Chemistry is the science of change. But why do chemical reactions take place? Why do chemicals react with each other? The answer is in thermodynamics and kinetics.In a document type is Article, the author is Culkin, Darcy A. and a compound is mentioned, 97239-80-0, 1,1′-Bis(diisopropylphosphino)ferrocene, introducing its new discovery. 97239-80-0
Carbon-carbon bond-forming reductive elimination from arylpalladium complexes containing functionalized alkyl groups. Influence of ligand steric and electronic properties on structure, stability, and reactivity
A series of arylpalladium alkyl complexes of the formula [(DPPBz)Pd(Ar)(R)] (DPPBz = 1,2-bis(diphenylphosphino)benzene; R = methyl, benzyl, enolate, cyanoalkyl, trifluoroalkyl, or malonate) has been prepared to reveal the influence of steric and electronic parameters on structure, stability, and reactivity. Arylpalladium enolate and cyanoalkyl complexes ligated by EtPh 22P, 1,1-bis(diisopropylphosphino)ferrocene (D iPrPF), and BINAP were prepared to evaluate the effect of the ancillary ligand. The coordination modes of the enolate and cyanoalkyl complexes were determined by spectroscopic methods, in combination with X-ray crystallography. In the absence of steric effects, the C-bound isomer was favored electronically if the enolate or cyanoalkyl group was located trans to a phosphine, and the O-bound isomer was favored if the enolate was located trans to an aryl group. The thermodynamic stability of the enolate and cyanoalkyl complexes was controlled by the steric properties of the enolate or cyanoalkyl group, and complexes with more substitution at the alpha-carbon were less stable. Arylpalladium methyl, benzyl, enolate, cyanoalkyl, and trifluoroethyl complexes underwent carbon-carbon bond-forming reductive elimination upon heating. Reductive elimination was faster from complexes with electron-withdrawing substituents on the palladium-bound aryl group and with sterically hindered alkyl groups. The electronic properties of the alkyl group had the largest impact on the rate of reductive elimination: electron-withdrawing groups on the alpha-carbon retarded the rate of reductive elimination. The rates of reductive elimination correlated with the Taft polar substituent constants of the groups on the carbon alpha to the metal.
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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate