143618-53-5

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• 81218-61-3 (Cu(P(C₆H₅)3))⁽¹⁺⁾ 

Relevant academic research and scientific papers

Synthesis, characterization and optical non-linearity of two heterobimetallic copper clusters containing tetraselenometalates

Cluster [{MoCu3Se3Br}(PPh3)3Se]·THF·H2O (1·3THF·H2O) was prepared from reaction of [Et4N]2[MoSe]4, Cu(PPh3)2NO3 and Et4N·Br in CH2Cl2 solution; also, 1 can be also obtained from the reaction of [MoSe4Cu4Py6Br2] and excess PPh3 in a DMFCH2Cl2 mixture solvent. The 95Mo NMR technique was used to monitor the above two reaction processes. X- ray crystallographic structure determination shows that it contains a strongly distorted cubane-like {MoCu3Se3Br} core. The coordination of the central Mo atom and each Cu atom are distorted from tetrahedral. Cluster [{WCu3Se3C1}(PPh3)3Se] (2) was synthesized by the reaction of [Et4N]2[WSe]4 and Cu(PPh3)2Cl in the solid state for nonlinear optical (NLO) studies. Its structure was reported by Ibers (Inorg. Chem. 31 (1992) 4365). The NLO properties of clusters 1 and 2 were studied. Both NLO absorption and refraction were obtained, and their effective third-order non- linearities were detected with α2 = 3.4 x 10-10 and 5.9 x 10-10 m/W and n2 = - 1.5 X 10-17 and - 1.3 x 10-17 m2/W, respectively, for the same concentration CH2C12 solution of 1 and 2. Influence of skeletal atoms to nonlinear absorption is also discussed in the paper. (C) 2000 Elsevier Science B.V.

Interactions of coinage-group cations with the tetraselenotungstate anion: Multinuclear NMR spectroscopic results and crystal structures of (μ-WSe4)[(PMe2Ph)2Cu]2, (μ-WSe4)[(PMePh2)Au]2, and (μ3-Cl)(μ3-WSe4)[(PPh 3)Cu]3

Reaction of a CH3CN solution of [NPr4]2[WSe4] with 2 equivalents of Cu+, Ag+, or Au+ in the presence of excess PMe2Ph affords (μ-WSe4)[(PMe2Ph)2M]2 (M = Cu (1), Ag (2), or Au (3)). (μ-WSe4)[(PMe2Ph)2Cu]2 crystallizes with four formula units in the monoclinic space group C2h6-C2/c in a cell of dimensions a = 19.315 (7) A?, b = 15.575 (4) A?, c = 16.829 (7) A?, and β = 127.99 (1)° (T = 113 K). Full anisotropic refinement of the structure led to a value of R(F) = 0.032 (Rw(F) = 0.042) for 196 variables and 4047 unique reflections. The molecule possesses a crystallographic 2-fold axis; the W center is tetrahedrally coordinated to four Se atoms that bridge to the Cu atoms; coordination of each Cu atom to two P atoms completes the distorted tetrahedral geometry about each Cu atom. Substitution of PMePh2 for PMe2Ph with M = Au+ affords (μ-WSe4)[(PMePh2)Au]2 (4). This compound crystallizes with four molecules in the monoclinic space group P21/c in a cell of dimensions a = 14.647 (5) A?, b = 14.161 (5) A?, c = 15.319 (6) A?, and β = 106.65 (1)° (T = 113 K). A value of R(F) = 0.088 (Rw(F) = 0.081) for 186 variables and 5859 unique reflections was obtained from anisotropic refinement of the heavy atoms. The structure is similar to that of 1, except that the geometry around the Au atoms is distorted trigonal planar. The 77Se NMR spectra of solutions of 1-4 exhibit a single peak; for 1-3 this peak shifts to lower field with increasing atomic number of the coinage metal. The 31P NMR spectra also consist of a single resonance. Reaction of [NPr4]2[WSe4] with [(PPh3)2Cu(BH3)(CN)]2 in CH2Cl2 in the presence of NH4Cl affords the cubane-like compound (μ3-Cl)(μ3-WSe4)-[(PPh 3)Cu]3 (5). Its structure, which has analogues in the MoSe42- and the WS42- systems, is that of a cubane in which each Cu center is bonded tetrahedrally to a P atom, a Cl atom, and two Se atoms and the W center is bonded tetrahedrally to four Se atoms. Consistent with this solid-state structure, the 77Se NMR spectrum of a solution of 5 displays two resonances at δ 1651 and 1232 ppm. The compound crystallizes with four molecules in the orthorhombic space group D24-P212121 in a cell of dimensions a = 12.88 (1) A?, b = 17.72 (1) A?, and c = 22.59 (1) A? (T = 113 K). The structure has been refined anisotropically to a value of R(F) = 0.063 (Rw(F) = 0.069) for 570 variables and 8950 observations.