Solvent-controlled selective synthesis of a trans-configured benzimidazoline-2-ylidene palladium(II) complex and investigations of its Heck-type catalytic activity

Abstract

Reaction of N,N′-dimethylbenzimidazolyl iodide (A) with Pd(OAc) 2 in DMSO gives selectively trans-bis(N,N′- dimethylbenzimidazoline-2-ylidene) palladium(II) diiodide (trans-2) in 77% yield. The selective formation of the trans-coordination isomer and thus the cis-trans rearrangement is driven by the insolubility of trans-2 in DMSO. X-ray single-crystal diffraction analysis and 13C NMR spectroscopy confirm the trans-geometry of the square planar Pd(II) complex. Catalytic studies show that cis-1 and trans-2 are highly efficient in the Mizoroki-Heck coupling reaction of aryl bromides and activated aryl chlorides both in DMF and [N(n-C4H9)4]Br as ionic liquid. The catalytic activities of Pd(II) complexes with N-heterocyclic carbene ligands derived from benzimidazole are comparable to their imidazole-derived analogues. © 2005 Elsevier B.V. All rights reserved.