
TY  - JOUR
A1  - Grillo, Vincent A. 
A1  - Hambley, Trevor W. 
A1  - Gahan, Lawrence R. 
A1  - Hanson, Graeme R. 
A1  - Stranger, Robert 
A1  - Moubaraki, Boujemaa 
A1  - Murray, Keith S. 
T1  - Synthesis of [Cu<emph tye="8">2</emph>(Me<emph tye="8">2</emph>[9]aneN<emph tye="8">2</emph>S)<emph tye="8">2</emph>(OH)<emph tye="8">2</emph>](PF<emph tye="8">6</emph>)<emph tye="8">2</emph>, a Hydroxo-Bridged Copper(<emph type="6">II</emph>) Complex of <emph type="2">N</emph>,<emph type="2">N&#8242;</emph>-Dimethyl-1-thia-4,7-diazacyclononane (Me<emph tye="8">2</emph>[9]aneN<emph tye="8">2</emph>S). X-Ray Structural Analysis, Magnetic Susceptibility, E.P.R. and Visible Spectroscopy
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1999
VL  - 52
IS  - 9
SP  - 861
EP  - 866
KW  - 
UR  - https://doi.org/10.1071/CH97084 
N2  - The bis(&#181;-hydroxo) complex &#91;Cu 2 (Me 2 &#91;9&#93;aneN 2 S) 2 (OH) 2 &#93; (PF 6 ) 2 (Me 2 &#91;9&#93;aneN 2 S = N,N&#8242;-dimethyl-1-thia-4,7- diazacyclononane) results after reaction of &#91;Cu(Me 2 &#91;9&#93;aneN 2 S)(MeCN)&#93; (PF 6 ) with dioxygen at &#8722;78&#176;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) &#197;, 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&#183;&#183;&#183;Cu 2.866(1) &#197;. The solid-state magnetic susceptibility study reveals ferromagnetic coupling, the fitting parameters being J = +46&#177;5 cm &#8722;1 , g = 2.01&#177;0.01 and &thetas; = &#8722;0.58&#177;0.03 K. The frozen-solution e.p.r. spectrum in dimethyl sulfoxide is characteristic of a monomeric copper(II) ion (g &Verbar; 2.300, g &bottom; 2.063; A &Verbar;156.2 &#215; 10 &#8722;4 cm &#8722;1 , A &bottom; 9.0 &#215; 10 &#8722;4 cm &#8722;1 ) with an N 2 O 2 donor set. Thioether coordination to the copper(II) in solution is supported by the presence of an intense absorption assigned to a &#963;(S)&rarr;Cu II LMCT transition at c. 34000 cm &#8722;1 . The single-crystal spectrum of &#91;Cu 2 (Me 2 &#91;9&#93;aneN 2 S) 2 (OH) 2 &#93; (PF 6 ) 2 (273 K) reveals d&rarr;d transitions at 14500 and 18300 cm &#8722;1 and a weak &pi;(S)&rarr;Cu II charge-transfer band at approximately 25000 cm &#8722;1. 
ER  -

