CHIRAL BISPHOSPHANES - 6 - CHELATE COMPLEXES OF PLATINUM(II) WITH RACEMIC AND OPTICALLY PURE TRANS-CYCLOPENTANE-1,2-DIYL-BIS(PHOSPHONOUS ACID DIESTER) LIGANDS AND TRANS-CYCLOPENTANE-1,2-DIYL-BIS(PHOSPHONOUS ACID DIAMIDE) LIGANDS - SYNTHESIS, STRUCTURES AND C-H ACTIVATION REACTIONS

New bidentate ligands of the type C5H8(PX2)(2) [PX2 = P(OMe)(2) (2), P (OPh)(2) (3), P[OCH(Me)Et-(S)](2) (4), P[OC6H9(Me)Pr-i-(1R)](2) (5), P [OCH(CO2Pri)-(R)-](2) (6), P[N(CH2)(5)-cyclo](2) (7), P[N(CH2)(4)O-cyc lo](2) (8)] were prepared from rac-C5H8(PCl2)(2) (1) and the correspon ding alcohols, diols, and secondary amines. These reacted with [(1,5-C 8H12)Pt(CH2CMe3)(2)] to give Pt(II) derivatives, [C5H8{P(OR)(2)}(2)Pt( CH2CMe3)(2)] [P(OR)(2) = P(OMe)(2) (9), P(OPh)(2) (10), P[OCH(Me)Et-(S )](2) (11), P[OC6H9(Me)Pr-i-(1R)](2) (12), P[OCH(CO2Pri-(R)-](2) (13)] and [C5H8{P(NR2)(2)}(2)Pt(CH2CMe3)(2) [P(NR2)(2) = P[N(CH2)(5)-cyclo] (2) (14), P[N(CH2)(4)O-cyclo](2) (15)], respectively. Controlled acido lysis of 9, 10, 12, and 13 yielded the chloro neopentyls [C5H8{P(OR)(2 )}(2)Pt(Cl)CH2CMe3] [(P(OR)(2) = P(OMe)(2) (16), P(OPh)(2) (17), P[OC6 H9(Me)Pr-i-(1R)](2) (18), P[OCH(CO2Pri)-(R)-](2) (19)]. Their P-N-bond ed analogues [C5H8{P(NR2)(2)}(2)Pt(Cl)CH2CMe3] [P(NR2)(2) = P[N(CH2)(5 )-cyclo](2) (20), P[N(CH2)(4)O-cyclo], (21)] were obtained by substitu ting the diene ligand of [(1,5-C8H12)Pt(Cl)CH2CMe3] for bidentates 7 a nd 8. Treatment of 20 and 21 with Na[BH(OMe)(3)] in THF provided neope ntyl hydrides, [C5H8{P(NR2)(2)}(2)Pt(H)CH2CMe3] [P(NR2)(2) = P[N(CH2)( 4)-cyclo](2) (23), P[N(CH2)(4)O-cyclo](2) (24)], which exhibited simil ar inertness toward reductive elimination at temperatures below 60 deg rees C as did the previously investigated P-C-substituted derivative [ C5H8{P(C6H11-cyclo)(2)}(2)Pt(H)CH2CMe3]. The crystal structures of [(1 S, 2S)-C5H8 {P[OC6H9(Me)Pri-(1R)](2)}(2)Pt(CH2CMe3)(2)], (1S,2S)-12, [ C5H8{P[N(CH2)(4)O-cyclo](2)}(2)Pt(CH2CMe3)(2)], 15, [(1S,2S)-C5H8{P[OC 6H9(Me)Pr-i- (1R)](2)}(2)Pt(Cl)CH2CMe3], (1S,2S)-18, and also of [C5H8 {P(OPh)(2)}PtCl2], 22, were determined by X-ray diffraction.