RELATIONSHIPS BETWEEN BASICITY, REDOX BEHAVIOR OF FERROCENYLAMINES AND THEIR REACTIVITY WITH PT[II] COMPOUNDS

pK(b) values for the ferrocenylamines, [(eta-C5H4(CH2)(x)NH2)FeCp] x = 1, 2, 3; [(eta-C5H4CH2NHR)FeCp] R = Me, 4, Ph, 5; {[eta-C5K4CHR'NR2]F eCp} R'/R = H/Me, 6, R'/R = H/Ph, 7, Me/Me, 8; [{eta-C5H4CHRNMe2)(2)Fe ] R = H 9, Me 10; [{1,2 eta-C5H3(CH2NMe2)(PPh2)}FeCp] 11, {1,2 eta-C5H 3[CH(Me)NMe2](PR2}}Fe[eta-C5H4(PPh2)(n)] n = 0, R = Pr-i 12, Ph 13, n = 1, R = Me 14, are correlated with inductive, neighbouring group and steric effects. Corresponding salts have been synthesised. The pK(b) h as a marked influence on their chemistry. Protonation competes with co mplexation but cis-PtCl2L2 L = 1-3, 5, 7, and cis-Pt(N-N)Cl-2 L = 8, 9 , have been characterised. Two reversible couples [Fc(+)A/FcA], [Fc(+) AH(+)/FcAH(+)] (A = amine function) and an irreversible oxidation/prot onation of A are linked by a EECE mechanism, but potentials for the fi rst two are independent of the amine and similar to ferrocene. Nucleop hilic attack by ferrocenylamines at the nitrile, protonation and ligan d substitution are all observed with cis-[PtCl2(NCR)(2)]. (C) 1998 Els evier Science S.A. All rights reserved.