Homo- and Heterodinuclear Ir and Rh Imine-functionalized Protic NHC Complexes: Synthetic, Structural Studies, and Tautomerization/Metallotropism Insights

Chemistry : a European Journal
Fan HePierre Braunstein

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 H3 N2 (DippNCMe)-κN3}] (1 a) (cod=1,5-cyclooctadiene, Dipp=2,6-diisopropylphenyl) with TlPF6 gave [Ir(cod){C3 H3 N2 (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 H3 N2 (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{C3 H3 N2 (DippNCMe)-κN3}] (1 b) at room temperature afforded [Rh(cod){C3 H3 N2 (DippNCMe)-κN3}2 ](+) [PF6 ](-) (6 b(+) [PF6 ](-) ) and [Rh(cod){C3 H3 N2 (DippNCMe)-κ(2) (C2,Nimine )}](+) [PF6 ](-) (3 b(+) [PF6 ](-) ) (minor); the reaction yielded exclusively the latter product ...Continue Reading

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Citations

Mar 18, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·D BrackemeyerF E Hahn
Aug 8, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiaoyu RenPierre Braunstein
Jun 26, 2018·Chemical Reviews·Shigeki Kuwata, F Ekkehardt Hahn

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