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A theoretical study on CO 2 insertion into an M(bond)H bond (M = Rh and Cu)
Author(s) -
Sakaki Shigeyoshi,
Musashi Yasuo
Publication year - 1996
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1996)57:3<481::aid-qua22>3.0.co;2-5
Subject(s) - chemistry , bond energy , bond length , sextuple bond , single bond , hydride , bond order , quadruple bond , insertion reaction , bent bond , crystallography , bond strength , molecular geometry , triple bond , computational chemistry , double bond , metal , molecule , catalysis , crystal structure , polymer chemistry , organic chemistry , alkyl , adhesive , layer (electronics)
Insertion of CO 2 into the transition metal‐hydride bond of [Rh III H 2 (PH 3 ) 3 ] + , Cu I H(PH 3 ) 2 , and Rh I H(PH 3 ) 3 was theoretically investigated with ab initio MO/MP 4, SD‐CI , and CCD methods. The geometries of reactants, transition states ( TS ), and products were optimized at the Hartree‐Fock level, and then MP 4, SD‐CI , and CCD calculations were performed on those optimized structures. The TS of the CO 2 insertion into the Cu I (bond)H bond is the most reactantlike, while the TS of the CO 2 insertion into the Rh III (bond)H bond is the most productlike. The activation energy ( E a ) and the reaction energy (Δ E ) were calculated to be 6.5 and −33.5 kcal/mol for the CO 2 insertion into the Cu 1 (bond)H bond, 21.2 and −7.0 kcal/mol for the CO 2 insertion into the Rh 1 (bond)H bond, and 51.3 and −1.1 kcal/mol for the Rh 111 (bond)H bond at the SD‐CI level, where negative Δ E represents exothermicity. These results are discussed in terms of the M(bond)H bond energy and the trans ‐influence of the hydride ligand. © 1996 John Wiley & Sons, Inc.