Insight into the Mechanism of R-R Reductive Elimination from the Six-Coordinate d6 Complexes L2Pt(R)4 (R = vinyl, Me)

被引：27

作者：

Ariafard, Alireza ^{[1
]}

Ejehi, Zeinab ^{[1
]}

Sadrara, Hoda ^{[1
]}

Mehrabi, Tahmineh ^{[1
]}

Etaati, Shohreh ^{[1
]}

Moradzadeh, Azadeh ^{[1
]}

Moshtaghi, Mahshid ^{[1
]}

Nosrati, Hadis ^{[1
]}

Brookes, Nigel J. ^{[2
]}

Yates, Brian F. ^{[2
]}

机构：

[1] Islamic Azad Univ, Cent Tehran Branch, Fac Sci, Dept Chem, Tehran, Iran

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

来源：

ORGANOMETALLICS | 2011年 / 30卷 / 03期

基金：

澳大利亚研究理事会;

关键词：

EFFECTIVE CORE POTENTIALS; MAIN-GROUP ELEMENTS; C-H BONDS; ELECTROPHILIC PLATINUM COMPLEXES; CYCLOMETALATED PT(IV) COMPLEXES; CARBON-CARBON; MOLECULAR CALCULATIONS; POLARIZATION FUNCTIONS; DENSITY FUNCTIONALS; BASIS-SETS;

D O I：

10.1021/om1005512

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

We have used density functional theory to investigate the reductive elimination from platinum(IV) structures of the form L2PtR4 where L = PMe3, PH3, PF3, CO, NH3 and R = vinyl, Me. We conclude that reductive elimination occurs via the L-predissociation pathway for R = Me, irrespective of ligand L. But when R = vinyl, direct elimination is the preferred pathway if the L ligand is PMe3; otherwise both pathways are competitive for R = vinyl. We also note that if L is more pi-electron accepting and less a-electron donating, the reductive elimination from the six-coordinate complexes L2PtR4 will be more rapid. Reductive elimination from the five-coordinate complexes LPtR4 proceeds more easily if the ligand trans to the two R groups being coupled is more a-electron donating and the ligands cis to the two R groups are more pi-electron accepting.

引用

页码：422 / 432

页数：11

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