2 (129.6 mg, 1.0 mmol)13mL of ethanol solution,Add to the solution4,4'-ditBu-bpy (271 mg, 1.0 mmol)7mL of ethanol solution,After the reaction solution was heated to reflux for 10 hours,The reaction solution is filtered,The filtrate was concentrated to give a green solid 358 mg (90% yield).The solid was recrystallized from methanol.
[tetrakis(μ-acetate)diaquadiruthenium(II,III)] hexafluorophosphate[ No CAS ]
[ 72914-19-3 ]
tris-(4,4’-di-tert-butyl-2,2’-bipyridine)ruthenium(II) hexafluorophosphate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%
In methanol; ethanol; for 6h;Reflux; Inert atmosphere;
[Ru2(mu-O2CCH3)4(H2O)2](PF6) (0.100 g, 0.162 mmol) was dissolved in a minimal amount of methanol (?15-25 mL) producing a dark orange solution. A 6-fold molar ratio of 4,4?-di-t-butyl-2,2?-bipyridine (0.259 g, 0.950 mmol) was dissolved in a minimal amount of methanol (?10-20 mL. Upon mixing, the reaction mixture was refluxed for 6 h under argon. The resulting solution was placed in the refrigerator (?4 C). After approximately 24 h crystals were suction filtered, washed with ?2 mL of methanol and dried in vacuo overnight. Anal. Calc. for C54H72N6RuP2F12: C, 54.22; H, 6.07; N, 7.03. Found: C, 53.92; H, 6.19; N, 7.06%.
Example 5 [0071] Os3(CO)12 (0.2 g, 0.221 mmol), 4,4?-di-tert-butyl-2,2?-bipyridine (173 mg, 0.684 mmol) and the product of Synthesis Example 1 (185 mg, 0.684 mmol) were disposed in a 150 ml reaction flask, followed by adding 50 ml diethylene glycol monomethyl ether and heating at 180 C. for 24 hours under a nitrogen gas atmosphere. After the reaction was finished, the reaction mixture was cooled to room temperature, followed by reduced pressure distillation to remove diethylene glycol monomethyl ether. Next, the mixture was subjected to column chromatography, in which a mixture of ethyl acetate and hexane (ethyl acetate:hexane=1:1) was used as an eluent. Thereafter, recrystallization was conducted using dichloromethane and hexane to obtain a yellow solid product (0.162 g, 0.205 mmol, 31% yield). The yellow solid product (0.1 g, 0.127 mmol) was dissolved in diethylene glycol monomethyl ether, followed by adding trimethylamine N-oxide (20 mg, 0.267 mmol) and stirring at room temperature for 1 hour. Thereafter, the mixture was added with 4,4?-diethoxycarbonyl-2,2?-bipyridine (41.98 mg, 0.14 mmol), followed by heating under reflux for 24 hours under a nitrogen gas atmosphere. Next, diethylene glycol monomethyl ether was removed by means of reduced pressure distillation. Thereafter, the mixture was subjected to column chromatography, in which a mixture of ethyl acetate and hexane (ethyl acetate:hexane=1:2) was used as an eluent to obtain a black solid product (39.6 mg, 0.041 mmol, 41.9% yield). [0072] The black solid product (0.1 g, 0.103 mmol) was dissolved in 50 ml acetone, followed by adding 5 ml of a sodium hydroxide solution (2M) and stirring at room temperature for 8 hours. Next, acetone was removed by means of reduced pressure distillation, followed by adding 20 ml deionized water and adjusting pH of the reaction mixture to about 3 using a hydrogen chloride solution (2N). A filtration process was conducted and a filter cake was collected, followed by washing the filter cake using deionized water and dichloromethane to obtain a dark brown solid product (86 mg, 0.088 mmol, 86% yield) (hereinafter referred to as osmium complex A-5). [0073] The spectrum analysis for the osmium complex A-5 is: 1H NMR (400 MHz, CDCl3, 294K), delta (ppm): 8.99 (s, 1H), 8.97 (s, 1H), 8.74 (s, 1H), 8.66 (s, 1H), 7.98 (d, 3JHH=6 Hz, 1H), 7.95 (d, 3JHH=6 Hz, 1H), 7.68 (d, 3JHH=5.6 Hz, 1H), 7.65 (d, 3JHH=4.8 Hz, 1H), 7.52 (d, 3JHH=6.4 Hz, 1H), 7.42 (d, 3JHH=6 Hz, 1H), 7.37 (d, 3JHH=6 Hz, 1H), 7.27 (d, 3JHH=4.8 Hz, 1H), 1.40 (s, 9H), 1.34 (S, 9H); 19F-{1H} NMR (470 MHz, d5-dimethyl sulfoxide, 294K), delta (ppm): -61.55 (s, CF3), -61.8 (s, CF3); MS (FAB): m/z 974 [M]+. [0074] The chemical structure of the osmium complex A-5 is
4,4′-di-tert-butyl-2,2′-bipyridin-N-oxide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76%
With 3-chloro-benzenecarboperoxoic acid; In chloroform; at 20℃; for 20h;Inert atmosphere; Schlenk technique; Sealed tube;
A solution of dtbpy (1.34 g, 5.0 mmol, 1.0 eq.) in CHCl3 was stirred at 0 C for 35 min; then, a solution of m-chloroperbenzoic acid (1.03 g, 6.0 mmol, 1.2 eq.) in CHCl3 was added dropwise to the mixture slowly, and the mixture was stirred at room temperaturefor 20 h. Then, the solution was washed with 5% aqueous Na2CO3 solution, dried over anhydrousNa2SO4, and concentrated. The Na2CO3 washings were extracted with CHCl3. The extract was dried over anhydrous Na2SO4 and concentrated. Each residue oil was put together and then purified by column chromatography using a PE:EA ratio of 10:1 to get the target product as a light yellow solid,(1.08 g, 3.8 mmol, yield = 76%). (The spectral data were in accordance with literature [54]). 1H-NMR(400 MHz, Acetone-d6) 9.00 (dd, J = 0.7, 2.0 Hz, 1H), 8.50 (dd, J = 0.7, 5.2 Hz, 1H), 8.10-8.08 (m, 2H),7.35-7.32 (m, 2H), 1.25 (s, 9H), 1.24 (s, 9H); 13C NMR (400 MHz, Acetone-d6) 159.7, 150.2, 149.2, 148.7,145.8. 140.0, 124.3, 122.9, 122.2, 121.1, 34.6, 34.3.
