INOR 437 |
| Evidence suggests that the Pt(II)-catalyzed hydroamination of (1-allyl-cyclohexylmethyl)benzylamine with [PtCl2(PPh3)]2 proceeds through initial coordination of the amine to the Pt(II) center, followed by intramolecular ligand exchange and attack of the pendant amine on the newly formed Pt-olefin complex I leading to the zwitterionic intermediate II. Rapid loss of HCl forms the neutral bicycle III, which is the catalyst resting state. Protonolysis occurs presumably through a Pt(IV) hydride complex (IV), but not before the stereocenter of III isomerizes. The process is found to be second order in Pt, first order in secondary olefinic amine, and inverse first order in Cl-. This suggests that loss of Cl- from IV mediated by a second equivalent of Pt is rate limiting.
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Organometallic: Catalysis
9:00 AM-12:00 PM, Monday, 11 September 2006 Moscone Center -- Room 310, Oral
Division of Inorganic Chemistry |
