Tetraazacyclotetradecane (L: cyclam and derivatives) complexes of 3d metal ions (M), [M(L)X2]+ (X = halide or pseudohalide), have been thoroughly studied. Yet, acetylide chemistry based on M(L) units is grossly underdeveloped. Our laboratory has explored the synthesis and properties of the trans-[M(cyclam)(C2R)2]+ type compounds with M as CrIII, FeIII and CoIII, and C2R as both simple acetylides and cross conjugated gem-DEE. In the case of CoIII, the stepwise alkynylation has allowed the isolation of the trans-[Co(cyclam)(C2R)Cl]+, {trans-[Co(cyclam)Cl]2(m-C2n)}2+ and trans-[Co(cyclam)(C2R)(C2R´)]+ type compounds. Similar alkynylation chemistry has been extended to compounds based on cyclam derivatives, such as NiII-TMC (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and CrIII-HMC (5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane), yielding acetylide compounds that are significantly different from those based on M(cyclam). Also to be discussed are the voltammetric, spectroscopic and computational studies of these compounds.

Sustainable acetylide chemistry: 3d metals and tetraazamacrocycles

251st National Meeting (2016)

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