Unprecedented Mixed-Valence Cu(I)/Cu(II) Complex Derived from N-Methyl-1,3,5-triaza-7-phosphaadamantane: Synthesis, Structural Features, and Magnetic Properties

作者：Kirillov Alexander M^*; Filipowicz Malgorzata; Guedes da Silva M Fatima C; Klak Julia; Smolenski Piotr; Pombeiro Armando J L

来源：Organometallics, 2012, 31(22): 7921-7925.

DOI：10.1021/om3005564

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.

• 出版日期2012-11-26