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 oxorhenium­(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.