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Chemical Structure| 448-61-3 Chemical Structure| 448-61-3

Structure of 448-61-3

Chemical Structure| 448-61-3

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Feliciano-Carmona, Alberto ; Wang, Xiqu ; Hughes, Russell P ; Daugulis, Olafs ; Brookhart, Maurice ;

Abstract: We have prepared cationic palladium complexes possessing a new zwitterionic ligand bis-N,N’−1-(2,4,6-triphenylpyridyl) oxalamide [(N∧N)Pd(Me)(L)]+ [BArF], (BArF = 3,5-(CF3)2C6H3, L = NCMe, CO). The structure of [(N∧N)Pd(Me)(CO)]+ [BArF] was determined by X-ray diffraction analysis. Energy Decomposition Analysis (EDA) indicates this N∧N zwitterionic ligand is more electron-donating relative to bidentate diimine ligands. Low temperature NMR analysis shows the existence of linkage isomers with the N∧N isomer the most stable. Structures were assigned using NMR and DFT analysis. Barriers to interconversion of isomers are ΔG = 10−12 kcal/mol. Kinetics of acetonitrile displacement from [(N∧N)Pd(Me)-(NCCH3)]+ [BArF] by CD3CN, ethylene and t Bu3P were measured and mechanisms of exchange determined. The ethylene complex, [(N∧N)Pd(Me)(C2H4)]+ was generated at −45 °C, and the barrier of migratory insertion was determined at 0 °C (ΔG = 23.4 kcal/mol) and compared to related diimine complexes. The methyl carbonyl complex undergoes migratory insertion in the presence of CO at −70 to −55 °C (ΔG = ca. 15.7 kcal/mol) to yield the acyl carbonyl complex. The neutral bistrimethylsilylmethyl complex, (N∧N)Pd(CH2SiMe3)2 was prepared and characterized by X-ray diffraction analysis. It displays dynamic behavior at very low temperatures in the NMR spectrum (−90 °C, ΔG = 7.9 kcal/mol) which, supported by DFT analysis, is ascribed to rotation of the bulky −CH2SiMe3 groups.

Purchased from AmBeed: ;

Rosko, Michael C. ; Espinoza, Eli M. ; Arteta, Sarah ; Kromer, Sarah ; Wheeler, Jonathan P. ; Castellano, Felix N.

Abstract: Four Cu(I) bis(phenanthroline) photosensitizers formulated from a new ligand structural motif (Cu1-Cu4) coded according to their 2,9-substituents were synthesized, structurally characterized, and fully evaluated using steady-state and time-resolved absorption and photoluminescence (PL) measurements as well as electrochem. The 2,9-disubstituted-3,4,7,8-tetramethyl-1,10-phenanthroline ligands feature the following six-membered ring systems prepared through photochem. synthesis: 4,4-dimethylcyclohexyl (1), tetrahydro-2H-pyran-4-yl (2), tetrahydro-2H-thiopyran-4-yl (3), and 4,4-difluorocyclohexyl (4). Universally, these Cu(I) metal-to-ligand charge transfer (MLCT) chromophores display excited-state lifetimes on the microsecond time scale at room temperature, including the three longest-lived homoleptic cuprous phenanthroline excited states measured to date in de-aerated CH2Cl2, τ = 2.5-4.3μs. This series of mols. also feature high PL quantum efficiencies (ΦPL = 5.3-12% in CH2Cl2). Temperature-dependent PL lifetime experiments confirmed that all these mols. exhibit reverse intersystem crossing and display thermally activated delayed PL from a 1MLCT excited state lying slightly above the 3MLCT state, 1050-1490 cm-1. Ultrafast and conventional transient absorption measurements confirmed that the PL originates from the MLCT excited state, which remains sterically arrested, preventing an excessive flattening distortion even when dissolved in Lewis basic CH3CN. Combined PL and electrochem. data provided evidence that Cu1-Cu4 are highly potent photoreductants (Eox* = -1.73 to -1.62 V vs Fc+/0 in CH3CN), whose potentials are altered solely based on which heteroatoms or substituents are resident on the 2,9-appended ring derivatives It is proposed that long-range electronic inductive effects are responsible for the systematic modulation observed in the PL spectra, excited-state lifetimes, and the ground state absorption spectra and redox potentials. Cu1-Cu4 quant. follow the energy gap law, correlating well with structurally related cuprous phenanthrolines and are also shown to triplet photosensitize the excited states of 9,10-diphenylanthracene with bimol. rate constants ranging from 1.61 to 2.82 x 108 M-1 s-1. The ability to tailor both photophys. and electrochem. properties using long-range inductive effects imposed by the 2,9-ring platforms advocates new directions for future MLCT chromophore discovery.

