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Deuterium isotope effects and bonding in carbonylvanadium complexes
Author(s) -
Rehder Dieter,
Hoch Martin,
Jameson Cynthia J.
Publication year - 1990
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.1260280209
Subject(s) - chemistry , kinetic isotope effect , deuterium , isotope , cyclopentadienyl complex , computational chemistry , organic chemistry , catalysis , atomic physics , nuclear physics , physics
Abstract The effects of one‐bond and two‐bond 2 H, 13 CO and C 18 O isotope shifts on 51 V shielding in various carbonyl–Cp–vanadium complexes (Cp = n 5 ‐cyclopentadienyl) are reported and discussed with respect to the sensitivity of 51 V shifts to bond extensions, and the rovibrationally averaged values of such bond extensions. These isotope effects provide some insight into the bonding situation in these complexes. It is shown that the rate‐determining step in the reaction between V(CO) 6 and C 5 H 5 D, which leads to CpV(CO) 4 , is not subject to a kinetic isotope effect. The deuterium solvent isotope effects on 51 V shielding in [V(CO) 6 ]‐ and [VO 4 ] 3‐ are also investigated.