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X-ray spectroscopic and diffraction study of the structure of the active species in the Ni(II)-catalyzed polymerization of isocyanides. |
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| Authors: | 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 |
| Institution: | Institute for Molecules and Materials, University of Nijmegen, 1 Toernooiveld, 6525 ED Nijmegen, The Netherlands. |
| 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. |
| Keywords: | isocyanide nickel catalysis polymerization X‐ray absorption spectroscopy |