A NEW CYCLAM WITH A TRIPHENYLPHOSPHINE-PENDANT AND ITS METAL-COMPLEXES

A new triphenylphosphine-pendant cyclam (triphenylphosphine = TPP; cyc lam = 1,4,8,11-tetraazacyclotetradecane) was synthesized by reaction o f an ethyl cinnamate derivative bearing a diphenylphosphine group at t he ortho position of the phenyl group with 2,3,2-tetraamine (= 1,9-dia mino-3,7-diazanonane) in refluxing MeOH, followed by BH3 reduction. Tr iphenylphosphine oxide-pendant cyclam (triphenylphosphine oxide = TPPO ) was derived by treatment of TPP-pendant cyclam with benzyl alcohol i n CCl4. The TPP-pendant cyclam formed stable 1:1 metal inclusion compl exes with Ni-II and Mn-III. The TPPO-pendant cyclam yielded a 1:1 Ni-I I complex which was the best catalyst among the cyclam-Ni-II and -Mn-I II complexes for epoxidation of trans-stilbene with NaClO in CH2Cl2. G old(I) reacted with TPP-pendant cyclam to yield a stable 1:1 complex, in which Au-I binds only to the pendant phosphine. On the other hand, gold(III) reacted with TPP-pendant cyclam to give an Au-III-inclusion complex with the pendant TPP coordination. The Au-I complex reacted wi th [Au-III(dien)Cl](2+) in CH3CN to yield an Au-I(out)-Au-III(in-cycla m) mixed complex. The Ni-II complex with TPP-pendant cyclam reacted wi th Au-I(PEt(3))Cl in CH2Cl2, yielding a novel Au-I(out)-Ni-II(in-cycla m) binuclear complex.