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

Abstract

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, beta = 93.349(1) degrees, V = 2853.74(8) A3, and Z = 8. 2: space group = P2(1)/n, a = 12.5964(4) A, b = 15.7773(4) A, c = 13.9781(4) A, beta = 116.6280(10) degrees, V = 2483.32(12) A3, and Z = 2. 3: space group = P2(1)/c, a = 8.7137(8) A, b = 13.5493(14) A, c = 11.8847(12) A, beta = 106.179(2) degrees, 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 susceptibility measurements.

Transition metal complexes with Girard reagent-based ligands. Part IV. Synthesis and characterization of pyridoxilidene Girard-T hydrazone complexes. Crystal structure of the copper(II) complex

“…The X-ray analysis of a binuclear [Cu(3,5-Me 2 pz) 2 Cl 2 ] 2 complex has shown the existence of two structurally identical mononuclear halves. Its low-temperature crystal structure determined by a single crystal X-ray analysis has already been published [36], showing very similar unit cell dimensions and the same molecular structure as we established for our compound. Hence, we will not discuss in this work the crystal structure of [Cu(3,5-Me 2 pz) 2 Cl 2 ] 2 complex.…”

“…Besides, a dimer [Cu(3,5-Me 2 pz) 2 Cl 2 ] 2 has already been described. Namely, in a paper [36] the reaction of CuCl 2 and bis(3,5-dimethylpyrazolyl)methylphosphinosulfide in dichloromethane was reported yielding a complex identical with ours by composition and structure. The complex was formed with this pyrazole derivative as a consequence of breaking the phosphorus-nitrogen bond.…”

“…By the reaction of CuCl 2 with Girard-T and acetylacetone in a molar ratio 1:1:1.5 in MeOH in a mildly acidic medium, a mixture of single crystals was obtained, the X-ray analysis of which showed that instead of the expected copper(II) complex with acetylacetone Girard-T hydrazone a mixture of Cu(II) complexes with 3,5-dimethylpyrazole was isolated: brown [Cu(acac) 2 ] Á 2[Cu(3,5-Me 2 pz) 2 Cl 2 ], green [Cu(3,5-Me 2 pz) 2 Cl 2 ] 2 , and blue Cu(acac) 2 , the latter two previously characterized [35,36]. Here a cyclization reaction of the condensed hydrazide moiety of Girard-T with acetylacetone occurred resulting in the formation of a pyrazole derivative and elimination of trimethylammoniumacetyl-moiety in the presence of metal ions as a consequence of a weaker NH-CO bond due to coordination.…”

Tetrakis(2,2′-bipyridyl)dichloridodi-μ3-hydroxido-di-μ2-hydroxido-tetracopper(II) dinitrate hexahydrate

“…20871065) Recently, some tetranuclear hydroxo-bridged copper(II) complexes with cubane and the chair-like structure have been reported (Zheng & Lin, 2002;Sletten et al, 1990;Albada et al, 2002;Lu et al, 2007;Chandrasekhar et al, 2000). In this paper, the crystal structure of a new copper(II) complex exhibiting a chair-like tetranuclear motif is presented.…”

“…For the structures of related complexes, see: Albada et al (2002); Chandrasekhar et al (2000); Lu et al (2007); Sletten et al (1990); Zheng & Lin (2002).…”