The Quest for Ring Opening of Oxaphosphirane Complexes: A Coupled-Cluster and Density Functional Study of CH3PO Isomers and Their Cr(CO)5 Complexes
✍ Scribed by Oliver Krahe; Frank Neese; Rainer Streubel
- Publisher
- John Wiley and Sons
- Year
- 2009
- Tongue
- English
- Weight
- 671 KB
- Volume
- 15
- Category
- Article
- ISSN
- 0947-6539
No coin nor oath required. For personal study only.
✦ Synopsis
Abstract
Opening gambit: A high‐level theoretical study on the relative stabilities of oxaphosphirane isomers and their Cr(CO)~5~ complexes is reported (see picture). Furthermore, thermodynamics and kinetics of possible ring‐opening reactions of these complexes in the presence of a {Cp~2~Ti^III^Cl} fragment are theoretically investigated. The CO bond cleavage is predicted to be the most efficient pathway, thus leading to reactive intermediates that are attractive for synthetic applications.magnified image
A high‐level theoretical study on the relative stabilities of oxaphosphirane isomers and their Cr(CO)~5~ complexes is reported. Furthermore, thermodynamics and kinetics of possible ring‐opening reactions of these complexes in the presence of a {Cp~2~Ti^III^Cl} fragment are theoretically investigated. The CO bond cleavage is predicted to be the most efficient pathway thus leading to reactive intermediates that are attractive for synthetic applications. The ring‐opening reaction is predicted to not lead to the most favorable product (a coordinated phosphinidene oxide species). Rather, the ring‐opening product is separated by a substantial barrier of about 24 kcal mol^−1^ from the thermodynamically most favorable species.