Functionalized N-Heterocyclic Carbene Nonspectator Ligands upon Internal Alkyne Activation Reactions

被引：32

作者：

Fernandez, Francys E. ^{[1
]}

del Carmen Puerta, Maria ^{[1
]}

Valerga, Pedro ^{[1
]}

机构：

[1] Univ Cadiz, Dept Ciencia Mat & Ingn Met & Quim Inorgan, Fac Ciencias, Cadiz 11510, Spain

来源：

INORGANIC CHEMISTRY | 2013年 / 52卷 / 11期

关键词：

C-H ACTIVATION; TRANSITION-METAL-COMPLEXES; HALF-SANDWICH COMPLEXES; CARBON-CARBON BONDS; TERMINAL ALKYNES; VINYLIDENE REARRANGEMENT; RUTHENIUM(II) COMPLEXES; TRANSFER HYDROGENATION; REDUCTIVE ELIMINATION; MIGRATORY INSERTION;

D O I：

10.1021/ic400433z

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

When studying the activation of 3-arylpropiolates by [TpRu(picolyl-I-R)Cl]/NaBAr4F (picolyl-I-Me = 3-methyl-1-(2-picolyl)imidazol-2-ylidene (1); picolyl-(BI)-B-Me = 3-methyl-1-(2-picolyl)benzoimidazol-2-ylidene (2)) a migratory insertion of the NHC into a ruthenium-carbon bond and an unprecedented C-N bond activation of the chelating picolyl-NHC ligand take place to give the new ruthenium metallacycles [TpRu(kappa(3)-C,N,N'-=C(Ph)-C(CH2Py)(CO2Me)(I-Me)][BAr4F] 3a and 4a and [TpRu(kappa(3)-C,N,N'-=C(4-CF3Ph)-C(CH2Py)(CO2Me)(I-Me)][BAr4F] 3b and 4b. X-ray crystal structures of 3a and 3b are reported, and a mechanistic pathway is proposed. In contrast, activation of internal alkynones by a mixture of [TpRu(picolyl-I-Me)Cl] complex (1) and NaBAr4F led to isolation and characterization of the corresponding disubstituted vinylidene complexes. Also, structures of [TpRu(picolyl-I-Me)(=CC(COR)(Ph)][BAr4F] (R = Me (6a); Ph (6b)) are reported.

引用

页码：6502 / 6509

页数：8

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