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Synthesis of Heterobimetallic Complexes by Coordination of Rhodium(III) and Iridium(III) Poly-N,O-NHC Complexes to Silver(I), Copper(II), and Zinc(II)

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journal contribution
posted on 18.05.2018, 18:22 by Michael Tegethoff, Florian Roelfes, Christian Schulte to Brinke, Tristan Tsai Yuan Tan, Florian Kampert, Guo-Xin Jin, F. Ekkehardt Hahn
The reaction of [RhCl2(Cp*)]2 with 2-trimethylsiloxyphenyl isocyanide (1) led to the mononuclear diisocyanide complex [RhCl­(Cp*)­(1)2]. Cleavage of the Si–O bonds of the coordinated isocyanide ligands with a catalytic amount of KF and H2O gave the neutral rhodium­(III) complex [RhCl­(Cp*)­(NH,O-NHC)­(N,O-NHC)] ([2]) bearing a C2-metalated N,O-benzoxazolinato ligand and an NH,O-benzoxazolin-2-ylidene ligand. In the presence of AgBF4 the same reaction sequence with [MCl2(Cp*)]2 (M = Rh, Ir) and 1 led to the removal of all halogeno ligands and formation of the complexes [M­(Cp*)­(NH,O-NHC)­(N,O-NHC)2] (M = Rh, [3]; M = Ir, [4]) bearing one C-metalated NH,O-NHC benzoxazolin-2-ylidene and two C-metalated N,O-benzoxazolinato ligands. Deprotonation of the remaining N–H function in complexes [3] and [4] generated complexes with three amido donor functions which act as tripodal metalloligands for the coordination to additional transition metals such as AgI, CuII, and ZnII, thus allowing the preparation of the polynuclear heterobimetallic complexes [5]–[10] bearing C/N-metalated benzoxazolinato ligands.