Structural Diversity of Cadmium Complexes with N‐Heterocyclic Carbene‐Isothiocyanate Zwitterionic Ligand

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Abstract
In this study, we discuss the synthesis and structural characterization of three N‐heterocyclic carbene isothiocyanate zwitterionic ligands, 1,3‐bis(2,6‐diisopropylphenyl)‐2‐N‐phenyl‐thiocarbamoyl imidazolium (ImDipp‐CSNPh, L1), 1,3‐bis(tert‐butyl)‐2‐N‐phenylthiocarbamoyl imidazolium (ImtBu‐CSNPh, L2) and 1,3‐bis(2,4,6‐trimethylphenyl)‐2‐N‐phenylthiocarbamoyl imidazolium (ImMes‐CSNPh, L3) and their cadmium complexes, [(ImDipp‐CSNPh)2CdCl][CdCl3] (1) and [(ImtBu‐CSNPh)Cd(μ‐Cl)Cl]2 (2). Both bench‐stable cadmium complexes were synthesized by directly reacting the corresponding NHC‐CSNPh adducts with anhydrous cadmium chloride. The solid‐state structures of zwitterionic NHC‐isothiocyanate betaine adducts (L1‐L3) and cadmium complexes (1 and 2) were investigated with the assistance of single crystal X‐ray diffraction analysis. A steric modification of N‐substituent on NHC governs a unique structural change from betaine ImDipp‐CSNPh coordinated cationic cadmium complex to neutral dimeric cadmium complex with ImtBu‐CSNPh.

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