Formation and structures of Pd(II) N,S-heterocyclic carbene-pyridyl mixed-ligand complexes

Mononuclear mixed-ligand complexes of Pd(II) containing a N,S-heterocyclic carbene (NSHC) with a secondary alkyl N-substituent and pyridyl ligand, with the general formula [PdI2(C10H11NS)L] (C10H11NS = 3-isopropylbenzothiazolin-2-ylidene; L = pyridine, 2-aminopyridine, 3-iodopyridine and 4-tert-butyl-pyridine) have been synthesized and characterized by X-ray single-crystal crystallography. Both solution and solid-state structures, as evident from their 1H NMR spectra and X-ray structures, show anagostic γ-hydrogen interactions of metal with methine of the substituent on the carbene or pyridyl ligand giving 5-membered-chelate-like structures.

Graphical abstractIntroduction of an isopropyl substituent on nitrogen in the benzothiazolium ring or an amine at the α-position to the pyridyl provides a motif for double γ-hydrogen interactions with the metal. This results in pseudo-5-membered-ring chelate and a source of stabilization for d8 carbene structures.Figure optionsDownload full-size imageDownload as PowerPoint slide