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首页> 外文期刊>Chemistry: A European journal >Edge-Bridging and Face-Capping Coordination of Alkenyl Ligands in Triruthenium Carbonyl Cluster Complexes Derived from Hydrazines:Synthetic,Structural,Theoretical,and Kinetic Studies
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Edge-Bridging and Face-Capping Coordination of Alkenyl Ligands in Triruthenium Carbonyl Cluster Complexes Derived from Hydrazines:Synthetic,Structural,Theoretical,and Kinetic Studies

机译：肼衍生的三钌羰基簇络合物中烯基配体的桥接和封端配位：合成，结构，理论和动力学研究

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The reactions of the triruthe-nium cluster complex [Ru_3(mu-H)(mu_3-eta~2-HNNMe_2)(CO)_9](1;H_2NNMe_2 = l,l-dimethylhydrazine)with alkynes(PhC(ident to)CPh,HC(ident to)CH,MeO_2CG(ident to)CCO_2Me,PhC(ident to)CH,MeO_2CC(ident to)CH,HOMe_2CCC(ident to)CH,2-pyG(ident to)CH)give tri-nuclear complexes containing edge-bridging and/or face-capping alkenyl li-gands.Whereas the edge-bridged products are closed triangular species(three Ru-Ru bonds),the face-capped products are open derivatives(two Ru-Ru bonds).For terminal alkynes,products containing gem(RCCH_2)and/or trans(RHCCH)alkenyl ligands have been identified in both edge-bridging and face-capping positions,except for the complex [Ru_3(mu_3-eta~2-HNNMe_2)(mu_3-eta~3-HCCH-2-py)(eta-CO)(CO)_7],which has the two alkenyl H atoms in a cis ar-rangement.Under comparable reaction conditions(1:1 molar ratio,THF at reflux,time required for the consumption of complex 1),some reactions give a single product,but most give mixtures of isomers(not all the possible ones),which were separated.To determine the effect of the hy-drazido ligand,the reactions of [Ru_3(mu-H)(mu_3-eta~2-MeNNHMe)(CO)_9](2;HMeNNHMe = 1,2-dimethylhydrazine)with PhC(ident to)CPh,PhC(ident to)CH,and HC(ident to)CH were also studied.For edge-bridged alkenyl complexes,the Ru-Ru edge that is spanned by the alkenyl ligand depends on the position of the methyl groups on the hydrazido ligand.For face-capped alkenyl complexes,the relative orientation of the hydrazido and alkenyl ligands also depends on the position of the methyl groups on the hydrazido ligand.A kinetic analysis of the reaction of 1 with PhG(ident to)CPh revealed that the reaction follows an associative mechanism,which implies that incorporation of the alkyne in the cluster is rate-limiting and precedes the release of a CO ligand.X-ray diffraction,IR and NMR spectroscopy,and calculations of minimum-energy structures by DFT methods were used to characterize the products.A comparison of the absolute energies of isomeric compounds(obtained by DFT calculations)helped rationalize the experimental results.
机译：三钌簇复合物[Ru_3（mu-H）（mu_3-eta〜2-HNNMe_2）（CO）_9]（1; H_2NNMe_2 = 1，l-二甲基肼）与炔烃（PhC（与）CPh的反应） ，HC（与CH相同），MeO_2CG（与CCO_2Me相同），PhC（与CH相同），MeO_2CC（与CH相同），HOMe_2CCC（与CH相同，2-pyG（与CH相同））得到三核配合物包含桥接的和/或具有封端的烯基配体。封边的产物是封闭的三角形物质（三个Ru-Ru键），而具有封端的产物是开放衍生物（两个Ru-Ru键）。末端炔烃，含有gem（RCCH_2）和/或反式（RHCCH）烯基配体的产物已在边缘桥连和封盖位置被鉴定，除了复合物[Ru_3（mu_3-eta〜2-HNNMe_2）（mu_3- η〜3-HCCH-2-py）（eta-CO）（CO）_7]，它具有两个顺式排列的烯基H原子。在可比的反应条件下（1：1摩尔比，THF回流，消耗配合物1）所需的时间，有些反应只能生成一种产物，而大多数只能生成异构体的混合物（并非全部） [Ru_3（mu-H）（mu_3-eta〜2-MeNNHMe）（CO）_9]（2; HMeNNHMe = 1还研究了具有PhC（与CPh相同），PhC（与CH）相同和HC（与CH）相同的2-二甲基肼。对于边缘桥连的烯基配合物，Ru-Ru边缘被烯基配体跨越取决于肼基配体上甲基的位置。对于具有封端的烯基配合物，肼基和烯基配体的相对取向也取决于肼基配体上甲基的位置。具有PhG（与CPh相同）的图1揭示了该反应遵循缔合机制，这意味着炔烃在团簇中的掺入是限速的，并且先于CO配体的释放。并用DFT方法计算最小能量结构来表征产物。绝对能量的比较异构体化合物（通过DFT计算获得）有助于合理化实验结果。

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