[{(dimethylglyoxime)Cu(4,4′-ditertbutyl-2,2’-bipyridine)}2ClCo-(4,4′-bipyridine)-CoCl{(dimethylglyoxime)Cu(4,4′-ditertbutyl-2,2’-bipyridine)}2](ClO4)4[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68%
With triethylamine; In ethanol; water; N,N-dimethyl-formamide; for 6h;Reflux;
General procedure: The complexes [{dmgCu(N-N)}2ClCo-(4,4?-bpy)-CoCl{dmgCu(N-N)}2](ClO4)4 (3-9) and as linked ligands, N-N=2,2?-bipyridine (bpy), 1,10-phenanthroline (phen), 3,3?-dicarboxy-2,2?-bipyridine (dcbpy), 4,5-diazafluoren-9-one (dafo), 1,10-phenanthroline-5,6-dione (dione), 4,4?-ditertbutyl-2,2?-bipyridine (dtbpy) and 4,5-diazafluorene-9-oxime (dafoxi) containing these multinuclear complexes were synthesized according to the reported analogous procedure with some modifications. The complex (1) (0.5 g, 0.62 mmol) was added to Et3N (5 mL) in absolute ethanol-DMF-H2O (80:5:3 mL) and the mixture was stirred for 1 h. The separated solution of Cu(ClO4)2·6H2O (0.94g, 2.48mmol) for all of multinuclear [{dmgCu(N-N)}2ClCo-(4,4?-bpy)-CoCl{dmgCu(N-N)}2](ClO4)4 in absolute ethanol (20 mL) and 2,2?-bipyridine (0.40 g, 2.48 mmol), 1,10-phenanthroline monohydrate (0.49 g, 2.48 mmol), 3,3?-dicarboxy-2,2?-bipyridine (0.60 g, 2.48 mmol), 4,5-diazafluoren-9-one (0.48 g, 2.48 mmol), 1,10-phenanthroline-5,6-dione (0.52 g, 2.48 mmol), 4,4?-ditertbutyl-2,2?-bipyridine (0.67 g, 2.48 mmol) and 4,5-diazafluorene-9-oxime (0.49 g, 2.48 mmol) in absolute ethanol (15 mL) was successively added to the resulting mixture, which was boiled under reflux for 6 h. Then, the mixtures left to 48 h for precipitating. The solvent was evaporated slowly at room temperature and the products were recrystallized from EtOH/H2O (1:2) to give different color crystals which were filtered, then washed with EtOH, MeOH and Et2O and dried in air. Color: brown; Yield (%): 68, m.p: 202C, Anal. Calc. for [C98H128N18O24Cl6Cu4Co2] (F.W: 2527.0g/mol): C, 46.58; H, 5.11; N, 9.98. Found: C, 46.53; H, 5.08; N, 10.04%. LambdaM=252Omega-1cm2mol-1, mueff=1.48 [B.M]. (for per Cu(II) ion), LC-MS (Scan ES+): m/z (%) 2528.2 (18) [M+H]+, FT-IR (KBr pellets, numax/cm-1): 3072-3025 nu(Ar-CH), 2967-2871 nu(Aliph-CH), 1618 nu(C=N of oxime), 1550 nu(C=N of pyridine), 1483-1414 nu(C=C), 1236 nu(N-O), 1093 and 624 nu(ClO4), 509 nu(Co-N) and 469 nu(Cu-O). UV-Vis (lambdamax, nm, FontWeight="Bold" FontSize="10" = shoulder peak): 231 FontWeight="Bold" FontSize="10" , 253, 298 and 309 (in C2H5OH); 241, 261, 299 and 386 FontWeight="Bold" FontSize="10" (in DMSO).
With manganese; nickel(II) bromide trihydrate; In N,N-dimethyl-formamide; at 20 - 60℃; for 20h;Inert atmosphere;
General procedure: On the benchtop, a 50 mL round-bottomed flask equipped with a inch Teflon coated magnetic stir bar was charged with NiBr2·3H2O(401 mg, 1.47 mmol) and DMF (20.0 mL). The vessel was stopperedwith a rubber septum and heated to 60 C until a green homogeneoussolution resulted (approx. 20 min). Once homogeneity wasachieved, the vessel was removed from the heat and allowed to coolto r.t. Once at r.t., <strong>[81167-60-4]4-tert-butyl-2-chloropyridine</strong> (2a; 4.99 g, 29.4mmol) and Mn powder (-325 mesh, 3.30 g, 60.0 mmol) were added,and the vessel was resealed with the septum, purged with argon, andheated again to 60 C for the duration of the reaction. Reactionprogress was monitored by GC analysis of aliquots of the crude reactionmixture. In general, the reaction turns very dark brown orblack in color when complete, and the color change is a reliable indicatorfor the reaction endpoint. Upon completion, the reactionmixture was cooled to r.t., diluted with Et2O (80 mL), and filteredthrough a short pad of Celite (approx. 2 in × 2 in × 2 in) that hadbeen wetted with Et2O to remove metal salts. The reaction vesselwas washed with Et2O (2 × 40 mL) and the washings were thenpassed through the filter. The combined filtrates were transferred toa separatory funnel and washed with aq 1 M NaOH (200 mL). Abrown emulsion formed in the separatory funnel during the workupthat slowly separated. Care was taken to keep the brown emulsion with the organics. Once separated, the aqueous layer was extractedwith additional Et2O (3 × 150 mL). The combined organic extracts and brown emulsion were washed with brine (500 mL). Again carewas taken to keep the brown emulsion with the organics. The organicswere dried with copious amounts of MgSO4. The solid dryingagent was removed by filtration, ground into a fine powder, andwashed with additional Et2O (3 × 150 mL). The filtrate was evaporated to dryness to give 3a (3.57 g) as faintly yellow crystals in 90%yield. This material was judged analytically pure by NMR and combustion analysis. If necessary the product can be further purified bysublimation (140 C/300 mtorr).
[In(4,4'-di-tert-butyl-2,2'-bipyridine)Cl3(DMSO)].2DMSO[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
74%
A solution of 4,4-di-tert-butyl-2,2-bipyridine (0.30 g, 1.12 mmol) in methanol (15 mL) was added to a solution of InCl3.4H2O (0.34 g, 1.12 mmol) in methanol (15 mL), and the resulting colorless solution was stirred for 30 min at 45C. Suitable crystals for X-ray diffraction measurement were obtained by methanol diffusion to a colorless solution of 1 in DMSO over one week (yield 0.60 g, 74.0%, m.p. > 300C). IR (CsI, cm-1): 3055w, 2968m, 2865w, 1614s, 1551m, 1478m,1411s, 1366m, 1310m, 1255s, 1204m, 1105w, 1027s, 991s,950s, 950s, 898s, 859s, 725w, 610m, 550m, 480w, 430s, 340m,282s. UV-Vis: lambdamax (DMSO, nm), 315. 1H NMR (DMSO-d6,ppm): 1.45 (s, 9H), 7.97 (d, 1H), 8.77 (s, 1H), and 9.13 (d, 1H). 13C{1H} NMR (DMSO-d6, ppm): 30.5(s), 36.3 (s), 120.8 (s),124.5 (s), 145.9 (s), 147.4 (s) and 166.4 (s). Anal. Calcd. C,39.81; H, 5.80; N, 3.87. Found: C, 39.45; H, 5.75; N, 3.84%.
General procedure: In a two-necked, 100 mL round-bottom flask equipped with a blanket of nitrogen (N2) was placed 60 mL of 96% ethanol. [ClCo(LH)2(4-t-BuPy)] (2) complex (0.40 g, 0.66 mmol) and Et3N (3 mL) were added slowly with stirring to this solution, consecutively. The solution was brought to reflux for over 1 h. To this solution were successively added separated solutions of Cu(ClO4)2.6H2O (0.50 g, 1.32 mmol) in 96% ethanol (10 mL) and 2,2'-bipyridine (bpy) (0.21 g, 1.32 mmol), 1,10-phenanthroline monohydrate (phen) (0.26 g, 1.32 mmol), 1,10-phenanthroline-5,6-dione (dione) (0.27 g, 1.32 mmol), and 4,4'-ditertbutyl-2,2'-bipyridine (dtbpy) (0.35 g, 1.32 mmol) in 96% ethanol (15 mL) as linked ligands followed by boiling under reflux for 5 h to synthesize three new trinuclear complexes having a general formula [{Cu(N-N)}2ClCo(L)2(4-t-BuPy)](ClO4)2 (4-7). The dark brown color of the mononuclear [ClCo(LH)2(4-t-BuPy)] (2) complex changed to pale brown or green upon formation of the three trinuclear [{Cu(N-N)}2ClCo(L)2(4-t-BuPy)](ClO4)2 (4-7) complexes. Then the mixtures were left for 48 h to precipitate. The solvent was evaporated slowly at room temperature and the products were recrystallized from CH2Cl2/EtOH (1:2) to give pale brown or green crystals that were filtered, then washed with water and Et2O, and dried in air.
