TY - JOUR
T1 - Mechanistic studies of ligand fluxionality in [M(η-Cp)(ηC-Cp)(L) 2]n
AU - Ariafard, Alireza
AU - Tabatabaie, Elham S.
AU - Yates, Brian F.
PY - 2009/3/26
Y1 - 2009/3/26
N2 - Density functional theory has been used to provide a thorough investigation of the mechanistic factors affecting Cp ligand fluxionality in a series of organometallic complexes, [M(η5-Cp)(η1-Cp)(L) 2]n, involving different metals, different oxidation states, and different ligands. Excellent agreement with experiment for the barrier heights for the 1,5-shift were obtained for the complexes [Fe(η5-Cp*)(η1-Cp)(CO)2] and [Fe(η5-Cp)(η1-Cp)- (CO)2]. For the range of complexes studied, the barriers have been successfully rationalized in terms of hyperconjugation, metal-Cp bond strength, and steric effects. In addition, the η1-η5 interconversion of the Cp binding mode is shown to be a high-energy process, consistent with experimental observations. The L substitution reactions by η1-Cp are quite sensitive to the nature of the metal center and ancillary ligand. A detailed theoretical explanation of the factors involved in all of these transformations is provided.
AB - Density functional theory has been used to provide a thorough investigation of the mechanistic factors affecting Cp ligand fluxionality in a series of organometallic complexes, [M(η5-Cp)(η1-Cp)(L) 2]n, involving different metals, different oxidation states, and different ligands. Excellent agreement with experiment for the barrier heights for the 1,5-shift were obtained for the complexes [Fe(η5-Cp*)(η1-Cp)(CO)2] and [Fe(η5-Cp)(η1-Cp)- (CO)2]. For the range of complexes studied, the barriers have been successfully rationalized in terms of hyperconjugation, metal-Cp bond strength, and steric effects. In addition, the η1-η5 interconversion of the Cp binding mode is shown to be a high-energy process, consistent with experimental observations. The L substitution reactions by η1-Cp are quite sensitive to the nature of the metal center and ancillary ligand. A detailed theoretical explanation of the factors involved in all of these transformations is provided.
UR - http://www.scopus.com/inward/record.url?scp=63849144235&partnerID=8YFLogxK
U2 - 10.1021/jp810032a
DO - 10.1021/jp810032a
M3 - Article
AN - SCOPUS:63849144235
SN - 1089-5639
VL - 113
SP - 2982
EP - 2989
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 12
ER -