Abstract
The first molybdenum complexes of widely used NHC-based CNC and C^N^C pincer ligands are described, viz. [Mo(L)(CO)3] (L=2,6-bis(mesityl-imidazolylidene)pyridine≡CNC-Mes, 1; α,α′-(diimidazolylidene-dodecamethylene)lutidine≡C^N^C-12, 2). These complexes have been thoroughly characterised in solution and the solid-state, revealing different stereochemical preferences of the tridentate ligands. In the case of flexible C^N^C-12 an uncommon fac-coordination geometry is observed, whilst the complex of rigid CNC-Mes adopts the expected mer-configuration. For the combination of donors associated with the ligands, DFT calculations establish preferential fac-coordination, however, within the CNC (ΔΔG=+63.1kJ·mol−1) and C^N^C (ΔΔG=+20.0kJ·mol−1) scaffolds this conformation is significantly destabilised relative to the mer-alternative.
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