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Synthesis and structures of the WOS(3)Cu(3)Pz(3)Cl and [PPh4](4)[{WOS3(CuNCSe)(3)}(2)] clusters (Pz = pyrazole), and structure of [PPh4](2)[Cu(NCS)(4)]

Lookup NU author(s): Emeritus Professor Bill CleggORCiD

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Abstract

Reaction of CuCl and pyrazole (Pz) with [NH4](2)[WOS3] in acetone yields a new cluster WOS(3)Cu(3)PZ(3)Cl (1), forming a one-dimensional polymer through secondary Cu-Cl bonding, while [PPh4](4)[{WOS3(CuNCSe)(3)}(2)] (2) with selenocyanate bridges in the dimeric anion is formed by the reaction of CuCl and KSeCN With [PPh4](2)[WOS3] in acetone solution. The title compounds have been characterized by single-crystal X-ray diffraction, IR and UV-Vis spectroscopy. We also present the temperature-dependent H-1 NMR spectrum of WOS(3)Cu(3)PZ(3)Cl. Crystals of [PPh4](2)[Cu(NCS)(4)] (3) have been obtained during the slow evaporation of dichloromethane solution of [PPh4](2)[Co(WO2S2)(2)(CuNCS)(2)]. The two compounds I and 2 contain approximately tetrahedral WOS3 units and all metal atoms and sulfur atoms form incomplete cubane-type frameworks; the eighth vertex opposite W is vacant. Thiotungstate groups in 1 and 2 act as bidentate ligands through two sulfur atoms chelating copper atoms. This is consistent with the infrared spectra, which exhibit low frequency W-S-b stretching hands. There is no coordination of oxygen atoms to copper. In each of 1 and 2 two distinctly different coordination geometries of copper are found: two copper atoms adopt trigonal planar geometry, while the third one adopts distorted tetrahedral geometry. Compound 3 has an essentially regular tetrahedral geometry, unusual for Cu(II). (C) 2002 Elsevier Science Ltd. All rights reserved.


Publication metadata

Author(s): Beheshti A, Clegg W, Hyvadi R, Hekmat HF

Publication type: Article

Publication status: Published

Journal: Polyhedron

Year: 2002

Volume: 21

Issue: 16

Pages: 1547-1552

ISSN (print): 0277-5387

ISSN (electronic): 1873-3719

Publisher: Pergamon

URL: http://dx.doi.org/10.1016/S0277-5387(02)01012-4

DOI: 10.1016/S0277-5387(02)01012-4


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