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-Me2Pz)2, 1, with anhydrous CuCl2 affords a tetranuclear copper cluster[Cu2Cl2(3,5-Me2Pz)3(MePO3)]2, 2, and a dinuclear compound Cu2Cl4(3,5-Me2Pz)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) A, b = 8.7364(2) A, c = 21.4490(3) A, β = 93.349(1)°, V = 2853.74(8) A3, and Z = 8. 2:  space group = P21/n, a = 12.5964(4) A, b = 15.7773(4) A, c = 13.9781(4) A, β = 116.6280(10)°, V = 2483.32(12) A3, and Z = 2. 3:  space group = P21/c, a = 8.7137(8) A, b = 13.5493(14) A, c = 11.8847(12) A, β = 106.179(2)°, V = 1347.6(2) A3, 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 sus...