Ligand-substitution reactions of cationic .sigma.-vinylplatinum(II) triflate species. Single-crystal molecular structure of trans-(CH3)2C:CHPt(PPh3)2I

Abstract

A wide variety of nucleophiles readily react with the cationic (σ-R 2 C=CR')(Ph 3 P) 3 PtOTf complex, under mild conditions, resulting in ligand substitution. Neutral nucleophiles such as pyridine, CH 3 CN, and CO give the corresponding trans cationic complexes via net replacement of the trans-Ph 3 P ligand. Reactions with an excess of more basic phosphines such as Ph 2 MeP and triphos yield the respective cationic complexes with replacement of all three Ph 3 P ligands. Interaction with charged nucleophiles such as I − , Br − , Cl − and PhS − results in the neutral trans complexes (σ-R 2 C=CR)(Ph 3 P) 2 PtX