Marites A. Guino-o, A. Zureick, N. Blank
Sep 19, 2012
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0
Influential Citations
13
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Journal
Organometallics
Abstract
The complexes Pt((R,R)-Me-DuPhos)(Ph)(Cl) (1) and Pt((R,R)-i-Pr-DuPhos)(Ph)(Cl) (2) have been used as catalyst precursors in Pt-catalyzed asymmetric alkylation of secondary phosphines. To investigate structure–reactivity–selectivity relationships in these reactions, analogous complexes with different bis(phospholane) ligands and/or Pt-hydrocarbyl groups were prepared. Treatment of Pt(COD)(R)(Cl) (R = Me, Ph) with BPE or DuPhos ligands gave Pt((R,R)-Me-BPE)(Me)(Cl) (3), Pt((R,R)-Ph-BPE)(Me)(Cl) (5), Pt((R,R)-Ph-BPE)(Ph)(Cl) (6), and Pt((R,R)-i-Pr-DuPhos)(Me)(Cl) (7). However, treatment of Pt(COD)(Me)(Cl) with (R,R)-Me-FerroLANE gave a mixture of products, which were converted upon heating to Pt((R,R)-Me-FerroLANE)(Me)(Cl) (8). A related mixture formed from Pt(COD)(Ph)(Cl) precipitated trans-[Pt((R,R)-Me-FerroLANE)(Ph)(Cl)]n (9T), which on treatment with AgOTf followed by LiCl gave cis-Pt((R,R)-Me-FerroLANE)(Ph)(Cl) (9) as the major product. The reaction of Pt(COD)(Ph)(Cl) with (R,R)-Me-BPE gave the dinucle...