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The Quest for Ring Opening of Oxaphosphirane Complexes: A Coupled‐Cluster and Density Functional Study of CH 3 PO Isomers and Their Cr(CO) 5 Complexes
Author(s) -
Krahe Oliver,
Neese Frank,
Streubel Rainer
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200801494
Subject(s) - chemistry , kinetics , ring (chemistry) , phosphinidene , cluster (spacecraft) , steric effects , cleavage (geology) , bond cleavage , coupled cluster , density functional theory , stereochemistry , crystallography , computational chemistry , molecule , catalysis , organic chemistry , materials science , physics , quantum mechanics , fracture (geology) , computer science , programming language , composite material
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.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.