Carbonyl insertion reaction into the Pt?C bond in heterobimetallic Pt(SnCl3)(PH3)2(CO)(CH3) compound: Theoretical study

✍ Scribed by Rocha, Willian R.; De Almeida, Wagner B.

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 232 KB
• Volume: 21
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/(sici)1096-987x(200006)21:8<668::aid-jcc6>3.0.co;2-9

✦ Synopsis

Quantum-mechanical calculations were carried out at the MP4(SDQ)//MP2 level of theory to determine the energies and reaction mechanism for the carbonyl insertion reaction (second step in the olefin hydroformylation catalytic cycle), using a heterobimetallic Pt(SnCl 3 )(PH 3 ) 2 (CO)(CH 3 ) compound as a model catalytic species. The results show that this reaction proceeds through a three-center transition state, with an activation energy of 26.4 kcal/mol, followed by an intramolecular rearrangement to the square-planar cis-Pt(SnCl 3 )(PH 3 ) 2 (MeCO) metal-acyl product. Analysis of the nature of the bonds shows that there is a negligible participation of the tin d-orbitals in the formation of the Pt-Sn bond.