Chloride labilization resulting from nucleophilic addition to cis-Ru(tpy)(CO)(2)Cl+PF6-: Synthesis and characterization of new CO2-bridged and formate complexes of ruthenium

被引：32

作者：

Gibson, DH ^{[1
]}

Sleadd, BA ^{[1
]}

Mashuta, MS ^{[1
]}

Richardson, JF ^{[1
]}

机构：

[1] UNIV LOUISVILLE,CTR CHEM CATALYSIS,LOUISVILLE,KY 40292

来源：

ORGANOMETALLICS | 1997年 / 16卷 / 20期

关键词：

D O I：

10.1021/om970493p

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of cis-Ru(tpy)(CO)(2)Cl+PF6- (1; tpy = 2,2':6',2 ''-terpyridyl) with aqueous Na2CO3 in acetonitrile yields the CO2-bridged complex cis,cis-(CH3CN)(CO)(tpy)Ru(CO2)Ru(tpy)(CO)(2)(2+)2PF(6)(-) (3). Reaction of 1 with aqueous NaOCHO yields the corresponding eta(1)-formato complex 4; reaction of 4 with aqueous Na2CO3 also provides 3. Reaction of 3 with CO results in displacement of acetonitrile and formation of 5, cis,cis-(CO)(2)(tpy)Ru(CO2)Ru(tpy)(CO)(2)(2+)2PF(6)(-). Reaction paths leading to 3 and 4 from 1 are thought to occur by base-assisted trans labilization of chloride resulting from conversion of a pi-acceptor ligand (CO) to a sigma-donor (COOH). Support for proposed steps in the reaction paths leading to 3 and 4 was provided by a trapping experiment in which 1 reacts with cis-Ru(bpy)(2)(CO)COOH+PF6- in the presence of aqueous Na2CO3 to give cis,cis-(CO)(bpy)(2)Ru(CO2)Ru(tpy)(CO)(2)(2+)2PF(6)(-) (7; bpy = 2,2'-bipyridyl), which has been structurally characterized. Parallels between these reactions and the halide labilizations which occur with ruthenium or rhenium polypyridyl complexes during photochemical or electrochemical reductions of CO2 are discussed.

引用

页码：4421 / 4427

页数：7

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