亚钌的

This article reviews recent progress in nucleophilic reactions of theα- carbon in vinylidene ruthenium complexes.

综述了近几年钌亚乙烯基络合物中间体α碳的亲核反应。

This article reviews recent progress in nucleophilic reactions of the α-carbon in vinylidene ruthenium complexes.

文摘：综述了近几年钌亚乙烯基络合物中间体α-碳的亲核反应。

This article reviews recent progress in nucleophilic reaction s of the a - carbon in vinylidene ruthenium complexes.

综述了近几年钌亚乙烯基络合物中间体α-碳的亲核反应。

In the photolysis of 9, phosphine dissociation is followed by addition of HCl yielding the neutral vinylidene complex Cl[Ru1]=C=CHC(CCl3)2 10, [Ru1] = Cp

当进行光裂解错合物的反应时，在加入氯化氢分子的状况下，产生一个中性的钌金属亚乙烯基错化合物Cl[Ru1]=C=CHC(CCl3)2 10， [Ru1] = Cp(PPh3Ru 并且伴随著一个三苯基磷分子的离去。

In order to develop an useful synthestic process, we have synthesized amides with various substitutents. The isoquinoline skeleton was constructed through Bischler-Napieralski reaction, followed by asymmetric reduction of the imine intermediates with a Ru complex to form the only chiral center. Finally, we connected the two phenyl groups by Heck reaction and effectively obtained optically active aporphine alkaloids.

为了发展一套实用的合成方法，我们首先制备於苯环上具有不同种取代基的苯乙醯胺，接著透过Bischler-Napieralski反应进行分子内合环，并利用钌金属对亚胺中间体进行不对称的还原反应，建立出产物中唯一的光学活性中心，最后再利用Heck反应连结两个苯环，就可以顺利得到具有光学选择性的阿朴吩类天然物。

In this dissertation, synthesis of benzylidene[1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene]dichlororuthenium (41) has been improved.

本论文首先改进了钌卡宾配合物[1，3-二-(2，6-甲苯基)-4，5-二氢咪唑基]-苯亚甲基-三苯基膦-二氯合钌(41)的合成方法。

It isconfirmed by ~1H NMR,~(13)C NMR and X-ray crystallographic analysis that complexes 60-63are monopyridine complexes and show distorted square pyramid geometries; complexes 64and 65 are bispyridine complexes and show pseudo-octahedral geometries, where twopyridine ligands are in cis arrangement and trans to the NHC and the benzylidene ligandrespectively, the bond length between ruthenium and pyridine ligand trans to the benzylideneligand is 16 pm longer than the bond length between ruthenium and pyridine ligand trans tothe NHC ligand.

1H NMR、~(13)C NMR及X射线单晶衍射分析证明，配合物60-63是单吡啶衍生物配位的钌卡宾配合物，具有变形的四方锥构型；配合物64、65为双吡啶衍生物配位的钌卡宾配合物，具有变形的八面体构型，其中两个顺式配位的吡啶衍生物分别处于氮杂环卡宾和苯亚甲基的反位，处于苯亚甲基反位的吡啶衍生物对应的钌-氮键长要比处于氮杂环卡宾反位的长出16 pm。

New ruthenium benzylidene complexes benzylidene[1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene] [k~2-diphenylphosphinoacetato] monochlororuthenium (46), benzylidene[1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene][k~2-3-propionato]monochlororuthenium (47), benzylidene[1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene] [k~2-2-benzonato]monochlororuthenium (48) featured five-membered, flexible six-membered and rigidsix-membered chelating rings respectively are prepared by reactions of complex 41 withcorresponding sodium phosphino-carboxylates. It is confirmed by X-ray crystallographicanalysis that the coordination geometries of complexes 46 and 47 are distorted squarepyramids with phosphino-carboxylate ligands chelating to ruthenium, and the coordinationbetween ruthenium and benzylidene ligands are strengthened.

用二苯基瞵乙酸盐、二苯基膦丙酸盐、二苯基膦苯甲酸盐与钌卡宾配合物41反应合成了三个新的钌卡宾配合物：含五元膦-氧螯合环的1，3-二-(2，6-二甲苯基)-4，5-二氢咪唑基1-苯亚甲基--一氯合钌(46)、含六元柔性膦-氧螯合环的[1，3-二-(2，6-二甲苯基)-4，5-二氢咪唑基1-苯亚甲基--一氯合钌(47)及含六元刚性膦-氧螯合环的[1，3-二-(2，6-二甲苯基)-4，5-二氢咪唑基]-苯亚甲基--一氯合钌(48)。X射线单晶衍射分析证明，配合物46、47都为变形的四方锥构型，膦-氧与钌形成螯合配位，其中苯亚甲基与钌的配位得以加强。

Benzylidene[1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene]dichloro(2-methylpyridine)ruthenium (62), benzylidene[1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene] dichloro(2,4-dimethylpyridine)ruthen ium (63) introduce ortho substituted pyridine as dissociating ligand to weaken Ru-N bondand accelerate dissociation of pyridine derivative ligand through steric hindrance.

在钌卡宾配合物[1，3-二-(2，6-二甲苯基)-4，5-二氢咪唑基]-苯亚甲基-(2-甲基吡啶)-二氯合钌(62)，1，3-二-(2，6-二甲苯基)-4，5-二氢咪唑基1-苯亚甲基-(2，4-二甲基吡啶)-二氯合钌(63)中，邻位取代的吡啶作为解离配体，通过邻位基团的空间效应削弱钌-氮配位键，使配体更易解离，提高了催化剂的初活性。

With Death guitarist Schuldiner adopting vocal duties, the band made a major impact on the scene.

随着死亡的吉他手Schuldiner接受主唱的职务，乐队在现实中树立了重要的影响。

But he could still end up breakfasting on Swiss-government issue muesli because all six are accused of nicking around 45 million pounds they should have paid to FIFA.

不过他最后仍有可能沦为瑞士政府&议事餐桌&上的一道早餐，因为这所有六个人都被指控把本应支付给国际足联的大约4500万英镑骗了个精光。