For comparison to Pt((R,R)-Me-DuPhos)(Ph)(Cl) and Pt((R,R)-i-Pr-DuPhos)(Ph)(Cl), catalyst precursors in Pt-catalyzed asymmetric alkylation of secondary phosphines, the complexes Pt((R,R)-Me-BPE)(Me)(Cl) (1), Pt((R,R)-Ph-BPE)(Ph)(Cl) (2), Pt((R,R)-Ph-BPE)(Me)(Cl) (3), Pt((R,R)-i-Pr-DuPhos)(Me)(Cl) (4), Pt((R,R)-Me-FerroLANE)(Me)(Cl) (5) and Pt((R,R)-Me-FerroLANE)(Ph)(Cl) (6) were prepared by treatment of Pt(COD)(R)(X) (R = Me, Ph) with chiral bis(phospholane) ligands. Complexes 1, 2, 4, and 5 were structurally characterized by X-ray crystallography. However, the analogous reaction of Pt(COD)(Ph)(Cl) with (R,R)-Me-BPE gave the dinuclear dication [(Pt((R,R)-Me-BPE)(Ph))2(�-(R,R)-Me-BPE))][Cl]2 (7), and treatment of Pt(COD)(Ph)(I) with (R,R)-Me-BPE gave Pt((R,R)-Me-BPE)(Ph)(I) (8), but not cleanly.  Investigation of alternative routes to Pt((R,R)-Me-BPE)(Ph)(Cl) via precursors like structurally characterized Pt((R,R)-Me-BPE)Cl2 (9) and Pt((R,R)-Me-BPE)I2 (10) will be described. Treatment of Pt((R,R)-Me-DuPhos)Cl2 with excess 9-phenanthryl magnesium bromide gave Pt((R,R)-Me-DuPhos)(9-phenanthryl)(Br) (11).  Structure-reactivity-selectivity relationships in this series of Pt catalyst precursors were investigated in catalytic phosphine alkylations.

New chiral platinum bis(phospholane) complexes: Synthesis, characterization, and structure-reactivity-selectivity relationships in catalysis

244th National Meeting (2012)

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