214355-14-3Relevant academic research and scientific papers
Chirale Bisphosphane VI. Chelatkomplexe von Platin(II) mit racemischen und optisch reinen trans-Cyclopentan-1,2-diyl-bis(phosphonigsaeurediester)- und trans-Cyclopentan-1,2-diyl-bis(phosphonigsaeurediamid)-Liganden: Synthesen, Strukturen und C-H-Aktivierungsreaktionen1
Dahlenburg, Lutz,Becker, Corinna,Hoeck, Juergen,Mertel, Stefan
, p. 155 - 166 (2008/10/08)
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)Pri-(1R)]2 (5), P[OCH(CO2Pri)-(R)-]2 (6), P[N(CH2)5-cyclo]2 (7), P[N(CH2)4O-cyclo]2 (8)] were prepared from rac-C5H8(PCl2)2 (1) and the corresponding alcohols, diols, and secondary amines. These reacted with [(1,5-C8H12)Pt(CH2CMe3)2] to give Pt(II) derivatives, [C5H8{P(OR)2}2Pt(CH2CMe3)2] [P(OR)2=P(OMe)2 (9), P(OPh)2 (10), P[OCH(Me)Et-(S)]2 (11), P[OC6H9(Me)Pri-(1R)]2 (12), P[OCH(CO2Pri)-(R)-]2 (13)] and [C5H8{P(NR2)2}2Pt(CH 2CMe3)2] [P(NR2)2=P[N(CH2)5-cyclo]2 (14), P[N(CH2)4O-cyclo]2 (15)], respectively. Controlled acidolysis of 9, 10, 12, and 13 yielded the chloro neopentyls [C5H8{P(OR)2}2Pt(Cl)CH2CM e3] [(P(OR)2=P(OMe)2 (16), P(OPh)2 (17), P[OC6H9(Me)Pri-(1R)]2 (18), P[OCH(CO2Pri)-(R)-]2 (19)]. Their P-N-bonded analogues [C5H8{P(NR2)2}2Pt(Cl)CH2CMe3] [P(NR2)2=P[N(CH2)5-cyclo]2 (20), P[N(CH2)4O-cyclo]2 (21)] were obtained by substituting the diene ligand of [(1,5-C8H12)Pt(Cl)CH2CMe3] for bidentates 7 and 8. Treatment of 20 and 21 with Na[BH(OMe)3] in THF provided neopentyl hydrides, [C5H8{P(NR2)2}2Pt(H)CH2CMe3] [P(NR2)2=P[N(CH2)5-cyclo]2 (23), P[N(CH2)4O-cyclo]2 (24)], which exhibited similar inertness toward reductive elimination at temperatures below 60°C as did the previously investigated P-C-substituted derivative [C5H8{P(C6H11-cyclo)2}2Pt(H)CH2CMe3]. The crystal structures of [(1S,2S)-C5H8{P[OC6H9(Me)Pri-(1R)]2}2Pt(CH2CMe3)2] , (1S,2S)-12, [C5H8{P[N(CH2)4O-cyclo]2} 2Pt(CH2CMe3)2], 15, [(1S,2S)-C5H8{P[OC6H9(Me)Pri-(1R)]2}2Pt(Cl)CH2CMe3], (1S,2S)-18, and also of [C5H8{P(OPh)2}PtCl2], 22, were determined by X-ray diffraction.