General procedure: In a two-necked, 100 mL round-bottom flask equipped with a blanket of nitrogen (N2) was placed 60 mL of 96% ethanol. To this solution was added mononuclear organocobaloxime [PhCH2Co(LH)2(4-t-BuPy)] (3) complex (0.50 g, 0.75 mmol) slowly with stirring, followed by Et3N (5 mL). The solution was brought to reflux over 2 h. To this mixture, the separated solution of Cu(ClO4)2.6H2O (0.57 g, 1.50 mmol) for all the trinuclear complexes [{Cu(N-N)}2PhCH2Co(L)2(4-t-BuPy)](ClO4)2 (8-11) complexes in 96% ethanol (10 mL) and 2,2'-bipyridine (bpy) (0.24 g, 1.50 mmol), 1,10-phenanthroline monohydrate (phen) (0.29 g, 1.50 mmol), 1,10-phenanthroline-5,6-dione (dione) (0.31 g, 1.50 mmol), and 4,4'-ditertbutyl-2,2'-bipyridine (dtbpy) (0.40 g, 1.50 mmol) in 96% ethanol (20 mL) as linked ligands was successively added separately, and then the mixture was boiled under reflux for 6 h. The gold yellow color of the mononuclear organocobaloxime [PhCH2Co(LH)2(4-t-BuPy)] (3) complex changed to brown or green upon formation of the trinuclear complexes [{Cu(N-N)}2PhCH2Co(L)2(4-t-BuPy)](ClO4)2 (8-11). Then the mixtures were left for 48 h to precipitate. The solvent was evaporated slowly at room temperature and the products were recrystallized from CH2Cl2/EtOH (1:2) to give brown or green crystals that were filtered, then washed with water and Et2O, and dried in air.
[iridium(III)(μ-chloro)(2-phenylpyridine)2]2[ No CAS ]
ammonium hexafluorophosphate[ No CAS ]
[ 72914-19-3 ]
[ 676525-77-2 ]
Yield
Reaction Conditions
Operation in experiment
77%
A magnetically stirred suspension of 4,4?-di-tert-butyl-2,2?-dipyridyl (118 mg, 0.44 mmol) and tetrakis(2-phenylpyridine-C2,N?)(mu-dichloro)-diiridium (214 mg, 0.2 mmol) in 10 mL of 1,2-ethanediol under nitrogen was heated to 150 C. The mixture was kept at this temperature for 15h. All the solids dissolved to yield a clear, yellow solution. After cooling the mixture to room temperature, 150 mL of water was added. The excess of bipyridine ligand was removed through three extractions with diethyl ether (50 mL), and the aqueous layer was subsequently heated to 60-70 C. NH4PF6 (1 g) in 10 mL of water was added, and the PF6 salt of the chromophore immediately precipitated. After cooling the suspension to 5 C, the yellow solid was separated through filtration, dried, and recrystallized through acetonitrile/ether diffusion. Yield: 280 mg (77%).
66%
Synthesis of [Ir(ppy)2(dtbbpy)](PF6) was adapted from literature procedures6 for the analogousunsubstituted complex. A stirred suspension of 4,4-di-tert-butyl-2,2-dipyridyl (0.44 g, 0.88mmol) and tetrakis(2-phenylpyridine-C,N)(mu-dichloro)diiridium, A (0.428g, 0.400 mmol) in 20mL of 1,2-ethanediol under nitrogen was heated to 150 C for 15 h. All the solids dissolved toyield a clear, yellow solution. After cooling the mixture to room temperature, 200 mL of waterwere added. The excess of the bipyridine ligand was removed through three extractions withdiethyl ether (3 × 50 mL), and the aqueous layer was subsequently heated to 70 C. NH4PF6 (2 g)in 20 mL of water was added, and the PF6 salt of the iridium complex immediately precipitated.After cooling the suspension to 5 C, the yellow solid was separated through filtration, dried, andrecrystallized through acetonitrile/ether. Yield: 0.50 g (66%). 1H NMR (acetone-d6, 400 MHz):delta 8.88 (d, J =2.0 Hz, dtb-bpy-H3, 2H), 8.24 (ppy-H6, pyridine, 2H, d, J = 8), 7.99-7.93 ( m,dtb-bpy-H6, 2H, ppy-H5, pyridine, 2H), 7.90 (ppy-H3, phenyl, 2H, dd, J = 7.2, 0.8 Hz), 7.79(ppy-H6, phenyl, 2H, d, J = 6 Hz), 7.71 (dtb-bpy-H5, 2H, dd, J = 6.0, 2.0 Hz), 7.14 (ppy-H4,pyridine, 2H, dt, J = 7.2, 1.6 Hz), 7.04 (ppy-H4, phenyl, 2H, dt, J= 7.6, 0.8 Hz), 6.91 (ppy-H5,phenyl, 2H, dt, J = 6.8, 1.2 Hz), 6.34 (ppy-H3, pyridine, 2H, d, J = 8), 1.42 (18H, s).HRMS (ESI) m/z calculated for C40H40N4Ir+ ([M - PF6]+) 769.2876, found 769.2866.
Bis-(mu)-chlorotetrakis(2-(4,6-difluoromethylphenyl)-pyridinato-C2,N)diiridium(III) (0.09 mmol, 0.13 g) was heated to reflux with 4,4?-di-tert-butyl-2,2?-dipyridyl (0.20 mmol, 0.054g) in ethylene glycol (6.0 mL) under nitrogen with constant stirring for 15h. Upon cooling to room temperature, the mixture was transferred to a separatory funnel with water (60 mL) and washed with hexanes (3×30 mL). The aqueous layer was heated to 85 C for 5 min to remove residual hexanes. A 10 mL aqueous ammonium hexafluorophosphate solution (1.0g in 10 mL deionized water) was added to the reaction mixture, producing a yellow-green amorphous powder. This precipitate was filtered, dried, and recrystallized by acetone:pentane vapor diffusion, giving the pure product, [Ir(dF(CF3)ppy)2(<strong>[72914-19-3]dtbbpy</strong>)]-(PF6). Yield: 0.15 g (75%).
121 mg
General procedure: Heteroleptic iridium 4xy were synthesized in a two-step procedure[42,43]. In the first step, chloro-bridged dimer was synthesized by charging a two-necked reaction flask with magnetic stir bar, iridium(III) chloride (1 equiv), ligand (2.26 equiv), and a 2:1 v:v mixture of 2-methoxyethanol/water. The mixture was degased with Ar (via Ar bubbling) and heated under reflux at 120 C with constant stirring overnight. The reaction mixture cooled to room temperature and filtered. The precipitate was washed with water (3x10 mL), dried in air and taken onto the second step without further purification unless noted. In the second step, the chloro bridging dimer (1 equiv), bipyridyl ligand (2.2 equiv) and ethylene glycol were placed in a two-necked flask and then flushed with Ar. The mixture was heated at 150 C for 15 h and then cooled. The cooled reaction mixture was washed hexane (3 10 mL) and mixture was heated to 85 C for 5 min to remove residual hexane. Aqueous ammonium hexafluorophosphate (sat. solution) was added to the reaction mixture causing the iridium-PF6 salt to precipitate,which was filtered, dried and recrystallized (acetone/ether).
[RuII(2,2′-bipyrazyl)2(4,4′-bis(tert-butyl)-2,2′-bipyridyl)](PF6)2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
55%
General procedure: cis-RuII(bpz)2Cl2 (100 mg, 0.205 mmol) and bpy (64 mg, 0.410 mmol) were combined in an argon-purged flask. An argon-sparged mixture of 2-methoxyethanol (7 mL) and water (3 mL) was added and the mixture heated at reflux for 24 h. After cooling to room temperature, the solvents were removed under vacuum and a small amount of water was added. The suspension was filtered, and an excess of solid NH4PF6 was added to the filtrate to precipitate the crude product. The solid was filtered off and purified by column chromatography on silica gel eluting with 0.1 M NH4PF6 in acetonitrile. The main orange fraction was evaporated to dryness and the product washed extensively with ice-cold water, then dried to give an orange solid. Yield: 95 mg (56%).
