10.1021/acs.organomet.6b00570.s001
Leanna
K. Robbins
Leanna
K.
Robbins
Cassandra P. Lilly
Cassandra P.
Lilly
Roger D. Sommer
Roger D.
Sommer
Elon A. Ison
Elon A.
Ison
Effect of the Ancillary Ligand on the Mechanism for
CO Migratory Insertion in High-Valent Oxorhenium Complexes
American Chemical Society
2016
calculation
Mechanism
CO Migratory Insertion
psi
CO adducts
Carbonylation reactions
High-Valent Oxorhenium Complexes
carbonylation
mechanism
reactivity
derivative
acyl
DFT
formation
carbon monoxide
Ancillary Ligand
oxorhenium complexes
carbonyl ligand
alkyl
SSS pincer ligand
migration
2016-10-10 04:32:45
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Effect_of_the_Ancillary_Ligand_on_the_Mechanism_for_CO_Migratory_Insertion_in_High-Valent_Oxorhenium_Complexes/4003515
Several oxorhenium
complexes bearing an SSS pincer ligand were
isolated and characterized, and their reactivity with carbon monoxide
was explored. The corresponding oxorheniumÂ(V) acyl derivatives were
also isolated and characterized. Carbonylation reactions required
high pressures (400 psi) and temperatures (50 °C). The mechanism
for carbonylation was explored with DFT (M06) calculations and revealed
that the most likely mechanism for carbonylation involved stepwise
formation of CO adducts followed by migration of the carbonyl ligand
to the alkyl/aryl groups.