X-ray spectroscopic and diffraction study of the structure of the active species in the Ni(II)-catalyzed polymerization of isocyanides

Gerald A Metselaar; Erik Schwartz; René de Gelder; Martin C Feiters; Serge Nikitenko; Grigory Smolentsev; Galina E Yalovega; Alexander V Soldatov; Jeroen J L M Cornelissen; Alan E Rowan; Roeland J M Nolte

doi:10.1002/cphc.200700251

X-ray spectroscopic and diffraction study of the structure of the active species in the Ni(II)-catalyzed polymerization of isocyanides

Chemphyschem. 2007 Aug 24;8(12):1850-6. doi: 10.1002/cphc.200700251.

Authors

Gerald A Metselaar¹, Erik Schwartz, René de Gelder, Martin C Feiters, Serge Nikitenko, Grigory Smolentsev, Galina E Yalovega, Alexander V Soldatov, Jeroen J L M Cornelissen, Alan E Rowan, Roeland J M Nolte

Affiliation

¹ Institute for Molecules and Materials, University of Nijmegen, 1 Toernooiveld, 6525 ED Nijmegen, The Netherlands.

PMID: 17647252
DOI: 10.1002/cphc.200700251

Abstract

The structure of the active complex in the Ni-catalyzed polymerization of isocyanides to give polyisocyanides is investigated. It is shown by X-ray absorption spectroscopy (XAS), including EXAFS (extended X-ray absorption fine structure) and XANES (X-ray absorption near edge structure), and single-crystal X-ray diffraction, to contain a carbene-like ligand. This is the first structural characterization of a crucial intermediate in the so-called merry-go-round mechanism for Ni-catalyzed isocyanide polymerization.