RESUMEN
An efficient approach to the synthesis of diamides of 4,7-difluoro-1,10-phenanthroline-2,9-dicarboxylic acid was elaborated. Direct nucleophilic substitution with 4,7-dichloro-1,10-phenanthroline precursors opened access to difluoro derivatives in high yield. As a result, four new fluorinated ligands were prepared in up to 88% yield. Their structure was proved by a combination of spectral methods and X-ray data. A set of lanthanoid complexes was prepared to demonstrate the utility of new ligands. The structure of the complexes was studied in solid state (IR-spectroscopy, X-ray diffraction) and in solution (NMR-spectroscopy).
Asunto(s)
Elementos de la Serie de los Lantanoides , Fenantrolinas , Diamida , Elementos de la Serie de los Lantanoides/química , Ligandos , Espectroscopía de Resonancia Magnética , Modelos Moleculares , Fenantrolinas/químicaRESUMEN
The interaction of the pivalate complexes of iron(iii), [Fe3O(Piv)6(H2O)3]·HPiv, and cadmium(ii), [Cd(Piv)2], in Et2O resulted in one more type of "ferric wheel" family complex, namely [Fe8(Piv)16{Cd(Piv)2}(µ-OH)8]·Et2O (1). The complex is an octanuclear iron(iii) wheel with a {Cd(Piv)2} moiety asymmetrically incorporated into the ring.
RESUMEN
Molybdenum hexacarbonyl reacts with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (, dpp-BIAN) and 1,2-bis[(trimethylsilyl)imino]acenaphthene (, tms-BIAN) in toluene to produce (dpp-BIAN)Mo(CO)(4) () and (tms-BIAN)Mo(CO)(4) (), respectively. The reaction of [CpNi(CO)](2) with yields (dpp-BIAN)NiCp (). Metathesis between Li(2)(tms-BIAN) and NiCl(2)(dppe) affords the Ni(0) complex (tms-BIAN)Ni(dppe) (). The diamagnetic compounds , and have been characterized by (1)H, (29)Si and (31)P NMR spectroscopy, IR spectroscopy and elemental analysis. The ESR spectrum of the paramagnetic compound indicates the presence of Ni(i) coordinated by Cp and a neutral dpp-BIAN ligand. The molecular structures of have been determined by single-crystal X-ray analysis.