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• W1763275056 abstract "Abstract The reactions of quinoline‐2‐carbaldehyde (pyridine‐2‐carbonyl)hydrazone (HL) and [RuCl 2 (PPh 3 ) 3 ] in various solvents at different temperatures gave the three geometrical isomers trans(Cl,Cl) ‐, cis(Cl,Cl),trans(P,N) ‐, and trans(P,P) ‐[RuCl 2 (PPh 3 ) 2 {HL‐κ O (amide),κ N (imine)}] ( 1 , 2 , and 3 , respectively) as well as a linkage isomer trans(P,P) ‐[RuCl 2 (PPh 3 ) 2 {HL‐κ N (imine),κ N (quin)}] ( 4 ). The molecular and crystal structures of 1 – 4 , together with both E and Z configurational isomers (with respect to the C=N double bond) of the free ligand HL, were determined by X‐ray analysis. The ligand HL adopted a Z form and acted as a κ O (amide),κ N (imine) bidentate ligand in 1 – 3 , whereas it was an E isomer with a κ N (imine),κ N (quin) coordination mode in 4 . The gradual thermal conversions of 1 to 2 and of 2 to 3 were observed in dichloromethane and ethanol, respectively, but an interconversion between 3 and 4 was not detected. In dichloromethane, all complexes have a reversible Ru III/II redox couple in the range 110–412 mV (vs. Ag/Ag + ), and the redox potential was largely dependent on the coordination mode of HL and on the mutual configuration of the two PPh 3 ligands. Such a potential shift can be interpreted as a combination of Cl – /amide O π‐donor and PPh 3 /quinoline N π‐acceptor orbital contributions to the Ru II dπ orbitals [highest occupied molecular orbitals (HOMOs)]. Complexes 3 and 4 in acetonitrile showed a gradual spectral change, probably because of the substitution of the Cl – ligand by the acetonitrile solvent. In addition, 2 – 4 showed solvatochromic behavior even in noncoordinating solvents that resulted from a blueshift of the metal‐to‐ligand charge‐transfer (MLCT) transition band in polar solvents. These electrochemical and spectroscopic properties are also supported by DFT and time‐dependent DFT (TD‐DFT) calculations." @default.
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• W1763275056 date "2013-12-02" @default.
• W1763275056 modified "2023-10-17" @default.
• W1763275056 title "Linkage and Geometrical Isomers of Dichloridobis(triphenylphosphine)ruthenium(II) Complexes with Quinoline‐2‐carbaldehyde (Pyridine‐2‐carbonyl)hydrazone: Their Molecular Structures and Electrochemical and Spectroscopic Properties" @default.
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• W1763275056 doi "https://doi.org/10.1002/ejic.201301150" @default.
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