Abstract
We have used density functional theory to investigate the reductive elimination from platinum(IV) structures of the form L2PtR 4 where L = PMe3, PH3, PF3, CO, NH3 and 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 L 2PtR4 will be more rapid. Reductive elimination from the five-coordinate complexes LPtR4 proceeds 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.
Original language | English |
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Pages (from-to) | 422-432 |
Number of pages | 11 |
Journal | Organometallics |
Volume | 30 |
Issue number | 3 |
DOIs | |
Publication status | Published - 14 Feb 2011 |
Externally published | Yes |