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• W2171053485 abstract "Abstract The reactivity of the paramagnetic iridium(II) complex [Ir II (ethene)(Me 3 tpa)] 2+ ( 1 ) (Me 3 tpa= N , N , N ‐tris(6‐methyl‐2‐pyridylmethyl) amine) towards the diazo compounds ethyl diazoacetate (EDA) and trimethylsilyldiazomethane (TMSDM) was investigated. The reaction with EDA gave rise to selective CC bond formation, most likely through radical coupling of the Ir–carbenoid radical species [Ir III {CH . (COOEt)}(MeCN)(Me 3 tpa)] 2+ ( 7 ) and (the MeCN adduct of) 1 , to give the tetracationic dinuclear complex [(MeCN)(Me 3 tpa)Ir III {CH(COOEt)CH 2 CH 2 }Ir III (MeCN)(Me 3 tpa)] 2+ ( 4 ). The analogous reaction with TMSDM leads to the mononuclear dicationic species [Ir III {CH 2 (SiMe 3 )}(MeCN)(Me 3 tpa)] 2+ ( 11 ). This reaction probably involves a hydrogen‐atom abstraction from TMSDM by the intermediate Ir–carbenoid radical species [Ir III {CH . (SiMe 3 )}(MeCN)(Me 3 tpa)] 2+ ( 10 ). DFT calculations support pathways proceeding via these Ir–carbenoid radicals. The carbenoid–radical species are actually carbon‐centered ligand radicals, with an electronic structure best described as one‐electron‐reduced Fischer‐type carbenes. To our knowledge, this paper represents the first reactivity study of a mononuclear Ir II species towards diazo compounds." @default.
• W2171053485 created "2016-06-24" @default.
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• W2171053485 date "2008-08-25" @default.
• W2171053485 modified "2023-10-18" @default.
• W2171053485 title "Selective CC Coupling of Ir-Ethene and Ir-Carbenoid Radicals" @default.
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• W2171053485 doi "https://doi.org/10.1002/chem.200800262" @default.
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