Alkane Elimination Reactions between Yttrium Alkyls and Tungsten Hydrides

Alkane Elimination Reactions between Yttrium Alkyls and Tungsten Hydrides
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烷基钇与氢化钨之间的烷烃消除反应

DOI:
10.1002/ejic.201301476
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发表时间:
2014
影响因子:
2.3
通讯作者:
R. Kempe
R. Kempe
中科院分区:
化学3区
文献类型:
--
作者:
A. P. Sobacynski;J. Obenauf;R. Kempe

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钇单烷基[Cp 2 Y(CH 2SiMe 3)(thf)](Cp = N,thf =四氢呋喃,Me =甲基)与钨双羰基配合物[HW(CO)3Cp]在THF中进行烷烃消除反应,得到三核配合物[{CpW(CO)2(μ-CO)} 2 YCp(thf)3](1)。在反应过程中,每个钇的一个Cp配体被重新分配,从而导致形成[Cp 3 Y]作为副产物。为了避免观察到的配体再分布,研究了其他溶剂。[Cp 2 Y(CH 2SiMe 3)(thf)]与[HW(CO)3Cp]在乙腈中反应得到双核配合物[{CpW(CO)2(μ-CO)} YCp 2(NCMe)2](2)。钇二烷基络合物[Y(CH 2SiMe 3)2(OC 6 H3 tBu 2 - 2,6)(thf)2]与[HW(CO)3Cp]在甲苯中反应,得到高分子化合物[{CpW(CO)2(μ-CO)} 2 Y(OC 6 H3 tBu 2 - 2,6)]n(3),在THF中反应,得到分子化合物[{CpW(CO)2(μ-CO)} 2 Y(OC 6 H3 tBu 2 - 2,6)(thf)3](4)。钇三烷基络合物[Y(CH 2SiMe 3)3(thf)2]与[HW(CO)3Cp]在THF中反应导致形成[{CpW(CO)2(μ-CO)} 3 Y(thf)5](5)。[(Ap*)Y(CH 2SiMe 3)2(thf)] {Ap*H =(2,6-二异丙基苯基)-[6-(2,4,6-三异丙基苯基)吡啶-2-基]胺}与[HW(CO)3Cp]在THF中的反应意外地伴随着Ap* 配体的损失,并导致5 too的形成。异羰基键是Y和W络合物部分之间的主要相互作用。所有化合物均通过核磁共振、红外光谱和元素分析进行了表征。配合物1、2、4和5另外通过X射线晶体结构分析(X射线衍射)表征。
Alkane elimination of the yttrium monoalkyl [Cp2Y(CH2SiMe3)(thf)] (Cp = cyclopentadienyl, thf = tetrahydrofuran, Me = methyl) with the tungsten hydrido carbonyl complex [HW(CO)3Cp] in THF gave rise to the trinuclear complex [{CpW(CO)2(μ‐CO)}2YCp(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)3Cp] in acetonitrile afforded the dinuclear complex [{CpW(CO)2(μ‐CO)}YCp2(NCMe)2] (2). The reaction of the yttrium dialkyl complex [Y(CH2SiMe3)2(OC6H3tBu2‐2,6)(thf)2] with [HW(CO)3Cp] in toluene gave the polymeric compound [{CpW(CO)2(μ‐CO)}2Y(OC6H3tBu2‐2,6)]n(3), whereas reaction in THF gave the molecular compound [{CpW(CO)2(μ‐CO)}2Y(OC6H3tBu2‐2,6)(thf)3] (4). The reaction of the yttrium trialkyl complex [Y(CH2SiMe3)3(thf)2] with [HW(CO)3Cp] in THF led to the formation of [{CpW(CO)2(μ‐CO)}3Y(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)3Cp] in THF was unexpectedly accompanied by the loss of the Ap* ligand and resulted in the formation of5too. 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. Complexes1,2,4, and5were additionally characterized by X‐ray crystal structure analysis (X‐ray diffraction).
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