| Abstract |
The unique mixed-valence tetracopper(I/II) complex [Cu4I4(mu-N-3)(2)(N-3)(4)(mu-PTA-Me)(2)(PTA-Me)(2)]center dot 2H(2)O (1), composed of the hexaazido dicopper(II) core \Cu-2(mu-N-3)(2)(N-3)(4)\(2-) and two copper(I) \CuI2(mu-PTA-Me)-(PTA-Me)\(+) units, has been easily, generated by self assembly in water from copper(II) nitrate, N-methyl-1,3,5-triaza-7-phosphaadamantane iodide, [PTA-Me]I, and sodium azide. It has been characterized by IR, H-1 and P-31\H\ NMR, and EPR spectroscopies and elemental and single crystal X-ray diffraction analyses Apart from representing the first mixed valence metal compound bearing PTA or any cage like aminophosphine derivative, 1 also discloses a fare P,N-coordination mode of PTA Me ligands, which act, for the first time, as spacers between the Cu(I) and Cu(II) centers. Magnetic susceptibility and EPR studies reveal a ferromagnetic interaction (2J = +17.1 cm(-1)) between the Cu(II) atoms through mu-1,1-azido ligands. |
