Bibliographic Details
| Title: |
Insight into the Mechanism of R−R Reductive Elimination from the Six-Coordinate d6Complexes L2Pt(R)4(R = vinyl, Me). |
| Authors: |
Alireza Ariafard1, Zeinab Ejehi1, Hoda Sadrara1, Tahmineh Mehrabi1, Shohreh Etaati1, Azadeh Moradzadeh1, Mahshid Moshtaghi1, Hadis Nosrati1, Nigel J. Brookes1, Brian F. Yates1 |
| Source: |
Organometallics. Feb2011, Vol. 30 Issue 3, p422-432. 11p. |
| Subject Terms: |
*BIOCHEMICAL mechanism of action, *CHEMICAL reduction, *COORDINATION compounds, *DENSITY functionals, *PLATINUM, *ELIMINATION reactions, *LIGANDS (Chemistry), *ELECTRON donor-acceptor complexes |
| Abstract: |
We have used density functional theory to investigate the reductive elimination from platinum(IV) structures of the form L2PtR4where L = PMe3, PH3, PF3, CO, NH3and R = vinyl, Me. We conclude that reductive elimination occurs via the L-predissociation pathway for R = Me, irrespective of ligand L. But when R = vinyl, direct elimination is the preferred pathway if the L ligand is PMe3; otherwise both pathways are competitive for R = vinyl. We also note that if L is more π-electron accepting and less σ-electron donating, the reductive elimination from the six-coordinate complexes L2PtR4will be more rapid. Reductive elimination from the five-coordinate complexes LPtR4proceeds more easily if the ligand trans to the two R groups being coupled is more σ-electron donating and the ligands cis to the two R groups are more π-electron accepting. [ABSTRACT FROM AUTHOR] |
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| Database: |
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