Structure of 448-61-3
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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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.
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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.
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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 |
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 |
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 |
13.14 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
0.0 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
7.41 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
9.54 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
5.02 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
4.55 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
5.31 |
Log S (ESOL):? ESOL: Topological method implemented from |
-7.38 |
Solubility | 0.0000166 mg/ml ; 0.0000000418 mol/l |
Class? Solubility class: Log S scale |
Poorly soluble |
Log S (Ali)? Ali: Topological method implemented from |
-7.52 |
Solubility | 0.0000121 mg/ml ; 0.0000000304 mol/l |
Class? Solubility class: Log S scale |
Poorly soluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-8.35 |
Solubility | 0.00000179 mg/ml ; 0.0000000045 mol/l |
Class? Solubility class: Log S scale |
Poorly soluble |
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) |
Yes |
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) |
Yes |
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
No |
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) |
No |
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) |
Yes |
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) |
Yes |
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from |
-3.46 cm/s |
Lipinski? Lipinski (Pfizer) filter: implemented from |
1.0 |
Ghose? Ghose filter: implemented from |
None |
Veber? Veber (GSK) filter: implemented from |
0.0 |
Egan? Egan (Pharmacia) filter: implemented from |
1.0 |
Muegge? Muegge (Bayer) filter: implemented from |
2.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.55 |
PAINS? Pan Assay Interference Structures: implemented from |
0.0 alert |
Brenk? Structural Alert: implemented from |
2.0 alert: heavy_metal |
Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<2.0 |
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
3.65 |
* 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.
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