Syntheses and solid state structures of cyclam-based copper and zinc compounds

•Cyclam-based complexes of Cu(II) and Zn(II) are described.•Copper catalyses the N,N′-functionalization of cyclam with CH2OMe pending arms.•Complexes [{H2(MeOCH2)2Cyclam}Cu]X (X = SO4, CuCl4) are hybrid polymers.•[{H2(PhCH2)2Cyclam)}ZnCl]Cl displays trigonal bipyramidal geometry.

Copper(II) and zinc(II) complexes of general formula [{H2(4−BtuPhCH2)2Cyclam}Cu]SO4, 1, [{H2(PhCH2)2Cyclam}Cu]X, (X = SO4, 2; X = (CH3COO)2, 3), [{H2(PhCH2)2Cyclam}Zn]SO4, 5, and [{H2(PhCH2)2Cyclam)}ZnCl]Cl, 6, were prepared by reaction of H2Bn2Cyclam (Bn = PhCH2 or 4−BtuPhCH2) with one equiv. of the appropriate Cu(II) or Zn(II) salt.The preparation of Cu(II) complexes of general formula [{H2(MeOCH2)2Cyclam}Cu]X (X = SO4, 7, (CH3COO)2, 8, and CuCl4, 9) displaying a modified cyclam ligand with two N-CH2OMe pending arms was achieved by nucleophilic attack of methanol to the bridging methylene groups of 1,4,8,11-tetraazatricyclo[9.3.1.14,8]hexadecane in a Cu2+ mediated process.

Graphical abstractCompounds [{H2(4−BtuPhCH2)2Cyclam}Cu]SO4, 1, [{H2(PhCH2)2Cyclam}Cu]X, (X = SO4, 2; X = (CH3COO)2, 3), [{H2(PhCH2)2Cyclam}Zn]SO4, 5, and [{H2(PhCH2)2Cyclam)}ZnCl]Cl, 6, were prepared. The synthesis of the complexes [{H2(MeOCH2)2Cyclam}Cu]X (X = SO4, 7, (CH3COO)2, 8, and CuCl4, 9) was achieved by methanolysis of the bridging methylene groups of 1,4,8,11-tetraazatricyclo[9.3.1.14,8]hexadecane in a Cu2+ mediated process.Figure optionsDownload full-size imageDownload as PowerPoint slide