COPPER(I) AND COPPER(II) COMPLEXES – PRECURSORS FOR INCLUSION COMPOUNDS WITH CYCLODEXTRINES

Anca Silvestru1, Adina Rotar1, C. Sarbu1, and S. Farcas2

1 “Babes-Bolyai” University, Faculty of Chemistry & Chemical 
Engineering, 11 Arany Janos St., RO-400028 Cluj-Napoca, Romania;
E-mail:  ancas@chem.ubbcluj.ro
2 Institute for Isotopic and Molecular Technology, PO Box 700, RO- 3400, Cluj-Napoca 5, Romania

Metathesis reactions were performed between (Ph3P)2CuNO3 or CuCl2· 2 H2O and the potassium salt of the appropriate organophosphorus acid in a 1:1 or 1:2 molar ratio, respectively, in order to obtain new copper(I) and copper(II) derivatives of type (Ph3P)2CuL and CuL2 (L = [(SePPh2)2N]-, [(SPMe2)(SPPh2)N]-, [(OPMe2)(SPPh2)N]-, [(OPPh2)(SPMe2)N]-, [(SPPh2)(O2SMe)N]-, [(SPPh2)(O2SC6H4Me-4)N]-. Reduction of the copper(II) to copper(I) species was observed to occur in the investigated reactions. All isolated compounds were characterized by MS spectrometry. The paramagnetic Cu(II) derivatives were investigated by ESR spectroscopy. No hyperfine structure of the spectra could be observed, but a large line characteristic to a very strong exchange interaction between the copper ions. The isolated copper(I) compounds were studied by multinuclear NMR spectroscopy (1H, 13C, 31P). The crystal and molecular structure were established by single crystal X-ray diffraction for the tetrameric [Cu{(OPMe2)(SPPh2)N}]4 as well as for the monomeric (Ph3P)2Cu[(SPPh2)(O2SR)N] (R = Me, C6H4Me-4) species. The lipophilicity of these compounds and their capacity to form inclusion complexes with β-cyclodextrine were estimated by TLC.
	
[Cu{(OPMe2)(SPPh2)N}]4			    (Ph3P)2Cu[(SPPh2)(O2SMe)N]