General procedure: In a two-neck, 100-mL round-bottom flask and equipped with a blanket of nitrogen (N2) was placed 60 mL of 95% ethanol. To this solution was added [PhCH2CoIII(LH)2(4-t-BuPy)] (2) (0.60 g, 0.90 mM) slowly with stirring, followed by Et3N (5 mL). The solution was brought to reflux for 2 h. To this mixture, a separate solution of Cu(ClO4)2*6H2O (0.68 g, 1.80 mM) for all the three complexes [{Cu(N-N)}2PhCH2CoIII(L)2(4-t-BuPy)](ClO4)2 (7-10) in 95% ethanol (10 mL) and 2,2?-bipyridine (bpy) (0.29 g, 1.80 mM), 1,10-phenanthroline monohydrate (phen) (0.35 g, 1.80 mM)), 1,10-phenanthroline-5,6-dione (dione) (0.37 g, 1.80 mM), and 4,4?-ditertbutyl-2,2?-bipyridine (dtbpy) (0.48 g, 1.50 mM) in 95% ethanol (15 mL) was successively added separately, and then the mixture was refluxed for 8 h. The gold yellow color of mononuclear [PhCH2CoIII(LH)2(4-t-BuPy)] (2) changed to brown or green upon formation of the trinuclear [{Cu(N-N)}2PhCH2CoIII(L)2(4-t-BuPy)](ClO4)2 (7-10) complexes. Then the mixtures were left for 48 h to precipitate. The solvent was evaporated slowly at room temperature and the products were recrystallized from CH2Cl2/EtOH (1 : 2) to give brown or green crystals that were filtered, then washed with water and Et2O, and dried in air.
General procedure: In a two-neck, 100-mL round-bottom flask and equipped with a blanket of nitrogen (N2) was placed 70 mL of 95% ethanol. [ClCoIII(LH)2(4-t-BuPy)] (1) (0.50 g, 0.82 mM) and Et3N (3 mL) were added slowly with stirring to this solution, consecutively. The solution was brought to reflux over 1 h. To this solution were successively added separate solutions of Cu(ClO4)2*6H2O (0.62 g, 1.64 mM) in 95% ethanol (15 mL) and 2,2?-bipyridine (bpy) (0.26 g, 1.64 mM), 1,10-phenanthroline monohydrate (phen) (0.32 g, 1.64 mM), 1,10-phenanthroline-5,6-dione (dione) (0.34 g, 1.64 mM), and 4,4?-ditertbutyl-2,2?-bipyridine (dtbpy) (0.44 g, 1.64 mM) in 95% ethanol (10 mL) as bidentate ligands, followed by boiling unde rreflux for 6 h to synthesize three new multinuclear complexes having the general formulas [{Cu(N-N)}2ClCoIII(L)2(4-t-BuPy)](ClO4)2 (3-6). The dark brown color of the mononuclear [ClCoIII(LH)2(4-t-BuPy)] (1) changed to pale brown or green upon formation of the multinuclear [{Cu(N-N)}2ClCoIII(L)2(4-t-BuPy)](ClO4)2 (3-6) complexes. Then the mixtures were left for 48 h to precipitate. The solvent was evaporated slowly at room temperature and the products were recrystallized from CH2Cl2/EtOH (1 : 2) to give pale brown or green crystals that were filtered, then washed with water and Et2O, and dried inair.
tris-(4,4’-di-tert-butyl-2,2’-bipyridine)ruthenium(II) hexafluorophosphate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
28 mg
This synthesis was performed in accordance with the literature procedure [15]. 20mg (0.03mmol) of 2b were dissolved in 4ml EtOH/H2O 3:1 and the ligand tb-bpy was added. After refluxing for 3h a color change from purple to red occurred. Afterwards NH4PF6 was added for precipitation of 3b as an orange solid, which was washed with circa 20ml water and 40ml diethyl ether. Then it was repetitively dissolved in chloroform and filtrated until the filtrate was colorless. 3b was obtained as a red solid after solvent evaporation. Yield: 28mg (complete conversion). 1H NMR (400MHz, CDCl3) delta=8.23-8.11 (m, 6H, 3), 7.63 (d, J=6.0Hz, 6H, 6), 7.52 (dd, J=6.1, 2.0Hz, 6H, 5), 1.41 (s, 54H, CH3) (1H NMR is in accordance with the literature) [17]. MS-ESI: m/z=452 [M2+/2], 1051 [M2++PF6-].
dichlorobis(dimethyl sulfoxide)platinum(II)[ No CAS ]
[ 72914-19-3 ]
[ 138736-35-3 ]
Yield
Reaction Conditions
Operation in experiment
93.6%
In acetonitrile; for 24h;Inert atmosphere; Reflux;
Complex 1 was synthesized according to the proceduredescribed in the literature with minor modification [32], suchthat Pt(DMSO)2Cl2 [42] was used instead of PtCl2as thestarting material. Specifically, a mixture of Pt(DMSO)2Cl2(0.21 g, 0.5 mmol) and 1 equiv of dbbpy (0.31 g, 0.5 mmol)in acetonitrile(30 mL) was heated to reflux under N2for24 h. The reaction mixture was then cooled to 0 C, and theresulting yellow precipitate was filtered off, washed withhexane and ether, and dried (93.6% yield). All characterizationdata matched that previously reported [32]. 1H NMR(400 MHz, d6-DMSO): delta 9.342 (d, J = 6.0 Hz, 2 H, H6),delta8.279 (s, 2 H, H3),delta 7.827 (s, J = 6.0 Hz, H5),delta 1.409 (s, 18H, 6 × CH3) ppm; ESI-MS (Acetone) m/z (%): 534.52 for[1 + H]+ and 498.35 for [1 - Cl]+; elemental analysis calcd(%) for C18H24N2Cl2Pt:C 40.46, H 4.53, N 5.24; found: C40.23, H 4.72, N 5.20.
[RuCl(η6-C10H14)(4,4′-t-dibutyl-2,2'-bipyridine)]*PF6[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%
General procedure: The precursors were synthesized according to a previously reportedmethod. A solution of [RuCl2(eta6-C10H14)]2 (0.200 g, 0.31 mmol) with an excess of the desired N-N ligand (0.75 mmol) in methanol (25 mL) was stirred for 1 h. NH4PF6 (0.30 g; 1.00 mmol) was added to this solution, also dissolved in methanol (5 mL), and the mixture was stirred at room temperature for 1 h longer. The orange-yellow solid that precipitated was filtered off, washed with cold methanol and diethyl ether, and dried under vacuum.
[Sm(dibenzoylmethane)3(4,4'-di-tert-butyl-2,2'-bipyridyl)][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
25%
With sodium hydroxide; In methanol; ethanol; at 50 - 60℃; for 2.5h;
General procedure: In a three-neck round bottom flask, dibenzoylmethane (0.673 g, 3 mmol) and 2,2-bipyridyl (0.156 g, 1 mmol) were dissolved in hot ethanol (20 mL). To the solution mixture, 3 mL of sodium hydroxide (0.1 M) was added. The temperatureof the reaction mixture was maintained at 50-60C in which then Sm(NO3)3·6H2O (0.445 g, 1 mmol) in methanol (20 mL) was added dropwise with stirring for 30 min. After two hours, the reaction mixture was cooled to room temperature and the resulting precipitate was filtered using vacuum filtration, washed withdistilled water and followed by cold ethanol. The product was air dried overnight. Yield: 0.331 g, 45%.
(1,5-cyclooctadiene)(methoxy)iridium(I) dimer[ No CAS ]
[ 212-74-8 ]
[ 72914-19-3 ]
4,4,5,5-tetramethyl-2-(tetraphenylen-2-yl)-1,3,2-dioxaborolane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
25%
With nitrogen; triethylamine; In cyclohexane;
Synthesis of 4,4,5,5-tetramethyl-2-(tetraphenylen-2-yl)-1,3,2-dioxaborolane Tetraphenylene (10.6 g, 35.0 mmol), bis(pinacolato)diboron (8.8 g, 35.0 mmol), 4,4'-di-tert-butyl-2,2'-dipyridyl (1.9 g, 7.0 mmol), (1,5-Cyclooctadiene)(methoxy)iridium(I) dimer (2.3 g, 3.5 mmol), and anhydrous cyclohexane (250 mL) were mixed at room temperature (?22 C.). The reaction mixture was bubbled with nitrogen for 15 min. The resultant mixture was refluxed for 14 h. The solvent was removed in vacuo. The residue was purified by flash chromatography using 25%-40% dichloromethane (DCM)/hexane (both containing 0.5% triethylamine) to yield 4,4,5,5-tetramethyl-2-(tetraphenylen-2-yl)-1,3,2-dioxaborolane (3.8 g, 25% yield) as a white solid.
