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Russian Chemical Bulletin - The spatial and electronic structure of a series of pyridyl-containing phospholanes, which are potential ligands for the synthesis of luminescent transition metal...  相似文献   
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Russian Chemical Bulletin - Pyridoxine and its derivatives, pyridoxamine and pyridoxal, are the three main forms of vitamin B6, which play exceptionally important biological roles in living...  相似文献   
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Nickel complexes with new cyclic ligands containing phosphorus and nitrogen atoms as coordination sites are novel efficient catalysts for hydrogen oxidation. A systematic study of their electrochemical properties made it possible to classify the nickel systems in question into four groups according to the sequence of electron transfer processes in the reduction (MII-MI-M0) and to the nature of solvents and counterions. Regularities of catalytic transformations involving nickel complexes with P,N-cyclic ligands in the H2 oxidation reaction in the coordination sphere of the catalyst and a correlation between the structure of the complex and its redox properties were established. The most efficient catalysts contain phenyl and 2-pyridyl substituents at the phosphorus atom and benzyl or 2-pyridyl substituents at the nitrogen atom.  相似文献   
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Eight‐membered cyclic functional bisphosphines, namely 1,5‐di‐aryl‐3,7‐di(2‐pyridyl)‐1,5‐diaza‐3,7‐diphosphacyclooctanes (aryl=2‐pyridyl, m‐tolyl, p‐tolyl, diphenylmethyl, benzyl, (R)‐(+)‐(α‐methyl)benzyl), with 2‐pyridyl substituents on the phosphorus atoms have been synthesized by condensation of 2‐pyridylphosphine, formaldehyde, and the corresponding primary amine. The structures of some of these bisphosphines have been investigated by X‐ray crystallography. The bisphosphines readily form neutral P,P‐chelate complexes [(κ2‐P,P‐L)MCl2], cationic bis‐P,P‐chelate complexes [(κ2‐P,P‐L)2M]2+, or a five‐coordinate complex [(κ2‐P,P‐L)2NiBr]Br. The electrochemical behavior of two of the nickel complexes, and their catalytic activities in electrochemical hydrogen evolution and hydrogen oxidation, including the fuel‐cell test, have been studied.  相似文献   
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Reactions of 1,2-bis[(hydroxymethyl)(phenyl)phosphino]ethane with primary pyridylalkylamines gave earlier unknown 1-aza-3,6-diphosphacycloheptanes containing the pyridyl group in the exocyclic substituent. The reactions were found to be stereoselective, preferentially yielding the racemate with the RR/SS-configuration of the P atoms. A mixture of diastereomers of 3,6-diphenyl-1-[2-(2-pyridyl)ethyl]-1-aza-3,6-diphosphacycloheptane reacted with dichloro(cycloocta-1,5-diene)platinum(II) to give cis-P,P-chelate complexes from the meso-isomer and bridged oligomeric complexes from the racemate.  相似文献   
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Conformations and dynamics of 1,5-diaza-3,7-diphosphacyclooctane (1) with chiral l-menthyl substituents on the phosphorus atoms and several metal complexes thereof were investigated by a variety of DNMR methods. In solution 1 adopts a C(2) symmetrical "crown"-like conformation (CW) and the conformational preference and dynamics of the complexes depend on the type of metal: for the Cu complex the CW form is preferred, whereas the Pd, Pt, or Mo complexes exist in an equilibrium of two "chair-boat"-like conformations (CB/CB*). The barriers of interconversion between these two conformations for the Pd and Pt complexes are about 2 times higher than for the Mo complex. Quantum chemical calculations (B3LYP/6-31G(d)) are in agreement with experimental findings.  相似文献   
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