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Selective CC Coupling of Ir–Ethene and Ir–Carbenoid Radicals
Author(s) -
Dzik Wojciech I.,
Reek Joost N. H.,
de Bruin Bas
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800262
Subject(s) - carbenoid , chemistry , reactivity (psychology) , radical , medicinal chemistry , hydrogen atom abstraction , photochemistry , iridium , adduct , stereochemistry , rhodium , catalysis , organic chemistry , medicine , alternative medicine , pathology
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 CC 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.