Was dissolved in bis (pinacolato) diboron (7.16g, 28.21mmol) in 1,4-dioxane (60mL), then degassed by bubbling by blowing argon. (S) - (-) - nicotine (6.48mL,40.3mmol), followed by 4,4'-di -tert- butyl-2,2'-dipyridyl (650mg g, 2.42mmol)was added. Degassing continued for 10 minutes, followed by addition of methoxy(cyclooctadiene) iridium (I) dimer (753 mg, 1.21 mmol). The reaction mixturewas heated at reflux for 18 hours. The solvent was evaporated, the residue wasdissolved in MeOH (100mL). Water (100 mL) solution of copper bromide (II)(27.0g, 120.9mmol) was added and the reaction mixture was heated for 3 hours at80 C.. Ammonia solution (10% aqueous, 100 mL) was added to the reactionmixture, then it was extracted with ethyl acetate, MgSO 4 driedover. The solvent was evaporated and the crude product was purified by flashchromatography (5% in DCM MeOH), to give the title compound as an orange oil(6.14g, 63%). 1 H NMR (400 MHz, CDCl 3 ) Deruta =1.68-1.70 (M, 1H), 1.80-1.82 (M, 1H), 1.92-1.94 (M, 1H), 1.99-2.02 (M, 1H),2.03 ( s, 3H), 2.20-2.34 (yd, 1H), 3.08 (t, 1H), 3.20 (t, 1H), 7.86 (s, 1H),8.42 (s, 1H), 8.54 (s, 1H).
In tetrahydrofuran; at 20℃; for 24h;Inert atmosphere; Glovebox;
To a stirred solution of 4,4^-di-tert-butyl-2,2^-dipyridyl (Aldrich: 957 mg, 3.56 mmol) in dry THF (Baker; 16 mL, 0.2 M) was added NiBr2^DME (Stream; 1.00 g, 3.24 mmol) under inert atmosphere in glove box. The heterogeneous mixture was stirred at room temperature for 24 hours in glove box. The resulting mixture was cooled to room temperature and filtered through a glass filter funnel to collect the yellow solid. The resulting solid was washed with Et2O, ground to fine powder, and dried under reduced pressure using drying pistol technique at 140 C (xylenes) for 15 hours to afford (dtbbpy)·NiBr2 complex (1.50 g, 3.08 mmol, 95%).
cobalt(II)-4,4'-di(tert-butyl-2,2'-bipyridine) chloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%
In ethanol; at 20℃; for 24h;Inert atmosphere;
General procedure: 18.3 mmol of hexahydrate CoCl2 or trihydrate NiBr2 was entirely dissolved in 100ml of ethanol and then a solution of 18,3 mmol of the ligand in 100 ml of ethanol was added dropwise (during approximately 10min) to the stirred solution of metal salt at room temperature. After adding of entire ligand/ethanol solution, the stirring proceeded during 24 h. After that, the precipitate was filtered and washed first with two 40ml portions of glacial ethanol and then with one 20ml portion of diethyl ether. Drying of the precipitate under vacuum (-10 torr) at room temperature (t=23C) resulted in a powder.
nickel(II)-4,4'-di(tert-butyl-2,2'-bipyridine) bromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
79%
In ethanol; at 20℃; for 24h;Inert atmosphere;
General procedure: 18.3 mmol of hexahydrate CoCl2 or trihydrate NiBr2 was entirely dissolved in 100ml of ethanol and then a solution of 18,3 mmol of the ligand in 100 ml of ethanol was added dropwise (during approximately 10min) to the stirred solution of metal salt at room temperature. After adding of entire ligand/ethanol solution, the stirring proceeded during 24 h. After that, the precipitate was filtered and washed first with two 40ml portions of glacial ethanol and then with one 20ml portion of diethyl ether. Drying of the precipitate under vacuum (-10 torr) at room temperature (t=23C) resulted in a powder.
General procedure: To a solution of [{M(mu-Cl)(ptpy)2}2] (M=Rh, Ir) (0.15mmol) in 25mL of a mixture of CH2Cl2/MeOH/H2O (1:1:0.5) the bipyridine ligand (0.3mmol) was added and the mixture refluxed with stirring for 3h. After cooling to room temperature KPF6 (0.5mmol) was added and stirred for 20min. The solvent was removed to dryness in vacuo and the residue dissolved in dichloromethane and chromatographed on alumina with CH2Cl2/acetone (9:1) as the eluent. The resulting solution was evaporated to dryness and the residue was redissolved in 5ml of dichloromethane and the product was precipitated by slow diffusion of isohexane.
General procedure: To a solution of [{M(mu-Cl)(ptpy)2}2] (M=Rh, Ir) (0.15mmol) in 25mL of a mixture of CH2Cl2/MeOH/H2O (1:1:0.5) the bipyridine ligand (0.3mmol) was added and the mixture refluxed with stirring for 3h. After cooling to room temperature KPF6 (0.5mmol) was added and stirred for 20min. The solvent was removed to dryness in vacuo and the residue dissolved in dichloromethane and chromatographed on alumina with CH2Cl2/acetone (9:1) as the eluent. The resulting solution was evaporated to dryness and the residue was redissolved in 5ml of dichloromethane and the product was precipitated by slow diffusion of isohexane.
cobalt(II) trifluoromethanesulfonate hexahydrate[ No CAS ]
[ 72914-19-3 ]
C51H66CoN6(2+)*2CF3O3S(1-)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86%
In methanol; for 0.25h;
General procedure: Cobalt complexes 1, 2 and 3 were synthesized according to a literatureprocedure [22] by mixing 1 eq. of [Co(H2O)6](OTf)2 salt (1g, 2.8 mmol) with 3 eq. of the appropriate ligand (respectively 2,2'-bipyridine (bpy) (1.31 g, 8.4 mmol), 4,4'-dimethyl-2,2'-bipyridine(dmb) (1.55 g, 8.4 mmol), <strong>[72914-19-3]4,4'-di-tert-butyl-2,2'-bipyridine</strong> (dtb)(2.25 g, 8.4 mmol) in methanol solution. Solution was stirred for15 min, and the final product was obtained by evaporation undervacuum. All complexes were purified by dissolving the solid in aminimum amount of acetonitrile, followed by precipitation withdiethyl ether and drying at room temperature. Yield 1: 89% (2.06g, 2.5 mmol); Yield 2: 85% (2.16 g, 2.38 mmol); Yield 3: 86% (2.8g, 2.4 mmol). The diamagnetic oxidized form of the respectivecomplexes (for 1H NMR characterization) was obtained by addition of a slight excess of NOBF4 in acetonitrile followed by rotary evaporationof the solvent.
[(4,4'-di-tert-butyl-2,2'-bipyridine)2Zn2Eu2(NO3)2(1-naphthylacetate)8][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
47%
General procedure: Method b. A solution of Hnaphac(0.372 g, 2 mmol) in MeCN (10 mL) was added to a solutionof KOH (0.112 g, 2 mmol) in EtOH (5 mL). A solution of potassium1-naphthylacetate, formed after boiling of the original reactionmixture was added to a solution of Zn(NO3)26H2O (0.119 g, 0.4mmol) in MeCN (10 mL). The resulting solution was boiled andstirred for 10 min, then Eu(NO3)36H2O (0.178 g, 0.4 mmol) (for2) or Tb(NO3)36H2O (0.181 g, 0.4 mmol) (for 3) was added. After10 min of vigorous stirring and heating (80 C) a suspension wasformed and a flaky precipitate of KNO3 was filtered off. A solutionof 4,40-di-tert-butyl-2,20-bipyridine (0.107 g, 0.4 mmol) in MeCN (10 mL) was added to the filtrate. The resulting solution wasevaporated to 10 mL and left for crystallization. Fine crystallineprecipitate was formed after 3 weeks, which was separatedfrom the mother liquor by decantation, washed with cold MeCN(t = 18 C) and dried in air at t = 20 C. The yield of 2 synthesized by the method b was 0.266 g (47%against Eu(NO3)36H2O). The data of elemental analysis and IRspectra for samples of compound 2 synthesized by methods a andb are consistent. Found (%): C, 61.27; H, 4.58; N, 3.19. ForC132H120N6O22Zn2Eu2 (without solvent MeCN molecules) calcd (%):C, 61.52; H, 4.69; N, 3.26. IR (ATR), m/cm1: 2968 (m(CAH)CH3),1610 (mas(COO)), 1598 (mas(COO)), 1408 (ms (COO)), 1399(ms(COO)), 1366 (d(CA(CH3)3), 1293 (mas(NO2)), 792 (d(arCAH)(4,40-dtb-2,20-bpy)), 778 (d(COO)), 740 (d(arCAH)naphac), 607(d(ring)(4,40-dtb-2,20-bpy), 537 (d(ring)naphac), 416 (d(ring)(4,40-dtb-2,20-bpy)).
