Synthesis and characterisation of a series of tetra- and octa-copper(II) complexes with macrocyclic ligands
- 1 January 1991
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 2,p. 221-230
- https://doi.org/10.1039/dt9910000221
Abstract
A Series of seven tetracopper(II) and three octacopper(II) complexes has been synthesised using the tetranucleating macrocyclic ligands H4L1 and H4L2{13,26-dimethyl- and 13,26-di-tert-butyl-3,9,17,23-tetraazatetracyclo[23.3.1.111,15]triaconta-1(29),2,9,11,13,15(30),16,23,25,27-decaene-6,20,29,30-tetraol}. Four representative complexes have been structurally characterised by single-crystal X-ray diffraction studies: [Cu4(µ4-OH)L2][NO3]3·2H2O, 3·2H2O, monoclinic, a= 10.384(2), b= 18.515(5), c= 11.264(2)Å, β= 107.48(2)°, [{Cu4(µ5-O)L1(ClO4)}2][ClO4]2·2H2O, 7·2H2O, triclinic, a= 11.497(4), b= 12.714(3), c= 13.546(4)Å, α= 102.92(2), β= 113.15(2), γ= 100.36(3)°; [{Cu4(µ5-O)L2(ClO4)}2][ClO4]2·CH3OH, 9·CH3OH, monoclinic, a= 15.778(5), b= 17.384(8), c= 15.392(5)Å, β= 109.54(3)°; [Cu4(µ-N3)2L2(N3)2]·2CH3OH, 10·2CH3OH, monoclinic, a= 8.559(3), b= 18.719(6), c= 13.485(7)Å, β= 97.29(4)°. The tetranuclear complexes contain planar Cu4(µ4-OH) cores but the hydroxo donor can be replaced by two azido ligands to form 10, in which the four copper(II) atoms are no longer coplanar. In non-protic solvents, or with added base, the tetracopper(II) complexes dimerise with loss of the hydroxo proton to form octacopper(II) complexes which contain two Cu4-(µ5-O) units.Keywords
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