Trapping of anionic organic radicals by (TpMe2)2Ln (Ln = Sm, Eu).
(2007)
Journal - Inorganic chemistry (United States )
Abstract :
Stoichiometric reaction of [ Sm(Tp(Me2))2 ], 1, with a variety of reducible ketone- and quinone-type substrates gave thermally stable, isolable radical anions/ketyls in moderate to good yields. Thus reaction with benzophenone gave [Sm(Tp(Me2))2(OCPh2)], 2, with fluorenone [Sm(Tp(Me2))2(eta1-OC13H8)], 3, and di-tert-butylparaquinone [Sm(Tp(Me2))2(eta1-OC6H2(tBu)2O)], 4, each of which was structurally characterized. In the case of the less-hindered benzoquinone, an unimetallic semiquinone [Sm(Tp(Me2))2(OC6H4O)], 5, could be isolated, although it was unstable with respect to formation of the dimetallic complex [Sm(Tp(Me2))2]2(mu-OC6H4O), 6. Compound 6 was structurally characterized, as was its anthraquinone analogue [Sm(Tp(Me2))2]2(mu-OC14H8O), 7. When the analogous reaction was carried out between the less-reducing [Eu(Tp(Me2))2] and benzoquinone, only the europium analogue of the semiquinone 5, [Eu(Tp(Me2))2(OC6H4O)], 8, could be isolated. The use of the sterically hindered 3,5-di-tert-butyl-o-benzoquinone allowed isolation of [Sm(Tp(Me2))2(DTBSQ)], 9.
Facile pyrazolylborate ligand degradation at lanthanide centers: X-ray crystal structures of pyrazolylborinate-bridged bimetallics.
(2002)
Journal - Inorganic chemistry (United States )
Abstract :
Adventitious hydrolysis of a number of different complexes with the molecular formula Ln(Tp(Me2))(2)X [Tp(Me2) = (HB(dmpz)(3)), where X is a basic anionic ligand] in various solvents, yielded crystals of highly insoluble dimers of the general formula [Ln(Tp(Me2))(mu-BOp(Me2))](2) (1) [Ln = La, Ce, Sm; BOp(Me2) = (HBO(dmpz)(2))(2)(-); dmpzH = 3,5-dimethylpyrazole]. The results of several single-crystal X-ray determinations are reported. One metal nitrogen distance, that lying across from the two negatively charged bridging oxygen atoms, is 0.06 A longer than the others, suggesting an unusual trans influence at a lanthanide center. The formation of 1 is proposed to involve the intermediacy of Ln(Tp(Me2))(2)OH formed by protonolysis with adventitious water.