1,2,3-Triazolylidene ruthenium(II)(η6-arene) complexes: synthesis, metallation and reactivity

被引：36

作者：

Bagh, Bidraha ^{[1
]}

McKinty, Adam M. ^{[1
]}

Lough, Alan J. ^{[1
]}

Stephan, Douglas W. ^{[1
]}

机构：

[1] Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada

来源：

DALTON TRANSACTIONS | 2014年 / 43卷 / 34期

基金：

加拿大自然科学与工程研究理事会;

关键词：

N-HETEROCYCLIC CARBENE; C-H BOND; CATALYTIC-ACTIVITY; LIGANDS SYNTHESIS; TERMINAL ALKYNES; IRIDIUM COMPLEX; ACTIVATION; OXIDATION; RUTHENIUM(II); METATHESIS;

D O I：

10.1039/c4dt01174k

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Three bis(1,2,3-triazolylidene) silver(i) complexes were synthesized, and the ruthenium complexes ([RCH2N2(NMe)C2Ph)]RuCl2(p-cymene) (R = C6H2Me3 4a(1), C(6)H(2)lPr(3) 4b(1)) were isolated as major products with the minor C(sp(2))-H activated products ([RCH2N2(NMe)C2C6H4)]RuCl(p-cymene) (R = C6H2Me3 4a(2), C(6)H(2)iPr(3) 4b(2)). In the related case where R = Ph, the species ([PhCH2N2(NMe)C2Ph)]RuCl2(p-cymene) 4c(1) was obtained with two C(sp(2))-H activated products (PhCH2N2(NMe)C2C6H4)]RuCl(p-cymene) 4c(2) and [(C6H4)CH2N2(NMe)C2Ph)]RuCl(p-cymene) 4c(3) derived from metaltation of the N and C-bound arene rings. Heating a solution of 4a(1) at 45 degrees C over three weeks resulted in a ruthenium(II)(1,2,3-triazolylidene) complex [(C6H2Me3)CH2N2(NMe)C2Ph)]RuCl2 5a, where the pendant mesityl group on the triazotylidene moiety displaced the p-cymene ligand. The complexes 4a(1), 4b(1), 4c(1) and 5a displayed moderate catalytic activities in base-free oxidation of benzyl alcohols to benzaldehydes and oxidative homocoupling of benzyl amines to imines using oxygen as oxidant.

引用

页码：12842 / 12850

页数：9

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