PHOSPHINE COMPLEXES OF PLATINUM(II) CYCLOPLATINATED FERROCENYLAMINES

Platinocycles sigma,eta(5)-C(5)H(3)CH(2)NMe(2))](eta(2)-P-P)}(+) X(-) (P-P = dppm, dppe, dppb, dppf; X = Cl, ClO4, CF3SO3), igma,eta(5)-C(5) H(3)CH(2)NMe(2))]Cl}(2)(mu(2)-P-P) (P-P = dppb, dppbz), and ta(2)-C5H5 )Fe(sigma,eta(5)-C(5)H(3)CH(2)NME(2))]Cl (P-P = dppb, dppbz), with pot ential cytotoxic properties, have been synthesized by reaction of the ligand with C5H5)Fe(sigma,eta(5)-C(5)H(3)CH(2)NMe(2))](dmso)Cl and cha racterized by analytical, conductance, and spectroscopic data. Geometr ical isomers of 5)-C5H5)Fe(sigma,eta(5)-C5H3-CH(2)NMe(2))][eta(2)- )PP h(2))Fe(eta(5)-C(5)H(3)PPh(2)(CH(2)NMe(2))]}(+) and C5H5)Fe(sigma,eta( 5)-C(5)H(3)CH(2)NMe(2))][eta(1)- 4)PPh(2))Fe(eta(5)-C(5)H(3)PPh(2)(CH( 2)NMe(2))]Cl} with a pendant PPh(2) and/or CH(2)NMe(2) group are also described. Enantiomeric, diplatinum analogues, meso- and (5)-C(5)H(3)C H(2)NMe(2))(2)Fe](eta(2)-P-P)(2)}(2-) X(2)(-) (P-P = dppm, dppe, dppf; X = Cl, CF3SO3) were similarly prepared from meso- or sigma,eta(5)-C( 5)H(3)CH(2)NMe(2))(2)](dmso)(2)Cl-2 (the latter stereoisomers were sep arated by a new procedure). X-ray structures of the triflate salts of ,eta(5)-C(5)H(3)CH(2)NMe(2))](eta(2)-dppm)(2)}(2+) (orthorhombic, P2(1 )2(1)2(1), a = 12.755(2)Angstrom, b = 16.011(3)Angstrom, c = 18.710-(3 )Angstrom, Z = 4) and 5)-C(5)H(3)CH(2)NMe(2))(2)Fe](eta(2)-dppm)(2)}(2 +) (monoclinic P2(l)/n, a = 12.335(1)Angstrom, b = 16.102(1)Angstrom, c = 18.856(1)Angstrom; beta = 98.82(7)degrees, Z = 2) delineate the Pt (II) coordination spheres and show that the dppm chelate ring is strai ned. Structural and spectroscopic data show that coordination of the c helate ligand does not increase intramolecular contacts. Trends in the P-31 and Pt-195 NMR parameters correlate with chelate ring size.