Formation of a tetranuclear copper (II) cluster assembled by metal-assisted hydrolysis and desulfurization of bis(3,5-dimethylpyrazolyl)methylphosphine sulfide, MeP(S)(3,5-Me2Pz)2

The reaction of methylphosphine sulfide, MeP(S)(3,5-Me(2)Pz)(2), 1, with anhydrous CuCl2 affords a tetranuclear copper cluster[Cu2Cl2(3,5-Me(2)Pz)(3)(MePO3)](2), 2, and a dinuclear compound Cu2Cl4(3,5-Me(2)Pz)(4), 3. This reaction involves a metal-assisted desulfurization along with concomitant hydrolysis of P-N bonds. The X-ray structures of 1-3 have been determined, and the crystal parameters for these are the following, 1: space group C2/c, a = 15.2552(1) Angstrom, b = 8.7364(2) Angstrom, c = 21.4490(3) Angstrom, beta = 93.349(1)degrees, V = 2853.74(8) Angstrom(3), and Z = 8. 2: space group = P2(1)/n, a = 12.5964(4) Angstrom, b = 15.7773(4) Angstrom, c = 13.9781(4) Angstrom, beta = 116.6280(10)degrees, V = 2483.32(12) Angstrom(3), and Z = 2. 3: space group = P2(1)/c, a = 8.7137(8) Angstrom, b = 13.5493(14) Angstrom, c = 11.8847(12) Angstrom, beta = 106.179(2)degrees, V = 1347.6(2) Angstrom(3), and Z = 2. The structure of 2 shows that it comprises two dinuclear copper cores bridged together by two tripodal methylphosphinate, MePO3, ligands. 2 is weakly antiferromagnetically coupled, as revealed by variable temperature magnetic susceptibility measurements.