Stabilization of copper(I) in aqueous solutions by ligation with the saturated tetra-aza macrocyclic ligand 1,4,5,7,7,8,11,12,14,14,-decamethyl-1,4,8,11-tetra azacyclotetradecane

Synthesis, X-ray Structure, Electrochemical, and EPR Studies of a Pentacoordinated Mn(II) Tetramethylcyclam Complex

“…[16][17][18] As part of our work on the coordination chemistry of substituted cyclam macrocycles, 19,20 we investigated the complexation of manganese with the 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (tmc). In accordance with the well-established steric and electronic influences of N-substitution, [21][22][23][24][25] and contrary to the case of the unsubstituted homologues, no Mn(III) or dimer mixed valence species could be obtained.…”

Redox Chemistry of Nickel Complexes in Aqueous Solutions

“…(1) N-Alkylation of the macrocyclic ligand induces an increase of the cavity of the ligand because of the steric hindrance induced by the N-alkylation. 174 On the other hand, it was shown that an increase in the size of the macrocyclic ligand does not stabilize monovalent nickel complexes. 152b (2) Tertiary amines are poorer σ donors than secondary amines and thus stabilize low valent transition-metal complexes.…”

Synthesis, characterization, and electrochemistry of copper(II) and palladium(II) hydroporphyrins: the copper(I) octaethylisobacteriochlorin anion

“…[Pd(tmc)]2+ does not have a tetrahedral distortion, but does have a pyramidal distortion. The authors attribute the shifts in reduction potentials to these distortions and suggest that Pd(I) is favored by tetrahedral coordination.19 N-Peralkylation of macrocycles also increases the stability and lifetime of Cu(I) and Pd(I) complexes by steric inhibition of dimerization and of reaction at the metal 18,…”