Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, People's Republic of China.
Inorg Chem. 2011 Nov 21;50(22):11813-24. doi: 10.1021/ic2019499. Epub 2011 Oct 27.
The structurally characterized Tp(Me2)-supported rare earth metal monoalkyl complex (Tp(Me2))CpYCH(2)Ph(THF) (1) was synthesized via the salt-metathesis reaction of (Tp(Me2))CpYCl(THF) with KCH(2)Ph in THF at room temperature. Treatment of 1 with 1 equiv of PhC≡CH under the same conditions afforded the corresponding alkynyl complex (Tp(Me2))CpYC≡CPh(THF) (2). Complex 1 exhibits high activity toward carbodiimides, isocyanate, isothiocyanate, and CS(2); treatment of 1 with such substrates led to the formation of a series of the corresponding Y-C(benzyl) σ-bond insertion products (Tp(Me2))CpY[(RN)(2)CCH(2)Ph] (R = (i)Pr(3a), Cy(3b), 2,6-(i)Pr-C(6)H(3)(3c)), (Tp(Me2))CpY[SC(CH(2)Ph)NPh] (4), (Tp(Me2))CpY[OC(CH(2)Ph)NPh] (5), and (Tp(Me2))CpY(S(2)CCH(2)Ph) (6) in 40-70% isolated yields. Carbodiimides and isothiocyanate can also insert into the Y-C(alkynyl) σ bond of 2 to yield complexes (Tp(Me2))CpY[(RN)(2)CC≡CPh] (R = (i)Pr(7a), Cy(7b)) and (Tp(Me2))CpY[SC(C≡CPh)NPh] (9). Further investigation results indicated that 1 can effectively catalyze the cross-coupling reactions of phenylacetylene with carbodiimides. However, treatment of o-allylaniline with a catalytic amount of 1 gave only the benzyl abstraction product (Tp(Me2))CpY(NHC(6)H(4)CH(2)CH═CH(2)-o)(THF) (10), without observation of the expected organic hydroamination/cyclization product. All of these new complexes were characterized by elemental analysis and spectroscopic properties, and their solid-state structures were also confirmed by single-crystal X-ray diffraction analysis.
通过在室温下，在四氢呋喃（THF）中，盐-复分解反应使（Tp（Me2））CpYCl（THF）与 KCH2Ph 反应，合成了结构特征明确的 Tp（Me2）-支持的稀土金属单烷基配合物（Tp（Me2））CpYCH（2）Ph（THF）（1）。在相同条件下，用 1 当量的 PhC≡CH 处理 1，得到相应的炔基配合物（Tp（Me2））CpYC≡CPh（THF）（2）。复合物 1 对碳二亚胺、异氰酸酯、异硫氰酸酯和 CS2 表现出高活性；用这些底物处理 1，导致形成一系列相应的 Y-C（苯甲基）σ-键插入产物（Tp（Me2））CpY[(RN)（2）CCH（2）Ph]（R =（i）Pr（3a），Cy（3b），2,6-（i）Pr-C6H3（3c）），（Tp（Me2））CpY[SC（CH2Ph）NPh]（4），（Tp（Me2））CpY[OC（CH2Ph）NPh]（5）和（Tp（Me2））CpY（S2）CCH2Ph）（6），产率为 40-70%。碳二亚胺和异硫氰酸酯也可以插入 2 的 Y-C（炔基）σ键中，生成配合物（Tp（Me2））CpY[(RN)（2）CC≡CPh]（R =（i）Pr（7a），Cy（7b））和（Tp（Me2））CpY[SC（C≡CPh）NPh]（9）。进一步的研究结果表明，1 可以有效地催化苯乙炔与碳二亚胺的交叉偶联反应。然而，用催化量的 1 处理邻烯丙基苯胺，只得到了苯甲基提取产物（Tp（Me2））CpY（NHC6H4CH2CH═CH2-o）（THF）（10），而没有观察到预期的有机氢胺化/环化产物。所有这些新的配合物都通过元素分析和光谱性质进行了表征，并通过单晶 X 射线衍射分析确定了它们的固态结构。
