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Dynamic 15 N NMR studies of iron phosphine complexes containing coordinated dinitrogen
Author(s) -
Field Leslie D.,
Hazari Nilay,
Li Hsiu Lin,
Luck Ian J.
Publication year - 2003
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.1247
Subject(s) - chemistry , phosphine , intramolecular force , metal , nmr spectra database , dissociation (chemistry) , ligand (biochemistry) , crystallography , nuclear magnetic resonance spectroscopy , magnetization transfer , nitrogen , stereochemistry , spectral line , catalysis , organic chemistry , medicine , biochemistry , physics , receptor , astronomy , magnetic resonance imaging , radiology
The 15 N‐labelled iron dinitrogen complexes trans ‐[FeH(N 2 )(PP) 2 ] + [BPh 4 ] − (PP = dppe, depe, dmpe) and cis ‐[FeH(N 2 )(PP 3 )] + [BPh 4 ] − were prepared in situ by exchange of unlabelled coordinated dinitrogen with 15 N 2 . 15 N NMR chemical shifts and coupling constants are reported. The 15 N spectra exhibit separate signals for the metal‐bound and terminal nitrogen atoms of the coordinated N 2 . The 15 N resonances display 15 N, 15 N coupling as well as 31 P, 15 N coupling and long‐range 15 N, 1 H coupling when there is a metal‐bound hydrido ligand. Exchange between free and coordinated dinitrogen was monitored by magnetization transfer between 15 N‐labelled sites using an inversion–transfer–recovery experiment. Exchange between the metal‐bound and terminal nitrogen atoms of coordinated N 2 was also monitored by magnetization transfer and this could proceed by N 2 dissociation or by an intramolecular process. Copyright © 2003 John Wiley & Sons, Ltd.