Abstract
[(Bn(2)Cyclam)Y(N(SiMe(3))(2))] was prepared by reaction of H(2)Bn(2)Cyclam with Y[N(SiMe(3))(2)](3). The protonation of the macrocycle ligand in [(Bn(2)Cyclam)Y(N(SiMe(3))(2))] is observed upon reaction with [HNMe(3)][BPh(4)] leading to the formation of [(HBn(2)Cyclam)Y(N(SiMe(3))(2))][BPh(4)]. DFT analysis of [(Bn(2)Cyclam)Y(N(SiMe(3))(2))] showed that the HOMO is located on the anionic nitrogen atoms of the cyclam ring indicating that protonation follows orbital control. Addition of H(2)Bn(2)Cyclam and H(2)((3,5-tBu2)Bn)(2)Cyclam to a 1:3 mixture of YCl(3) and LiCH(2)SiMe(3) in THF resulted in the formation of [((C(6)H(4)CH(2))BnCyclam)Y(THF)(µ-Cl)Li(THF)(2)] and [Y{(η(3)-(3,5-tBu2)Bn)(2)Cyclam}Li(THF)], respectively. The reaction of H(2)(3,5-tBu2)Bn(2)Cyclam with Y(CH(2)SiMe(3))(3)(THF)(2) was studied and monitored by a temperature variation NMR experiment revealing the formation of [((3,5-tBu2)Bn(2)Cyclam)Y(CH(2)SiMe(3))]. Preliminary catalytic assays have shown that [Y{(η(3)-(3,5-tBu2)Bn)(2)Cyclam}Li(THF)] is a very efficient catalyst for the intramolecular hydroamination of 2,2-diphenyl-pent-4-enylamine.