Ruthenium/zirconium complexes containing C2 bridges with bond orders of 3, 2, and 1. Synthesis and structures of Cp(PMe3)2RuCHnCHnZrClCp2 (n = 0, 1, 2)
Ruthenium/zirconium complexes containing C2 bridges with bond orders of 3, 2, and 1. Synthesis and structures of Cp(PMe3)2RuCHnCHnZrClCp2 (n = 0, 1, 2)
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DOI：
10.1021/ja00022a039
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发表时间：
1991-10
影响因子：
15
通讯作者：
F. R. Lemke;D. Szalda;R. Bullock
中科院分区：
文献类型：
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作者：
F. R. Lemke;D. Szalda;R. Bullock
合成了一系列以C2键3、2和1键连接的Ru/Zr络合物，并用光谱分析和单晶X射线衍射法对其进行了表征。通过Cp(PMe3)2RuC=CH与Cp2Zr(CH3)Cl或Cp2Zr(NMe2)Cl反应，合成了双金属炔络合物Cp(PMe3)2RuC=CZrClCp2。这是第一个结构表征的炔的例子，它的一端被富电子的金属取代，另一端被缺电子的金属取代。Cp(PMe3)2RuC^CH与[Cp2Zr(H)Cl]“反应生成了双金属配合物Cp(PMe3)2RuCH=CHZrClCp2，它与乙烯基CH(PMe3)2RuCH之间存在三中心、两电子的无规相互作用。Cp(PMe3)2RuCH=CHZrClCp2与1 atm的CO反应生成ij2-酰基配合物Cp(PMe3)2RuCH=CHC(0)ZrClCp2。对该酰基化合物的光谱和结构数据的分析表明，两性离子共振形式在Ru上具有正式的正电荷，而在Zr部分具有负电荷，这是一种重要的贡献。Cp(PMe3)2RuCH=CHZrClCp2的水解反应生成已知的锆络合物[Cp2ZrCl20]20和Ru的乙烯基络合物Cp(PMe3)2RuCH=CH2。[Cp2Zr(H)Cl]“与Cp(PMe3)2RuCH=CH2反应生成双金属烷烃配合物Cp(PMe3)2RuCH2CH2ZrClCp2。光谱和结晶学数据的解释表明，该化合物也有一个原子之间的相互作用，其中的一个或两个以上的金属通过碳氢桥连接的有机金属络合物已被广泛研究作为物种的模型假定存在于几个重要的金属催化反应。*1详细研究这些可溶的络合物中金属-碳和碳-碳键的形成和断裂的方式可以提供有用的信息比较类似的过程发生在均相催化反应和在金属表面上。亚甲基桥联
A series of Ru/Zr complexes linked by C2 bridges of bond orders 3, 2, and 1 were prepared, and characterized by spectroscopic data and single-crystal X-ray diffraction. The dimetalioalkyne complex Cp (PMe3) 2RuC= CZrClCp2 was prepared by the reaction of Cp (PMe3) 2RuC= CH with either Cp2Zr (CH3) Cl or Cp2Zr (NMe2) Cl. This dimetalioalkyne is the first example of a structurally characterized alkyne that is substituted by an electron-rich metal at one end, and by an electron-deficient metal at the other. The reaction of Cp (PMe3) 2RuC^ CH with [Cp2Zr (H) Cl]„gives the dimetalloalicene complex Cp (PMe3) 2RuCH= CHZrClCp2, which has a three-center, two-electron agostic interaction between the Zr and the vinylic CH that is ß to Zr. Carbonylation of Cp (PMe3) 2RuCH= CHZrClCp2 with 1 atm of CO produces the ij2-acyl complex Cp (PMe3) 2RuCH= CHC (0) ZrClCp2. Analysis of the spectroscopic and structural data for this acyl compound indicates a substantial contribution from a zwitterionic resonance form that has a formal positive chargeat Ru and a negative charge on the Zr portion. Hydrolysisof Cp (PMe3) 2RuCH= CHZrClCp2 produces the known zirconium complex [Cp2ZrCl] 20 and the ruthenium vinyl complex Cp (PMe3) 2RuCH= CH2. Reaction of [Cp2Zr (H) Cl]„with Cp (PMe3) 2RuCH= CH2 gives the dimetalloalkane complex Cp (PMe3) 2RuCH2CH2ZrClCp2. Spectroscopic and crystallographic data are interpreted to indicate that this compound also has an agostic interaction between the Zr and a CH adjacentto Ru.Organometallic complexes in which two or more metals are linked by a hydrocarbon bridge havebeen studied extensively as models for species postulated to be present in several important metal-catalyzed reactions.* 1 Detailed investigations of the ways in which metal-carbon and carbon-carbon bonds are made and broken in these soluble complexes can provide useful information for comparison to similar processes that occur in homogeneous catalytic reactions and on metal surfaces. Methylene-bridged