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Transition metal derivatives of 1,10-phenanthroline-5,6-dione: Controlled growth of coordination polynuclear derivatives
Authors:Lucia Calucci  Calogero Pinzino
Institution:a Istituto per i Processi Chimico-Fisici, CNR, Area della Ricerca, Via G. Moruzzi 1, I-56124 Pisa, Italy
b Università di Pisa, Dipartimento di Chimica e Chimica Industriale, Via Risorgimento 35, I-56126 Pisa, Italy
Abstract:The synthesis and the characterization of several mono- and polymetallic derivatives of 1,10-phenanthroline-5,6,-dione (1) are presented.The reaction of 1 with M(CO)6 (M = Cr, Mo) gives compounds of general formula M(O,O′-C12H6N2O2)3, M = Cr (2), Mo (3).Compound 3 is also obtained starting from Mo(η6-CH3C6H5)2, whereas the reaction of Cr(η6-CH3C6H5)2 with 1 affords the ionic derivative Cr(η6-CH3C6H5)2]C12H6N2O2] (4), which has been studied by EPR spectroscopy and DFT calculations.FeCl2(N,N′-C12H6N2O2)2 (6), is obtained by thermal decomposition of Fe(N,N′-C12H6N2O2)3]Cl2 (5).Polymetallic compounds of general formula CrO,O′-C12H6N2O2-N,N′-MCl4]3,containing chromium and a Group 4 element M = Ti (7), Zr (8), Hf (9), are prepared from Cr(O,O′-C12H6N2O2)3 and the corresponding MCl4 or MCl4DME. Polynuclear derivatives of iron and chromium of formula Fe(N,N′-C12H6N2O2-O,O′-CrCl2(THF)2)3]PF6]2 (10), and CrO,O′-C12H6N2O2-N,N′-FeCl2(THF)]3 (11), are obtained by the reaction of Fe(N,N′-C12H6N2O2)3]PF6]2 with three equivalents of CrCl2(THF)2 and from Cr(O,O′-C12H6N2O2)3 and FeCl2(THF)1.5, respectively. Compound 11 reacts with 1 (3 equivalents in sym-C2H2Cl4 or 6 equivalents in ethanol) to give CrO,O′-C12H6N2O2-N,N′-FeCl2(N,N′-C12H6N2O2)]3 (12), and Cr(O,O′-C12H6N2O2-N,N′-Fe(N,N′-C12H6N2O2)2)3]Cl6 (13), respectively.
Keywords:Chromium  Molybdenum  1  10-Phenanthroline-5  6-dione  EPR  Polynuclear compounds
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