Purchased from AmBeed: ;

Alternative Products

Product Details of [ 448-61-3 ]

CAS No. :448-61-3
Formula : C23H17BF4O
M.W : 396.19
SMILES Code : F[B-](F)(F)F.C1(C2=CC=CC=C2)=CC(C3=CC=CC=C3)=CC(C4=CC=CC=C4)=[O+]1
MDL No. :MFCD00012001
InChI Key :VQYPWMWEJGDSTF-UHFFFAOYSA-N
Pubchem ID :9930615

Safety of [ 448-61-3 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302+H312+H332-H315-H319-H335
Precautionary Statements:P261-P264-P270-P271-P280-P302+P352-P304+P340-P305+P351+P338-P312-P330-P362+P364-P403+P233-P501

Computational Chemistry of [ 448-61-3 ] Show Less

Physicochemical Properties

Num. heavy atoms 29
Num. arom. heavy atoms 24
Fraction Csp3 0.0
Num. rotatable bonds 3
Num. H-bond acceptors 5.0
Num. H-bond donors 0.0
Molar Refractivity 109.61
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

13.14 Ų

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

0.0
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

7.41
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

9.54
Log Po/w (MLOGP)?

MLOGP: Topological method implemented from
Moriguchi I. et al. 1992 Chem. Pharm. Bull.
Moriguchi I. et al. 1994 Chem. Pharm. Bull.
Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.

5.02
Log Po/w (SILICOS-IT)?

SILICOS-IT: Hybrid fragmental/topological method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

4.55
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

5.31

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-7.38
Solubility 0.0000166 mg/ml ; 0.0000000418 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Poorly soluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-7.52
Solubility 0.0000121 mg/ml ; 0.0000000304 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Poorly soluble
Log S (SILICOS-IT)?

SILICOS-IT: Fragmental method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

-8.35
Solubility 0.00000179 mg/ml ; 0.0000000045 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Poorly soluble

Pharmacokinetics

GI absorption?

Gatrointestinal absorption: according to the white of the BOILED-Egg

Low
BBB permeant?

BBB permeation: according to the yolk of the BOILED-Egg

No
P-gp substrate?

P-glycoprotein substrate: SVM model built on 1033 molecules (training set)
and tested on 415 molecules (test set)
10-fold CV: ACC=0.72 / AUC=0.77
External: ACC=0.88 / AUC=0.94

Yes
CYP1A2 inhibitor?

Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.83 / AUC=0.90
External: ACC=0.84 / AUC=0.91

Yes
CYP2C19 inhibitor?

Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.80 / AUC=0.86
External: ACC=0.80 / AUC=0.87

No
CYP2C9 inhibitor?

Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set)
and tested on 2075 molecules (test set)
10-fold CV: ACC=0.78 / AUC=0.85
External: ACC=0.71 / AUC=0.81

No
CYP2D6 inhibitor?

Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set)
and tested on 1068 molecules (test set)
10-fold CV: ACC=0.79 / AUC=0.85
External: ACC=0.81 / AUC=0.87

Yes
CYP3A4 inhibitor?

Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set)
and tested on 2579 molecules (test set)
10-fold CV: ACC=0.77 / AUC=0.85
External: ACC=0.78 / AUC=0.86

Yes
Log Kp (skin permeation)?

