TY - JOUR
T1 - Synthesis of [Cu2(Me2[9]aneN2S)2(OH)2] (PF6)2, a hydroxo-bridged copper(II) complex of N,N′- dimethyl-1-thia-4,7-diazacyclononane (Me2[9]aneN2S). X-ray structural analysis. Magnetic susceptibility, E.P.R. and visible spectroscopy
AU - Grillo, Vincent A.
AU - Gahan, Laurence R.
AU - Hanson, Graeme R.
AU - Hambley, Trevor W.
AU - Stranger, Robert
AU - Moubaraki, Boujemaa
AU - Murray, Keith S.
PY - 1999
Y1 - 1999
N2 - The bis(μ-hydroxo) complex [Cu2(Me2[9]aneN2S)2(OH) 2](PF2)2 (Me2[9]aneN2S = N,N′-dimethyl-1-thia-4,7-diazacyclononane) results after reaction of [Cu(Me2[9]aneN2S)(MeCN)] (PF6) with dioxygen at-78°C in acetonitrile. The complex has been characterized by X-ray crystallography: orthorhombic, space group Pnma, with a 18.710(3), b 16.758(2), c 9.593(2) Å, and Z = 4. The structure refined to a final R value of 0.051. The complex contains two copper(II) ions bridged by two hydroxo groups with Cu⋯Cu 2.866(1) Å. The solid-state magnetic susceptibility study reveals ferromagnetic coupling, the fitting parameters being J = +46±5 cm-1, g = 2.01±0.01 and θ = -0.58±0.03 K. The frozen-solution e.p.r. spectrum in dimethyl sulfoxide is characteristic of a monomeric copper(II) ion (g∥ 2.300, g⊥ 2.063; A∥ 156.2 × 10-4 cm-1, A⊥9.0 × 10-4 cm-1) with an N2O2 donor set. Thioether coordination to the copper(II) in solution is supported by the presence of an intense absorption assigned to a σ(S)→CuII LMCT transition at c. 34000 cm-1. The single-crystal spectrum of [Cu2(Me2[9]aneN2S)2(OH)2] (PF6)2 (273 K) reveals d→d transitions at 14500 and 18300 cm-1 and a weak π(S)→CuII charge-transfer band at approximately 25000 cm-1.
AB - The bis(μ-hydroxo) complex [Cu2(Me2[9]aneN2S)2(OH) 2](PF2)2 (Me2[9]aneN2S = N,N′-dimethyl-1-thia-4,7-diazacyclononane) results after reaction of [Cu(Me2[9]aneN2S)(MeCN)] (PF6) with dioxygen at-78°C in acetonitrile. The complex has been characterized by X-ray crystallography: orthorhombic, space group Pnma, with a 18.710(3), b 16.758(2), c 9.593(2) Å, and Z = 4. The structure refined to a final R value of 0.051. The complex contains two copper(II) ions bridged by two hydroxo groups with Cu⋯Cu 2.866(1) Å. The solid-state magnetic susceptibility study reveals ferromagnetic coupling, the fitting parameters being J = +46±5 cm-1, g = 2.01±0.01 and θ = -0.58±0.03 K. The frozen-solution e.p.r. spectrum in dimethyl sulfoxide is characteristic of a monomeric copper(II) ion (g∥ 2.300, g⊥ 2.063; A∥ 156.2 × 10-4 cm-1, A⊥9.0 × 10-4 cm-1) with an N2O2 donor set. Thioether coordination to the copper(II) in solution is supported by the presence of an intense absorption assigned to a σ(S)→CuII LMCT transition at c. 34000 cm-1. The single-crystal spectrum of [Cu2(Me2[9]aneN2S)2(OH)2] (PF6)2 (273 K) reveals d→d transitions at 14500 and 18300 cm-1 and a weak π(S)→CuII charge-transfer band at approximately 25000 cm-1.
UR - http://www.scopus.com/inward/record.url?scp=0006735935&partnerID=8YFLogxK
U2 - 10.1071/CH97084
DO - 10.1071/CH97084
M3 - Article
SN - 0004-9425
VL - 52
SP - 861
EP - 866
JO - Australian Journal of Chemistry
JF - Australian Journal of Chemistry
IS - 9
ER -