180335-42-6Relevant academic research and scientific papers
A new cyclam with a triphenylphosphine-pendant and its metal complexes
Kimura, Eiichi,Kodama, Yorimitsu,Shionoya, Mitsuhiko,Koike, Tohru
, p. 151 - 158 (1996)
A new triphenylphosphine-pendant cyclam (triphenylphosphine = TPP; cyclam = 1,4,8,11-tetraazacyclotetradecane) was synthesized by reaction of an ethyl cinnamate derivative bearing a diphenylphosphine group at the ortho position of the phenyl group with 2,3,2-tetraamine (= 1,9-diamino-3,7-diazanonane) in refluxing MeOH, followed by BH3 reduction. Triphenylphosphine oxide-pendant cyclam (triphenylphosphine oxide = TPPO) was derived by treatment of TPP-pendant cyclam with benzyl alcohol in CCl4. The TPP-pendant cyclam formed stable 1:1 metal inclusion complexes with NiII and MnIII. The TPPO-pendant cyclam yielded a 1:1 NiII complex which was the best catalyst among the cyclam-NiII and -MnIII complexes for epoxidation of trans-stilbene with NaClO in CH2Cl2. Gold(I) reacted with TPP-pendant cyclam to yield a stable 1:1 complex, in which AuI binds only to the pendant phosphine. On the other hand, gold(III) reacted with TPP-pendant cyclam to give an AuIII-inclusion complex with the pendant TPP coordination. The AuI complex reacted with [AuIII(dien)Cl]2+ in CH3CN to yield an AuI(out)-AuIII(in-cyclam) mixed complex. The NiII complex with TPP-pendant cyclam reacted with AuI(PEt3)Cl in CH2Cl2, yielding a novel AuI(out)-NiII(in-cyclam) binuclear complex.
