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Spectroscopy and structures of two complete families, one mononuclear, the other binuclear, of 1: 2 CuX : dptu stoichiometry (X = Cl, Br, I; 'dptu' = N,N '-diphenylthiourea)
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Bowmaker, Graham A., Chaichit, Narongsak, Hanna, John V., Pakawatchai, Chaveng, Skelton, Brian W. and White, Allan H. (2009) Spectroscopy and structures of two complete families, one mononuclear, the other binuclear, of 1: 2 CuX : dptu stoichiometry (X = Cl, Br, I; 'dptu' = N,N '-diphenylthiourea). Dalton Transactions (No.39). pp. 8308-8316. doi:10.1039/b909167j ISSN 1477-9226.
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Official URL: http://dx.doi.org/10.1039/b909167j
Abstract
Crystallization of the copper(I) halides (CuX; X = Cl, Br, I) with N,N'-diphenylthiourea ('dptu' = (PhNH)(2)CS) in 1 : 2 ratio from acetonitrile solution in ambient conditions yields a mononuclear isomorphous series of complexes of the form [XCu(dptu)(2)]center dot H2O, an unusually complete array, with the central copper atoms in quasi-trigonal planar environments, as shown by single crystal X-ray studies, in turn providing a platform for comparative spectroscopic studies. Under anhydrous conditions, anhydrous compounds may be obtained, a full series again being accessible, but now of the binuclear form [(dptu) XCu(mu-S-dptu)(2)CuX(dptu)], the chloride being a bis(acetonitrile) solvate, the isomorphous bromide and iodide pair being unsolvated. A (solvated) sulfate salt is found to be of the form [Cu(dptu)(2)](2)(SO4), providing a novel example of a copper(I) atom being (quasi-) linearly coordinated by the pair of unidentate (dptu) sulfur ligands, Cu-S 2.1770(5), 2.1811(5) angstrom, S-Cu-S 162.18(2)degrees. The nu(CuX) vibrational frequencies are assigned in the far-IR spectra of [XCu(dptu)(2)]center dot H2O (X = Cl, Br, I) at 274, 207, and 190 cm(-1) respectively. The broadline static Cu-65 NMR spectra of [Cl2Cu2(dptu)(4)]center dot 2CH(3)CN and [X2Cu2(dptu)(4)] (X = Br, I) have been recorded at 9.4 and 7.05 T, and the spectra have been analysed to yield the Cu-65 nuclear quadrupole coupling and chemical shift parameters. The Cu-63,Cu-65 nuclear quadrupole resonance frequencies of [XCu(dptu)(2)]center dot H2O (X = Cl, Br, I) have also been measured, and the resulting Cu-65 quadrupole coupling constants are ca. 4 those of the dimeric [X2Cu2(dptu)(4)] compounds.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Physics | ||||
Journal or Publication Title: | Dalton Transactions | ||||
Publisher: | Royal Society of Chemistry | ||||
ISSN: | 1477-9226 | ||||
Official Date: | 2009 | ||||
Dates: |
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Number: | No.39 | ||||
Number of Pages: | 9 | ||||
Page Range: | pp. 8308-8316 | ||||
DOI: | 10.1039/b909167j | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access | ||||
Funder: | AINSE, Thailand Research Fund | ||||
Grant number: | 02190, 03011, RTA 4880008 |
Data sourced from Thomson Reuters' Web of Knowledge
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