[(4,4'-di-tert-butyl-2,2'-bipyridine)2Zn2Tb2(NO3)2(1-naphthylacetate)8][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
44%
The yield of 2 synthesized by the method a was 0.059 g (76%against [Zn2Eu(NO3)(Piv)6(MeCN)2]). Method b. A solution of Hnaphac(0.372 g, 2 mmol) in MeCN (10 mL) was added to a solutionof KOH (0.112 g, 2 mmol) in EtOH (5 mL). A solution of potassium1-naphthylacetate, formed after boiling of the original reactionmixture was added to a solution of Zn(NO3)26H2O (0.119 g, 0.4mmol) in MeCN (10 mL). The resulting solution was boiled andstirred for 10 min, then Eu(NO3)36H2O (0.178 g, 0.4 mmol) (for2) or Tb(NO3)36H2O (0.181 g, 0.4 mmol) (for 3) was added. After10 min of vigorous stirring and heating (80 C) a suspension wasformed and a flaky precipitate of KNO3 was filtered off. A solutionof 4,40-di-tert-butyl-2,20-bipyridine (0.107 g, 0.4 mmol) in MeCN (10 mL) was added to the filtrate. The resulting solution wasevaporated to 10 mL and left for crystallization. Fine crystallineprecipitate was formed after 3 weeks, which was separatedfrom the mother liquor by decantation, washed with cold MeCN(t = 18 C) and dried in air at t = 20 C. The yield of 3 synthesized by the method b was 0.251 g (44%with respect to Tb(NO3)36H2O). Found (%): C 61.40, H 4.71, N3.53. For C132H120N6O22Zn2Tb2 (without solvent MeCN molecules)calcd (%): C 61.19, H 4.67, N 3.24. IR (ATR), m/cm1: 2967(m(CAH)CH3), 1600 (mas(COO)), 1574 (m(CN)(4,40-dtb-2,20-bpy)),1510 (m(arCAC)naphac), 1396 (ms(COO)), 794 (d(arCAH)(4,40-dtb-2,20-bpy)), 779 (d(COO)), 745 (d(arCAH)naphac), 715(d(arCAH)(4,40-dtb-2,20-bpy)), 605 (d(ring)(4,40-dtb-2,20-bpy), 543(d(ring)naphac), 426 (d(ring)(4,40-dtb-2,20-bpy)).
[(4,4'-di-tert-butyl-2,2'-bipyridine)2Zn2Eu2(NO3)2(1-naphthylacetate)8][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76%
In acetonitrile; at 60℃;
Method a. The synthesis was carried out similarly to the preparationof 1 but with 4,40-di-tert-butyl-2,20-bipyridine instead of4,40-dimethyl-2,20-bipyridine (0.029 g, 0.11 mmol). The resultingsolution was transferred to the Schlenk flask and kept under thereduced pressure for three weeks. Colorless crystals suitable forXRD analysis were separated by decantation of the mother liquor,washed by cold MeCN (t = 18 C) and dried in air at t = 20 C. The yield of 2 synthesized by the method a was 0.059 g (76%against [Zn2Eu(NO3)(Piv)6(MeCN)2]).
[bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II)[ No CAS ]
[ 17985-72-7 ]
[ 72914-19-3 ]
C38H58N2RuSi4[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
14%
In hexane; at 55℃; for 18h;Inert atmosphere; Schlenk technique;
Under an argon atmosphere, a 100 mE Schlenk tube wascharged with (-1 ,5-cyclooctadiene)ruthenium(II) bis(3-2-methylallyl) complex (200 mg, 0.63 mmol), 1,2-bis(dim- ethylsilyl)benzene (243 mg, 1.26 mmol) and 4,4?-di-t-butyl- 2,2?-bipyridine (169 mg, 0.63 mmol). Degassed and dehydrated hexane (30 mE) was added thereto and thesystem was stirred at 55 C. for 18 hours. Following reactioncompletion, the system was dried in vacuo and the resultingdried product was dissolved in toluene (50 mE); the small amount of brown insoluble matter that formed as by-product was removed by centrifugal separation. Next, the toluene solution was dried in vacuo, washed with hexane (10 mE),and the remaining red powder was dissolved in 30 mE of toluene and re-crystallized at -35 C., giving RutheniumComplex F (67 mg/0.09 mmol/14%) which is typically represented by the above formula. FIG. 9 shows the structure of the Ruthenium Complex E obtained, and FIG. 10shows the results of ?H-NMR measurement.?H-NMR (C6D6, 600 MHz) oe=-11.2 (t, JHs=12.4 Hz,2H, Si-H), -0.07-1.05 (br s, 24H, SiMe2), 0.87 (s, 18H, C(CH3)3), 6.45 (d, JHH=6.9 Hz, 2H, C5H3N), 7.21-7.27 (m, 4H, C6H4), 7.58-7.70 (br s, 4H, C6H4), 8.00 (s, 2H, C5H3N),8.53 (d, JHH=6.9 Hz, 2H, C5H3N).29SiNMR (C6D6, 119 MHz) oe=13.2. IR (K13r pellet): v=2028 (vSH) cm?.Analysis:Calculated for C38H58N2RuSi4: C, 60.35; H, 7.73; N,3.70.Found: C, 60.03; H, 7.56; N, 3.46.
NiIIITol was synthesized according to a modified version of previously reported protocol81:In an argon-filled glovebox, a flame-dried 25 mL sealing tube equipped with a Teflon septumand magnetic stir bar was charged with Ni(cod)2 (250 mg, 0.9 mmol, 1.0 equiv.), 4,4-ditertbutyl-2,2-pyridine (244 mg, 0.9 mmol, 1.0 equiv.), anhydrous THF (7 mL) was added andthe mixture was stirred for 1 h to give a deep purple solution. The reaction vial was sealedtightly and removed from the glovebox, placed in a dry ice acetone bath, and set to stir. Next 2-iodotoluene (240 mg, 0.14 mL, 1.1 mmol, 1.2 equiv.) was added via syringe under an argonatmosphere. The reaction mixture was allowed to warm to ~ 10 oC. The reaction mixture wasdiluted into pentanes (50 mL) in another flask by a syringe under an argon atmosphere, andthe solution was allowed to stir for 1 h. The resulting red precipitate was collected on a frit,rinsed with pentane, and residual solvent was removed under vacuum to give the titlecompound as a brown powder (150 mg, 30% yield). The compound was used without furtherpurification.1H NMR (400 MHz, CD2Cl2) delta 9.55 (d, J = 5.9 Hz, 1H), 7.83 (d, J = 14.2 Hz, 2H), 7.57 (d, J =7.4 Hz, 1H), 7.45 (d, J = 5.9 Hz, 1H), 7.17 (d, J = 6.1 Hz, 1H), 6.86 - 6.79 (m, 2H), 6.79 - 6.73(m, 1H), 6.69 (t, J = 7.0 Hz, 1H), 2.96 (s, 3H), 1.40 (s, 9H), 1.34 (s, 9H).13C NMR (101 MHz, CD2Cl2) delta 163.72, 163.21, 156.18, 154.11, 153.52, 149.80, 148.20, 143.50,138.12, 127.83, 124.29, 124.12, 123.59, 122.60, 118.06, 117.65, 35.84, 34.63, 30.59, 30.39,27.05.The spectroscopic data matched the ones from the literature81.
