Metal-Induced Enhancement of Tetrel Bonding. The Case of C⋅⋅⋅X-Ir (X=Cl, Br) Tetrel Bond Involving a Methyl Group.

In X-ray structures of the isomorphic mer-[IrX(THT)(CNXyl)] (X=Cl 1, Br 2; THT=tetrahydrothiophene; Xyl=2,6-MeCH-) complexes, we revealed short intermolecular contacts between the C-atom of an isocyanide methyl group and halide ligands of another molecule. Geometrical consideration of the X-ray data and analysis of appropriate DFT studies allowed the attribution of these contacts to C⋅⋅⋅X-Ir (X=Cl, Br) tetrel bond. Specifically, through the application of DFT calculations and various theoretical models, the presence of tetrel bonding interactions was validated, and the contribution of the C⋅⋅⋅X-Ir interaction was assessed.