Carbon Oxygen Bond Forming Reductive Elimination from Cycloplatinated(IV) Complexes

被引：21

作者：

Aseman, Marzieh Dadkhah ^{[1
,2
]}

Nabavizadeh, S. Masoud ^{[1
,3
]}

Hosseini, Fatemeh Niroomand ^{[3
,4
]}

Wu, Guang ^{[3
]}

Abu-Omar, Mandi M. ^{[3
]}

机构：

[1] Shiraz Univ, Coll Sci, Dept Chem, Shiraz 7146713565, Iran

[2] Kharazmi Univ, Fac Chem, Tehran, Iran

[3] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA

[4] Islamic Azad Univ, Shiraz Branch, Dept Chem, Shiraz 7199337635, Iran

来源：

ORGANOMETALLICS | 2018年 / 37卷 / 01期

关键词：

C-O; PD-IV; MECHANISM; ISOMERIZATION; PALLADIUM(II); REACTIVITY; OXIDATION; CENTERS; LIGAND; ME;

D O I：

10.1021/acs.organomet.7b00745

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis of the two cycloplatinated(W) complexes [PtMe(OAc)2(C boolean AND N)(H2O)] (CAN = 2-phenylpyridinate (2a), benzo[h]quinolate, 2b) by reaction of [PtMe(C boolean AND N)(SMe2)] with PhI(OAc)(2) is described. Complexes 2 undergo carbon oxygen bond forming reductive elimination instead of C-C reductive elimination to produce MeOAc as protected methanol. The kinetics and mechanism of both Pt-O bond formation and C-O reductive elimination have been experimentally and theoretically investigated. The results suggest that formation of methyl acetate proceeds via nucleophilic attack of the dissociated acetate ligand at the methyl group carbon in a cationic five-coordinate intermediate cycloplatinated(W) complex.

引用

页码：87 / 98

页数：12

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