%0 Journal Article %A Tejel, Cristina %A Ciriano, Miguel A. %A López, José A. %A Lahoz, Fernando J. %A Oro, Luis A. %D 1998 %T Unusual Tautomers in Dinuclear Metal Chemistry and Their Role in Oxidative-Addition Reactions of Chlorocarbons %U https://acs.figshare.com/articles/journal_contribution/Unusual_Tautomers_in_Dinuclear_Metal_Chemistry_and_Their_Role_in_Oxidative-Addition_Reactions_of_Chlorocarbons/3781458 %R 10.1021/om970981x.s001 %2 https://acs.figshare.com/ndownloader/files/5892423 %K Dinuclear Metal Chemistry %K PhCH 2 Cl %K tautomeric equilibrium %K MeCO 2 CH 2 Cl %K CNBu %K Unusual Tautomers %K Ir %K MeCO 2 CH 2 %X The complex [{Ir(μ-Pz)(CNBut)2}2(Cl)(CH2Ph)] (2), obtained by reaction of [{Ir(μ-Pz)(CNBut)2}2] (1) with PhCH2Cl, presents a very unusual tautomeric equilibrium between the metal−metal-bonded and the mixed-valence complexes [(CNBut)2(Cl)Ir(μ-Pz)2Ir(CH2Ph)(CNBut)2] and [(CNBut)2Ir(μ-Pz)2Ir(Cl)(CH2Ph)(CNBut)2], respectively. This equilibrium allows the unprecedented oxidative-addition reaction of chloroalkanes such as PhCH2Cl and MeCO2CH2Cl to the diiridium(II) complex 2, resulting in the diiridium(III) complex [{Ir(μ-Pz)(CH2Ph)(CNBut)2}2(μ-Cl)]Cl and the mixed-dialkyl complex [(CNBut)2(MeCO2CH2)Ir(μ-Pz)2(μ-Cl)Ir(CH2Ph)(CNBut)2]Cl, respectively. %I ACS Publications