title: Homo- and Heterodinuclear Ir and Rh Imine-functionalized Protic NHC Complexes: Synthetic, Structural Studies, and Tautomerization/Metallotropism Insights.
abstract: The influence of the potentially chelating imino group of imine-functionalized Ir and Rh imidazole complexes on the formation of functionalized protic N-heterocyclic carbene (pNHC) complexes by tautomerization/metallotropism sequences was investigated. Chloride abstraction in [Ir(cod)Cl{C3 H3N2 (DippN=CMe)-κN3}] (1 a) (cod=1,5-cyclooctadiene, Dipp=2,6-diisopropylphenyl) with TlPF6 gave [Ir(cod){C3 H3N2 (DippN=CMe)-κ(2) (C2,Nimine )}](+) [PF6 ](-) (3 a(+) [PF6 ](-)). Plausible mechanisms for the tautomerization of complex 1 a to 3 a(+) [PF6 ](-) involving C2-H bond activation either in 1 a or in [Ir(cod){C3 H3 N2 (DippN=CMe)-κN3}2](+) [PF6 ](-) (6 a(+) [PF6 ](-)) were postulated. Addition of PR3 to complex 3 a(+) [PF6 ](-) afforded the eighteen-valence-electron complexes [Ir(cod)(PR3){C3 H3N2 (DippN=CMe)-κ(2) (C2,Nimine )}](+) [PF6 ](-) (7 a(+) [PF6 ](-) (R=Ph) and 7 b(+) [PF6 ](-) (R=Me)). In contrast to Ir, chloride abstraction from [Rh(cod)Cl{C3H3N2 (DippN=CMe)-κN3}] (1 b) at room temperature afforded [Rh(cod){C3 H3N2 (DippN=CMe)-κN3}2](+) [PF6 ](-) (6 b(+) [PF6 ](-)) and [Rh(cod){C3 H3N2 (DippN=CMe)-κ(2) (C2,Nimine )}](+) [PF6 ](-) (3 b(+) [PF6 ](-) ) (minor); the reaction yielded exclusively the latter product in toluene at 110 °C. Double metallation of the azole ring (at both the C2 and the N3 atom) was also achieved: [Ir2 (cod)2 Cl{μ-C3H2N2 (DippN=CMe)-κ(2) (C2,Nimine ),κN3}] (10) and the heterodinuclear complex [IrRh(cod)2 Cl{μ-C3H2N2 (DippN=CMe)-κ(2) (C2,Nimine ),κN3}] (12) were fully characterized. The structures of complexes 1 b, 3 b(+) [PF6 ](-) , 6 a(+) [PF6 ](-) , 7 a(+) [PF6 ](-), [Ir(cod){C3HN2 (DippN=CMe)(DippN=CH)(Me)-κ(2) (N3,Nimine )}](+) [PF6 ](-) (9(+) [PF6 ](-)), 10⋅ Et2 O⋅toluene, [Ir2 (CO)4 Cl{μ-C3H2N2 (DippN=CMe)-κ(2) (C2,Nimine ),κN3}] (11), and 12⋅2 THF were determined by X-ray diffraction.
authors.affiliation: Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081, Strasbourg Cedex, France.
authors.forename: Fan
authors.initials: F
authors.lastname: He
authors.affiliation: Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081, Strasbourg Cedex, France.
authors.forename: Marcel
authors.initials: M
authors.lastname: Wesolek
authors.affiliation: Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081, Strasbourg Cedex, France. danopoulos@unistra.fr.|Université de Strasbourg Institute for Advanced Study (USIAS), 4 rue Blaise Pascal, 67081, Strasbourg Cedex, France. danopoulos@unistra.fr.
authors.forename: Andreas A
authors.initials: AA
authors.lastname: Danopoulos
authors.affiliation: Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081, Strasbourg Cedex, France. braunstein@unistra.fr.
authors.forename: Pierre
authors.initials: P
authors.lastname: Braunstein
keywords: C−H activation; N-heterocyclic carbenes; imidazoles; iridium; rhodium