Base hydrolysis of acetonitrile coordinated to a ruthenium(II) polypyridine complex

被引：13

作者：

Fagalde, F ^{[1
]}

deKatz, NDL ^{[1
]}

Katz, NE ^{[1
]}

机构：

[1] UNIV NACL TUCUMAN, INST QUIM FIS, FAC BIOQUIM QUIM & FARM, RA-4000 S MIGUEL TUCUMAN, TUCUMAN, ARGENTINA

来源：

POLYHEDRON | 1997年 / 16卷 / 11期

关键词：

base hydrolysis; acetonitrile complexes; ruthenium(II); polypyridine; catalysis; pi-backbonding;

D O I：

10.1016/S0277-5387(96)00447-0

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

On coordination to Ru(terpy)(bipy)(2+) (terpy = 2,2': 6',2 ''-terpyridine, bipy = 2,2'-bipyridine), acetonitrile is converted to acetamide in aqueous basic solution, through hydroxide attack with a catalytic factor of ca 3 x 10(3) (k(OH) = 4.6 X 10(-3) M(-1) s(-1)). This is a remarkable effect for a d(6) transition metal in the (II) oxidation state, and can be ascribed to pi backbonding from the metal to the polypyridyl ligands, which makes the ruthenium(II) centre more electropositive than ruthenium(II) in the Ru(NH3)(5)(2+) moiety. The final hydrolysis product is the [Ru(terpy)(bipy)(OH)](+) complex, since amides, being poor pi-acceptor ligands, are rapidly released from the coordination sphere of ruthenium(II). (C) 1997 Elsevier Science Ltd.

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页码：1921 / 1923

页数：3

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