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. ISSN 1477-9226

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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
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Physics
Journal or Publication Title:	Dalton Transactions
Publisher:	Royal Society of Chemistry
ISSN:	1477-9226
Official Date:	2009
Number:	No.39
Number of Pages:	9
Page Range:	pp. 8308-8316
Identification Number:	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
URI:	http://wrap.warwick.ac.uk/id/eprint/17219

Data sourced from Thomson Reuters' Web of Knowledge

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