Migratory insertion of acetylene in N-heterocyclic carbene complexes of ruthenium: Formation of (ruthenocenylmethyl)imidazolium salts

被引：37
作者：
Becker, Eva
Sting, Verena
Dazinger, Georg
Mereiter, Kurt
Kirchner, Karl
机构：
[1] Vienna Univ Technol, Inst Appl Synth Chem, A-1060 Vienna, Austria
[2] Vienna Univ Technol, Inst Chem Technol & Analyt, A-1060 Vienna, Austria
来源：
ORGANOMETALLICS | 2007年 / 26卷 / 06期
关键词：
D O I：
10.1021/om060990i
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
With the parent acetylene and [RuCp(IPr)(CH3CN)(2)]PF6 (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) an unusual C-C coupling process takes place involving three acetylene molecules and migration of the NHC ligand to give the formal [2 + 2 + 1] cycloaddition product [RuCp(eta(4)-C5H5-eta(1)-CH-IPr)]PF6. This complex undergoes a facile 1,2-H shift to afford the (ruthenocenylmethyl)imidazolium salt [RuCp(eta(5)-C5H4-CH2-IPr)]PF6. The same reaction takes place with [RuCp(SIPr)(CH3CN)(2)]PF6 (SIPr = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene), giving [RuCp(eta(5)-C5H4-CH2-SIPr)]PF6. A conceivable mechanism for this reaction sequence is established by means of DFT/B3LYP calculations. The key step is the facile insertion of acetylene into the Ru-C bond of the NHC ligand, requiring merely 4.1 kcal/mol with 1,3-dimethylimidazol-2-ylidene but 17.2 kcal/mol with 1,3-diphenylimidazol-2-ylidene as model NHC ligands.
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页码：1531 / 1535
页数：5
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