4,4',4-tri-tert-butyl-2,2':6',2-terpyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%; 9%
With sodium; In tetrahydrofuran; paraffin oil; at 25℃; for 24h;
In this example, following Example 1, the synthesis of 4,4?-di-tert-butyl-2,2?-bipyridine was investigated. In this example, the synthesis was performed through the reaction of 4-tert-butylpyridine with SD at low concentrations in THF. 4-tert-Butylpyridine (0.5 mmol) was reacted with SD in an amount of molar equivalents with respect to 4-tert-butylpyridine as shown in FIG. 2 in THF. The usage amounts of THF, the reaction temperatures and the reaction times were set as shown in FIG. 2, and the synthesis was performed in the same manner as in Example 1. After the reaction, in the same manner as in Example 1, the production amounts of 4,4?-di-tert-butyl2,2?-bipyridine (Compound 2), which was the target reaction product, and 4-tert-butyl-1,4-dihydropyridine (Compound 1) and 4,4?,4?-tri-tert-butyl-2,2?:6?,2?-terpyridine (Compound 3), which were the possible reaction by-products, were measured, and their yields were calculated. The recovery rate of the unreacted 4-tert-butylpyridine was calculated in the same manner. The results are summarized in FIG. 2. It is found from these results that when 4-tert-butylpyridine (0.5 mmol) was reacted with SD in an amount of 1 to 2 mol equivalents with respect to the 4-tert-butylpyridine in 2 to 4 ml of THF at 25 to 50 C. for 1 to 24 hours, the 4,4?-di-tert-butyl-2,2?-bipyridine compound was obtained with a high yield in all of the cases. In particular, when 0.5 mmol 4-tert-butylpyridine was reacted with SD in an amount of 1 mol equivalent with respect to the 4-tert-butylpyridine in 2 ml of THF at 50 C. for 1 to 6 hours, the 4,4?-di-tert-butyl-2,2?-bipyridine compound was obtained with a high yield without the generation of reaction by-products. In addition, when 0.5 mmol 4-tert-butylpyridine was reacted with SD in an amount of 1 mol equivalent with respect to the 4-tert-butylpyridine in 4 ml of THF at 25 C. for 6 hours, the 4,4?-di-tert-butyl-2,2?-bipyridine compound was obtained with a high yield without the generation of reaction by-products. It was found that when SD in an amount of 2 mol equivalents was used, the yield decreased compared with the case of 1 mol equivalent, and the material balance also decreased. It was also found from comparison with Example 1 that the lower the concentrations of 4-tert-butylpyridine and SD were with respect to THF, the higher the yield was.
tris(4,4'-di-tert-butyl-2,2′-bipyridyl)cobalt(II) nitrate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81.8%
In ethanol; at 20℃;
General procedure: The paramagnetic [10,11] polypyridine-Co(II) complexes (containingthe anion (NO3)2) were synthesized according to literaturemethods, with slight modifications [12]: Co(NO3)2·6H2O was dissolvedin a minimum of absolute ethanol. A slight excess of the desired ligand(3.3 eq bipyridine for Co(N,N)32+ or 2.2 eq for Co(N,N,N)22+ terpyridine)was also dissolved in a minimum of absolute ethanol. The Co(NO3)2·6H2O solution was added dropwise to the respective ligand solution whilst stirring. The mixture was left to stir for 6-8 h. A precipitateformed in each case. The mixture was filtered and the precipitateleft to dry overnight in air. The electrochemical behaviour ofcomplexes 1, 2 and 5 has been reported previously (see Table 5), whilethat of complexes 3 and 4 is reported here for the first time.
[Pt(4,4'-ditertbutyl-2,2'-biyridine)2](PF6)2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
41.3%
A suspension of Pt(dbbpy)Cl2 (107 mg, 0.2 mmol), plusdbbpy (1.5 equiv, 81 mg, 0.3 mmol) in mixed solvent (60 mLethylene glycol and 30 mL ultrapure water) was stirred for24 h at 150 C until a clear yellow solution was obtained.Excess KPF6(184 mg, 1 mmol) was then added, whereuponpale yellow [Pt(dbbpy)2](PF6)2 precipitated immediately.The product was filtered off with a Teflon filter (pore diameter1 mum), washed twice with 20 mL of water, and driedunder vacuum (84 mg, 41.3% yield). 1H NMR (400 MHz,d6-DMSO): delta 8.932 (d, J = 6.0 Hz, 4 H, H6),delta 8.875 (s, 4 H,H3),delta 7.922 (s, J = 6.0 Hz, H5),delta 1.488 (s, 36 H, 12 × CH3)ppm; ESI-MS (Acetone) m/z (%): 876.75 for [2 - PF6]+;elemental analysis calcd (%) for C36H48F12N4P2Pt:C 42.32,H 4.74, N 5.48; found: C 42.09, H 4.85, N 5.32.
dihydrogen hexachloroplatinate(IV) hexahydrate[ No CAS ]
[ 67-68-5 ]
[ 72914-19-3 ]
[Pt(4,4'-di-tert-butyl-2,2'-bipyridine)Cl4].DMSO[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
73.2%
A solution of 4,4?-di-tert-butyl-2,2?-bipyridine (0.22g, 0.79mmol) in 5ml methanol was added to a solution of H2PtCl6·6H2O (0.41g, 0.79mmol) in 10ml methanol at 45C and stirred for 5min until a precipitate was formed. The precipitate gradually started to disappear when 15ml DMSO was added to the solution and the mixture was stirred at 45C for 15min. Suitable crystals for X-ray diffraction measurement were obtained by methanol diffusion to a yellow solution of 2 in DMSO over ten days (yield 0.35g, 73.2%, m.p.>300C). IR (CsI, cm-1): 3122w, 3048w, 2957m, 2908w, 2866w, 1613s,1548m, 1490m, 1421s, 1368m, 1303m, 1249m, 1206w, 1163w, 1084m, 1041s, 938m, 896w, 843m, 739w, 602m, 565m, 408m, 345s, 255s. UV-Vis: lambdamax (DMSO, nm), 262, 282, 314, 325. 1H NMR (DMSO-d6, ppm): 1.48 (s, 9H), 8.16 (d, 1H), 8.95 (s, 1H), and 9.36 (satellite, 1H, 4JHPt=12.8Hz, 1H). Elemental analysis: C20H30Cl4N2OPtS (%) (683.41); Anal.Calcd.C, 35.15; H, 4.39; N, 4.10. Found: C, 34.95; H, 4.36; N, 4.07%.
La2(ferrocene carboxylate)4(4,4′-di-tert-butyl-bipyridyl)2(nitrate)2[ No CAS ]
[Fe(4,4′-di-tert-butyl-bipyridyl)3](nitrate)2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
44.4%; 31.2%
La(NO3)3·6H2O (0.108 g, 0.25 mmol) and FcCOONa (0.063 g,0.25 mmol) were dissolved in methanol (2 mL), the solution was heatedat 80 C and stirred. After 30 min of stirring, 1 mL of methanol containingDTBbpy (0.067 g, 0.25 mmol) was added drop-wise. A colorchange from orange to red was immediately observed. The resultingsolution was stirred at 80 C for an additional 20 min and an orangeprecipitate was formed. The solution containing the precipitate wastransferred into a centrifuge tube and centrifuged. The resulting orangesolid was dried in air at room temperature. After recrystallization fromCH3CN / CH2Cl2 (1:1), 103.8 mg of an orange solid (1) was obtained.The mother solution was slowly evaporate at room temperature and redcrystals of [Fe(DTBbpy)3](NO3)2 (1a) were obtained. Yield: 44.4% (1);31.2% (1a). Complex 1 is air and water stable and is insoluble in polar and nonpolarsolvents which precludes its analysis in solution. However, it issparingly soluble in hot CH3CN/CH2Cl2 when freshly prepared.Complex 1 was characterized in the solid-state by SCXRD (see section3.1) and IR. IR (KBr, cm-1): 3468b, 2963 s, 2870 m, 1612 s, 1585 s,1547 s, 1474 s, 1385 s, 1358 s, 1300 s, 1250 m, 1192 m, 1107 m, 1026 s,922 m, 895 s, 841 s, 814 s, 787 sh, 775 m, 737 m, 714 m, 671 m, 609 s,559 m, 501 s, 486 sh, 447 m.
