Influence of geometry on reductive elimination of hydrocarbyl-palladium-carbene complexes

被引：37

作者：

Graham, DC

Cavell, KJ

Yates, BF

机构：

[1] Univ Tasmania, Sch Chem, Hobart, Tas 7001, Australia

[2] Cardiff Univ, Dept Chem, Cardiff CF10 3TB, S Glam, Wales

来源：

DALTON TRANSACTIONS | 2005年 / 06期

关键词：

D O I：

10.1039/b417111j

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The influence of spectator ligand bite angle and the twist angle of the carbene on the reductive elimination of N-heterocyclic carbenes (NHCs) from palladium bis-phosphine complexes has been investigated using density functional theory. The spectator bite angle was found to have a significant influence on both the activation energy (E-act) and the enthalpy of reaction. Widening of the bite angle was found to lower E-act and increase the enthalpy of reaction. In contrast, rotation of the carbene with respect to the PdL2 plane was found to have little influence on E-act. At carbene twist angles approaching 0degrees however, relief of the increased steric strain provides a considerable driving force for the decomposition reaction.

引用

页码：1093 / 1100

页数：8

共 54 条

[41] Kinetic and density functional studies on alkyl-carbene elimination from PdII heterocylic carbene complexes:: A new type of reductive elimination with clear implications for catalysis
McGuinness, DS
Saendig, N
Yates, BF
Cavell, KJ
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (17) : 4029 - 4040
[42] Reaction of CO with a methylpalladium heterocyclic carbene complex: Product decomposition routes-implications for catalytic carbonylation processes
McGuinness, DS
Cavell, KJ
[J]. ORGANOMETALLICS, 2000, 19 (23) : 4918 - 4920
[43] Unprecedented C-H bond oxidative addition of the imidazolium cation to Pt0:: a combined density functional analysis and experimental study
McGuinness, DS
Cavell, KJ
Yates, BF
[J]. CHEMICAL COMMUNICATIONS, 2001, (04) : 355 - 356
[44] Synthesis and reaction chemistry of mixed ligand methylpalladium-carbene complexes
McGuinness, DS
Green, MJ
Cavell, KJ
Skelton, BW
White, AH
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1998, 565 (1-2) : 165 - 178
[45] CONTRACTED GAUSSIAN-BASIS SETS FOR MOLECULAR CALCULATIONS .1. 2ND ROW ATOMS, Z=11-18
MCLEAN, AD
CHANDLER, GS
[J]. JOURNAL OF CHEMICAL PHYSICS, 1980, 72 (10) : 5639 - 5648
[46] Experimental and computational study of a reductive elimination mechanism in a methyl-Pd(II)-CNC carbene complex
Nielsen, DJ
Magill, AM
Yates, BF
Cavell, KJ
Skelton, BW
White, AH
[J]. CHEMICAL COMMUNICATIONS, 2002, (21) : 2500 - 2501
[47] CHEMISTRY OF PLATINUM AND PALLADIUM COMPOUNDS OF BULKY PHOSPHINES
OTSUKA, S
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1980, 200 (01) : 191 - 205
[48] A Pd complex of a tridentate pincer CNC bis-carbene ligand as a robust homogenous Heck catalyst
Peris, E
Loch, JA
Mata, J
Crabtree, RH
[J]. CHEMICAL COMMUNICATIONS, 2001, (02) : 201 - 202
[49] CHELATE EFFECT ON THE STRUCTURE AND REACTIVITY OF ELECTRON-RICH PALLADIUM COMPLEXES AND ITS RELEVANCE TO CATALYSIS
PORTNOY, M
MILSTEIN, D
[J]. ORGANOMETALLICS, 1993, 12 (05) : 1655 - 1664
[50] Theoretical study of oxidative addition and reductive elimination of 14-electron d10 ML2 complexes:: A ML2+CH4 (M = Pd, Pt; L = CO,PH3, L2 = PH′2CH2CH2PH2) case study
Su, MD
Chu, SY
[J]. INORGANIC CHEMISTRY, 1998, 37 (13) : 3400 - 3406

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