| Abstract |
(Bn(2)Cyclam)ZrCl2 reacts with silver salts to form either neutral or cationic species depending on the nature of the counterion. The reaction of (Bn(2)Cyclam)ZrCl2 with AgCF3COO affords (Bn(2)Cyclam)Zr(OCOCF3)(2) while with AgPF6 the cationic species [(Bn(2)Cyclam)ZrCl(CH3CN)]PF6 is formed. Cations of formulas [(All(2)Cyclam)ZrX(L)](+) (X=Me, L=CD2Cl2; X, L=eta(2)-CH2Ph), [((Me)All(2)Cyclam)Zr(eta(2)-CH2Ph)](+) and [(Bn(2)Cyclam)Zr(Bu-n)(THF)](+) were prepared by abstraction of one alkyl ligand from (R(2)Cyclam)ZrX2 (R= All, (Me)All, Bn; X = Me, CH2Ph, Bu-n) using B(C6F5)(3) or [PhMe2NH][B(C6F5)(4)]. (Bn(2)Cyclam)Zr(C6F5)(2) was obtained by reaction of (Bn(2)Cyclam) ZrCl2 with 2 equiv. of MgBrC6F5. The complex (Bn(2)Cyclam)ZrCl\(2)(k(2)-N,N -Bn(2)Cyclam) displaying a cyclam bridging ligand was obtained either from the 1:1 reaction of (Bn(2)Cyclam)ZrCl2 with LiNiPr2 and from the reaction of 2 equiv. of (Bn(2)Cyclam)ZrCl2 with Li-2(Bn(2)Cyclam)center dot(THF)(2) in THF. The reaction of LiCpC(Me)(2)CpLi with (Bn(2)Cyclam)ZrCl2 led to the formation of the mixed cyclam/cyclopentadienyl complex [(ansa-eta(5):eta(5)-Cp2CMe2)ZrCl(HBn(2)Cyclam)]. |