(4,4'-di-tert-butyl-2,2'-bipyridine)bis(2-phenylpyridine)iridium(III) hexafluorophosphate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
77%
A magnetically stirred suspension of 4,4?-di-tert-butyl-2,2?-dipyridyl (118 mg, 0.44 mmol) and tetrakis(2-phenylpyridine-C2,N?)(mu-dichloro)-diiridium (214 mg, 0.2 mmol) in 10 mL of 1,2-ethanediol under nitrogen was heated to 150 C. The mixture was kept at this temperature for 15h. All the solids dissolved to yield a clear, yellow solution. After cooling the mixture to room temperature, 150 mL of water was added. The excess of bipyridine ligand was removed through three extractions with diethyl ether (50 mL), and the aqueous layer was subsequently heated to 60-70 C. NH4PF6 (1 g) in 10 mL of water was added, and the PF6 salt of the chromophore immediately precipitated. After cooling the suspension to 5 C, the yellow solid was separated through filtration, dried, and recrystallized through acetonitrile/ether diffusion. Yield: 280 mg (77%).
With sodium acetate; In decalin; at 180℃; for 12h;Inert atmosphere;
General procedure: To a 100mL round-bottomed flask, decalin (20mL), tris (2,4-di-tert-butylphenyl) phosphite (dbtpitH2) (0.64g, 0.92mmol), Ir(tht)3Cl3 (0.52g, 0.92mmol), diimine ligands (2,2?-bipyridine (bpy), 4,4?-diterbutyl-2,2?-bipyridine (dbbpy) or 4,5-diaza-9, 9?-spirobifluorene (sb), 0.92mmol) and sodium acetate (0.38g, 4.6mmol) were added sequentially. The mixture was stirred 12h under nitrogen at 180C and then cooled to room temperature. After the solvent was removed, the residue was purified from silica gel column chromatography using CH2Cl2/ethyl acetate (3:1, v:v). Then the yellow crystals of iridium(III) complexes were obtained by the diffusion of hexane into a dichloromethane solution at room temperature.
tris(4,4'-di-tert-butyl-2,2'-bipyridine)ruthenium bis(tetrafluoroborate)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
63%
General procedure: Dried RuCl3 (0.20 g, 0.96 mmol) was dissolvedin dipropylene glycol (10 mL) and deionized water (1 mL).The solution was refluxed until the metal salt was dissolved,obtaining a dark green solution. Bipyridine (0.469 g; 3.0 mmol) wasadded, resulting in a brown solution. Ascorbic acid (0.177 g,1.0 mmol) was then added and the solution refluxed for 20 min at250 C, the brown colour changing to red. After cooling, the solutionwas diluted to 40 mL and the pH adjusted to 8 by addition of afew drops of NaOH solution (2.5 M). NaBF4 (4.0 g, 36 mmol) wasadded and the solution cooled on ice. After vacuum filtration,washing with cold water, and drying, 0.329 g [Ru(bpy)3](BF4)2product was obtained.
[Ir(2-(3,5-dimethoxyphenyl)quinoline)2(μ-Cl2)][ No CAS ]
[ 72914-19-3 ]
[Ir(2‐(3,5-dimethylphenyl)quinoline)2(4,4'-di-tert-butyl- 2,2'-bipyridyl)](+1)*PF6(-1)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
89.63%
(dmpq) 2Ir(mu-Cl2)Ir(dmpq)2 dimer (3.65g, 2.64mmol) and <strong>[72914-19-3]4,4'-di-tert-butyl-2,2'-bipyridine</strong> (<strong>[72914-19-3]dtbbpy</strong>) were added to the reaction flask. (1.65g, 6.15mmol),Add 150mL of mixed solution of CH2Cl2 and CH3OH (1:1, v/v),Under reflux with argon, the reaction was heated to reflux for 3 h.Then, excess KPF6 (3.29 g, 17.91 mmol) was added to the reaction mixture, and after stirring for 1 h, the solvent was removed, and the obtained solid was dissolved in dichloromethane and filtered to remove insolubles.The solvent in the filtrate was distilled off, and the obtained crude product was separated by silica gel column chromatography.The product was obtained as a pure reddish solid, 4.15 g, yield: 89.63%.
Heteroleptic iridium complex Ir1 was synthesized in a two-step procedure. In the first step, chloro-bridged dimer was synthesized by charging a two-necked reaction flask with magnetic stirbar, iridium (III) chloride (1 equiv), ligand (2.26 equiv), and a 2:1 v:v mixture of 2-methoxyethanol/water. The mixture was degassed with Ar and heated under reflux at 120C overnight. The reaction mixture was then cooled to room temperature and filtered. The precipitate was washed with water, dried under vacuum and taken to the second step without further purification. In the second step, the chloro bridging dimer (1 equiv), bipyridyl ligand (2.2 equiv) and ethylene glycol were placed in a two-necked flask and then flushed with Argon. The mixture was heated at 150C for 24 h and then cooled. The cooled reaction mixture was washed hexane and heated to 85C for 5 min to remove the residual hexane and aqueous ammonium hexafluorophosphate (2g for each 100 mg IrCl3) was added to the reaction mixture causing the iridium-PF6 salt to precipitate, which was filtered, purified on silica column using DCM/Hexane as eluent dried under vacuum for 6h and the Ir1 complex was isolated as yellow solid (74% yield).
pentaaquaoxovanadium(IV) di(trifluoromethanesulfonate)[ No CAS ]
[ 19455-23-3 ]
[ 72914-19-3 ]
[(VO)2O(piv)2(4,4'-di-tert-butyl-2,2′-bipyridine)2](otf)·H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
49.3%
A weighed amount of 4,4?-di-tert-butyl-2,2?-bipyridine (0.089g, 0.33mmol) was added to a solution of [VO(H2O)5](otf)2 (0.150g, 0.33mmol) in ethanol (30ml), and the reaction mixture was stirred at 22C for 5min. Then K(piv) (0.093g, 0.66mmol) was added to the green solution and the mixture was stirred for additional 20min. The resulting reddish-brown solution was concentrated in a Schlenk flask under reduced pressure. Dark green crystals suitable for X-ray diffraction were obtained within 5days. The crystals were separated from the mother liquor by filtration, washed with cold ethanol (t~-18C), and air-dried. The yield of 2 was 0.087g (49.3% based on the initial amount of [VO(H2O)5](otf)2). Anal. Calc for C47H70N4O12F3SV2: C, 52.21; H, 6.57; N, 5.22. Found: C, 52.54; H, 6.56; N, 5.55%. IR (KBr), nu/cm-1: 3466 br. w, 3121 vw, 3062 vw, 2967 m, 2910 w, 2874 w, 1716 vw, 1619 s, 1596 s, 1567 w, 1551 w, 1482 w, 1461 w, 1414 s, 1371 w, 1346 w, 1256 vs, 1225 m, 1159 m, 1082 vw, 1033 s, 975 w, 962 w, 937 vw, 899 w, 849 w, 784 vw, 766 vw, 752 vw, 742 vw, 721 vw, 639 s, 623 w, 609 w, 577 vw, 555 vw, 518 vw, 482 vw, 450 vw.
In the glove box, add [(PPhtBu2)Ag(mu-OCF3)]2 (1mmol) and substituted bipyridine (2mmol), acetonitrile (10mL) to the dried pressure-resistant reaction tube, oil at 40 After 1 hour of reaction in the bath, a colorless solution was obtained, which was allowed to stand and cool. After being taken into the glove box, it was filtered through a diatomite into a 100 mL egg-shaped bottle to obtain a colorless solution. After pumping it dry (one hour) using an oil pump, 960 mg of white was obtained. Solid I-4, yield 70%.