10.1021/om970981x.s001 Cristina Tejel Cristina Tejel Miguel A. Ciriano Miguel A. Ciriano José A. López José A. López Fernando J. Lahoz Fernando J. Lahoz Luis A. Oro Luis A. Oro Unusual Tautomers in Dinuclear Metal Chemistry and Their Role in Oxidative-Addition Reactions of Chlorocarbons American Chemical Society 1998 Dinuclear Metal Chemistry PhCH 2 Cl tautomeric equilibrium MeCO 2 CH 2 Cl CNBu Unusual Tautomers Ir MeCO 2 CH 2 1998-03-20 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Unusual_Tautomers_in_Dinuclear_Metal_Chemistry_and_Their_Role_in_Oxidative-Addition_Reactions_of_Chlorocarbons/3781458 The complex [{Ir(μ-Pz)(CNBu<sup>t</sup>)<sub>2</sub>}<sub>2</sub>(Cl)(CH<sub>2</sub>Ph)] (<b>2</b>), obtained by reaction of [{Ir(μ-Pz)(CNBu<sup>t</sup>)<sub>2</sub>}<sub>2</sub>] (<b>1</b>) with PhCH<sub>2</sub>Cl, presents a very unusual tautomeric equilibrium between the metal−metal-bonded and the mixed-valence complexes [(CNBu<sup>t</sup>)<sub>2</sub>(Cl)Ir(μ-Pz)<sub>2</sub>Ir(CH<sub>2</sub>Ph)(CNBu<sup>t</sup>)<sub>2</sub>] and [(CNBu<sup>t</sup>)<sub>2</sub>Ir(μ-Pz)<sub>2</sub>Ir(Cl)(CH<sub>2</sub>Ph)(CNBu<sup>t</sup>)<sub>2</sub>], respectively. This equilibrium allows the unprecedented oxidative-addition reaction of chloroalkanes such as PhCH<sub>2</sub>Cl and MeCO<sub>2</sub>CH<sub>2</sub>Cl to the diiridium(II) complex <b>2</b>, resulting in the diiridium(III) complex [{Ir(μ-Pz)(CH<sub>2</sub>Ph)(CNBu<sup>t</sup>)<sub>2</sub>}<sub>2</sub>(μ-Cl)]Cl and the mixed-dialkyl complex [(CNBu<sup>t</sup>)<sub>2</sub>(MeCO<sub>2</sub>CH<sub>2</sub>)Ir(μ-Pz)<sub>2</sub>(μ-Cl)Ir(CH<sub>2</sub>Ph)(CNBu<sup>t</sup>)<sub>2</sub>]Cl, respectively.