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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
Author(s) -
Metselaar Gerald A.,
Schwartz Erik,
de Gelder René,
Feiters Martin C.,
Nikitenko Serge,
Smolentsev Grigory,
Yalovega Galina E.,
Soldatov Alexander V.,
Cornelissen Jeroen J. L. M.,
Rowan Alan E.,
Nolte Roeland J. M.
Publication year - 2007
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200700251
Subject(s) - xanes , extended x ray absorption fine structure , x ray absorption spectroscopy , polymerization , x ray absorption fine structure , chemistry , crystallography , crystal structure , absorption spectroscopy , isocyanide , absorption (acoustics) , x ray crystallography , ligand (biochemistry) , spectroscopy , photochemistry , materials science , diffraction , stereochemistry , polymer , organic chemistry , optics , biochemistry , physics , receptor , quantum mechanics , composite material
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.