Skin permeation: QSPR model implemented from
Potts RO and Guy RH. 1992 Pharm. Res.

-3.46 cm/s

Druglikeness

Lipinski?

Lipinski (Pfizer) filter: implemented from
Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev.
MW ≤ 500
MLOGP ≤ 4.15
N or O ≤ 10
NH or OH ≤ 5

1.0
Ghose?

Ghose filter: implemented from
Ghose AK. et al. 1999 J. Comb. Chem.
160 ≤ MW ≤ 480
-0.4 ≤ WLOGP ≤ 5.6
40 ≤ MR ≤ 130
20 ≤ atoms ≤ 70

None
Veber?

Veber (GSK) filter: implemented from
Veber DF. et al. 2002 J. Med. Chem.
Rotatable bonds ≤ 10
TPSA ≤ 140

0.0
Egan?

Egan (Pharmacia) filter: implemented from
Egan WJ. et al. 2000 J. Med. Chem.
WLOGP ≤ 5.88
TPSA ≤ 131.6

1.0
Muegge?

Muegge (Bayer) filter: implemented from
Muegge I. et al. 2001 J. Med. Chem.
200 ≤ MW ≤ 600
-2 ≤ XLOGP ≤ 5
TPSA ≤ 150
Num. rings ≤ 7
Num. carbon > 4
Num. heteroatoms > 1
Num. rotatable bonds ≤ 15
H-bond acc. ≤ 10
H-bond don. ≤ 5

2.0
Bioavailability Score?

Abbott Bioavailability Score: Probability of F > 10% in rat
implemented from
Martin YC. 2005 J. Med. Chem.

0.55

Medicinal Chemistry

PAINS?

Pan Assay Interference Structures: implemented from
Baell JB. & Holloway GA. 2010 J. Med. Chem.

0.0 alert
Brenk?

Structural Alert: implemented from
Brenk R. et al. 2008 ChemMedChem

2.0 alert: heavy_metal
Leadlikeness?

Leadlikeness: implemented from
Teague SJ. 1999 Angew. Chem. Int. Ed.
250 ≤ MW ≤ 350
XLOGP ≤ 3.5
Num. rotatable bonds ≤ 7

No; 1 violation:MW<2.0
Synthetic accessibility?

Synthetic accessibility score: from 1 (very easy) to 10 (very difficult)
based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties,
trained on 12'782'590 molecules and tested on 40 external molecules (r2 = 0.94)

3.65

Application In Synthesis of [ 448-61-3 ]

* 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.

  • Downstream synthetic route of [ 448-61-3 ]

[ 448-61-3 ] Synthesis Path-Downstream   1~5

  • 1
  • [ 28466-26-4 ]
  • [ 448-61-3 ]
  • C26H20N3(1+)*BF4(1-)*BF3*FH [ No CAS ]
  • 2
  • [ 448-61-3 ]
  • [ 192130-34-0 ]
  • 1-(2-(4-(tert-butoxycarbonyl)piperazin-1-yl)ethyl)-2,4,6-triphenylpyridin-1-ium tetrafluoroborate [ No CAS ]
  • 3
  • [ 99071-54-2 ]
  • [ 448-61-3 ]
  • 2,4,6‐triphenyl-1‐(quinolin-6‐ylmethyl)pyridin‐1‐ium tetrafluoroborate [ No CAS ]
  • 4
  • [ 448-61-3 ]
  • [ 33024-60-1 ]
  • 2,4,6-triphenyl-1-(tetrahydro-2H-pyran-4-yl)pyridin-1-ium tetrafluoroborate [ No CAS ]
  • 5
  • [ 448-61-3 ]
  • [ 535936-86-8 ]
  • 1-(1-cyclopropyl-2-methoxy-2-oxoethyl)-2,4,6-triphenylpyridin-1-ium tetrafluoroborate [ No CAS ]
 

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