Alkane Elimination Reactions between Yttrium Alkyls and Tungsten Hydrides

作者：Sobaczynski Adam P; Obenauf Johannes; Kempe Rhett^*

来源：European Journal of Inorganic Chemistry, 2014, 2014(7): 1211-1217.

DOI：10.1002/ejic.201301476

• Bimetallic complexes
• Hydrides
• Yttrium
• Tungsten

Alkane elimination of the yttrium monoalkyl [Cp2Y(CH2SiMe3)(thf)] (Cp = cyclopentadienyl, thf = tetrahydrofuran, Me = methyl) with the tungsten hydrido carbonyl complex [HW(CO)(3)Cp] in THF gave rise to the trinuclear complex [{CpW(CO)(2)(-CO)}(2)YCp(thf)(3)] (1). In the course of the reaction, one Cp ligand per yttrium was redistributed, thus leading to the formation of [Cp3Y] as a side product. To avoid the observed ligand redistribution, other solvents were investigated. The reaction of [Cp2Y(CH2SiMe3)(thf)] with [HW(CO)(3)Cp] in acetonitrile afforded the dinuclear complex [{CpW(CO)(2)(-CO)}YCp2(NCMe)(2)] (2). The reaction of the yttrium dialkyl complex [Y(CH2SiMe3)(2)(OC(6)H(3)tBu(2)-2,6)(thf)(2)] with [HW(CO)(3)Cp] in toluene gave the polymeric compound [{CpW(CO)(2)(-CO)}(2)Y(OC(6)H(3)tBu(2)-2,6)](n) (3), whereas reaction in THF gave the molecular compound [{CpW(CO)(2)(-CO)}(2)Y(OC(6)H(3)tBu(2)-2,6)(thf)(3)] (4). The reaction of the yttrium trialkyl complex [Y(CH2SiMe3)(3)(thf)(2)] with [HW(CO)(3)Cp] in THF led to the formation of [{CpW(CO)(2)(-CO)}(3)Y(thf)(5)] (5). Reaction of [(Ap*)Y(CH2SiMe3)(2)(thf)] {Ap*H = (2,6-diisopropylphenyl)-[6-(2,4,6-triisopropylphenyl)pyridin-2-yl]amine} with [HW(CO)(3)Cp] in THF was unexpectedly accompanied by the loss of the Ap* ligand and resulted in the formation of 5 too. Isocarbonyl linkage is the dominating interaction between the Y and the W complex moieties. All compounds were characterized by NMR and IR spectroscopy as well as elemental analysis. Complexes 1, 2, 4, and 5 were additionally characterized by X-ray crystal structure analysis (X-ray diffraction).

• 出版日期2014-3