SYNTHESES, STRUCTURES AND PROPERTIES OF COPPER AND NICKEL COMPLEXES OF THE MACROCYCLIC LIGAND 5,6,11,12,17,18,23,24-OCTAHYDRO-TETRABENZO[B,F,J,N][1,5,9,13]TETRAAZACYCLO -HEXADECINE (H(8)TAAB)

摘要

The synthesis and characterization of the new macrocyclic copper complex [Cu(H(8)TAAB](ClO4)(2) are described (H(8)TAAB=5,6,11,12,17,18,23,24-octahydro-tetrabenzo[b,f,j,n][1,5,9,13]tet raazacyclohexadecine). The crystal structure of the complex ([Cu(H(8)TAAB)(H2O)(2)](ClO4)(2) . 2H(2)O) was determined. Crystal data: formula CuN4C28H36Cl(2)O(12), space group P (1) over bar, Z=2, a=9.475(2), b=9.457(1), c=18.222(4) Angstrom, alpha=90.07(2), beta=97.71(2), gamma=90.02(1)degrees. The nickel complex of H(8)TAAB ([Ni(H(8)TAAB)(O(H)CH3)(2)](ClO4)(2) . 2HOCH(3)) crystallizes in the space group P (1) over bar; formula NiN4C32H44Cl2O12, Z=2, a=11.322(5), b=16.752(9), c=9.703(3) Angstrom, alpha=101.24(4), beta=90.76(3), gamma=86.74(4)degrees. For the ligand H(8)TAAB which crystallized with one ethylacetate, formula N4C32H36O2, the space group P2(1)/c was found with Z=4, a=18.468(3), b=13.111(1), c=11.698(2) Angstrom, beta=96.36(1)degrees. A new macrocycle, Me(4)H(4)TAAB, was synthesized by methylation of H(8)TAAB and structurally characterized: formula N4C32H36, space group P (1) over bar with Z=2, a=12.150(1), b=12.344(2), c=9.324(1) Angstrom, alpha=90.642(9), beta=102.186(9), gamma=102.804(9)degrees. [References: 27]