1,10-Phenanthroline-5,6-dione as a building block for the synthesis of homo- and heterometallic complexes
作者:Fausto Calderazzo、Guido Pampaloni、Vincenzo Passarelli
DOI:10.1016/s0020-1693(01)00711-3
日期:2002.3
1,10-Phenanthroline-5.6-dione (C12H6N2O2 (1)) reacts with V(eta(6)-mesitylene)(2) and Ti(eta(6)-toluene)(2) affording coordination compounds of general formula M(O. O'-C12H6N2O2)(3) (M = Ti (2), M = V (3)) which further react with TiCl4 or TiCp2(CO)(2) yielding the tetrametallic species M(O.O'-C12H6N2O2-N,N')(3)(M'L-n), (M=V. M'L-n=TiCl4 (4): M=Ti. M'L-n = TiCp2 (5): M = V. M'L-n = TiCp2 (6)). The complex salt [Fe(NN'-C12H6N2O2)(3)][PF6](2) (7) has been obtained from iron(II) chloride tetrahydrate and 1 in the presence of NH4PF6. The reaction of 7 with TiCp2(CO)(2) affords the tetrametallic derivative [Fe(N,N'-C12H6N2O2-O,O')(3)(TiCp2)(3)][PF6](2) (8). TiCl2(THF)(2) reacts with MCp2(O.O'-C12H6N2O2) to give MCp2(O,O'-C12H6N2O2-N,N')TiCl2 (M=Ti (9). M=V (10)). By reaction of TiCp2(O.O'-C12H6N2O2-NN')TiCl2 (9) with C12H6N2O2. the bimetallic derivative TiCp2(O,O'-C12H6N2O2-NN')TiCl2(O.O'-C12H6N2O2) (11) has been prepared, which readily adds to TiCl4, to give the trimetallic titanium derivative TiCp2(O.O'-C12H6N2O2-N.N')TiCl2(O,O'-C12H6N2O2-N.N')TiCl4 (12). VCp2(O,O'-C12H6N2O2-NN')TiCl2 (10) reacts with the tris-chelate iron(II) cation 7 affording the heptametallic cationic complex [Fe(N,N'-C12H6N2O2-O,O')TiCl2(N,N'-C12H6N2O2-O,O')VCp2](3)(+2) isolated as the hexafluorophosphate 13. (C) 2002 Elsevier Science B.V. All rights reserved.