Alkyne Insertion into the M-P and M-H Bonds (M = Pd, Ni, Pt, and Rh): A Theoretical Mechanistic Study of the C-P and C-H Bond-Formation Steps

被引：43

作者：

Ananikov, Valentine P. ^{[1
]}

Beletskaya, Irina P. ^{[2
]}

机构：

[1] Russian Acad Sci, Zelinsky Inst Organ Chem, Moscow 119991, Russia

[2] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119899, Russia

来源：

CHEMISTRY-AN ASIAN JOURNAL | 2011年 / 6卷 / 06期

基金：

俄罗斯基础研究基金会;

关键词：

alkyne; catalysis; insertion; selectivity; transition metals; GENERALIZED GRADIENT APPROXIMATION; PHOSPHORUS-CARBON BOND; TERMINAL ALKYNES; ENANTIOSELECTIVE SYNTHESIS; ASYMMETRIC HYDROGENATION; INTERMOLECULAR HYDROALKOXYLATION; REDUCTIVE ELIMINATION; BIOLOGICAL EVALUATION; UNACTIVATED ALKENES; ADDITION-REACTIONS;

D O I：

10.1002/asia.201000840

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In hydrogen-metal-phosphorus (H-M-P) transition metal complexes (proposed as intermediates of H-P bond addition to alkynes in the catalytic hydrophosphorylation, hydrophosphinylation, and hydrophospination reactions), alkyne insertion into the metal-hydrogen bond was found much more facile compared to alkyne insertion into the metal-phosphorus bond. The conclusion was verified for different metals (Pd, Ni, Pt, and Rh), ligands, and phosphorus groups at various theory levels (B3LYP, B3PW91, BLYP, MP2, and ONIOM). The relative reactivity of the metal complexes in the reaction with alkynes was estimated and decreased in the order of Ni > Pd > Rh > Pt. A trend in relative reactivity was established for various types of phosphorus groups: PR2 > P(O)R-2 > P(O)(OR)(2), which showed a decrease in rate upon increasing the number of the oxygen atoms attached to the phosphorus center.

引用

页码：1423 / 1430

页数：8

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