HIGHLY SELECTIVE CARBON BOND FORMING REASTIONS BY MEANS OF DESIGNED LIGAND FIELDS OF RUTHENIUM

(1)由（C_5M_<e5>）RuCl（二烯）和银离子衍生的阳离子物种是丁二烯或异戊二烯[4+4]环二聚的高选择性催化剂。通过单晶X射线分析明确地确定了中间体1，3，7-辛三烯络合物的结构。在1，3-戊二烯的情况下，二烯的区域选择性线性二聚通过双（π-烯丙基）钌（IV）中间体的方式发生，该中间体的结构被确定。通过X射线分析。八元碳环的形成是由铼诱导配位的1，3，7-辛三烯配体形成C-C键的金属配位机理来解释的。(2)以2，5-二[4 '-（S）-异丙恶唑啉-2'-基]吡啶（ip-pybox）为三齿手性助剂的二氯乙烯钌（II）配合物催化重氮乙酸烷基酯与末端烯烃的不对称环丙烷化反应，具有很高的立体选择性和对映选择性.乙烯，一氧化碳 ...更多信息 氧化物和含RuC_（12）（pybox）片段的卡宾配合物，并对其结构和化学行为进行了研究，以阐明合理的机理。由（C_5M_）Ru碎片衍生的类卡宾钌（II）<e5>催化剂是一种有效的催化剂。(3)配合物Ru（COD）（COT）（COT= 1，3，5-环辛三烯; COD= 1，5-环辛二烯）能诱导两个丙炔酸烷基酯分子发生新的双环加成反应。一个炔以[6+2]环加成方式加成到COT配体上，而另一个炔以[2+2+2]环加成方式加成到COD配体上，最终形成双环[4.2.2]癸二烯骨架。(4)并苯乙炔或并蒽乙炔配体与三核铼羰基簇表面配位后经一氧化碳处理，得到了具有fulven部分结构的新的4，5-二氢衍生物。(5)合成<60>了过渡金属片段的新型C_2配合物，为C-C键的选择性形成开辟了新的配位场。少

(1) The cationic species derived from (C_5M_<e5>) RuCl (diene) and silver ion was founde to be highly selective catalysts for [4+4] cyclodimerization of butadiene or isoprene. The structure of an intermediate 1,3,7-octatriene complex was determined unequivocally by single crystal X-ray analysis. In the case of 1,3-pentadiene, regioselective linear dimerization of the diene took place by way of a bis (pi-allylic) ruthenium (IV) intermediate which structure was determined. by X-ray analysis. Formation of eight-membered caarbocyles is explained in terms of a metallacycle mechanism invovling rethenium induced C-C bond formation of the coordinated 1,3,7-octatriene ligand.(2) A dichloro (ethelene) ruthenium (II) complex involving designed terdentate chiral auxiliary, 2,5-bis [4'- (S)-isoproploxazolin-2'-yl] pyrdine (ip-pybox) was found to be highly stereo-and enantio-selective catalyst for asymmetric cyclopropanation of terminal alkenes with seberal alkyl diazoacetates. Ethylene, carbon mono … More xide, and carbene complexes involving the RuC12(pybox) fragment were prepared, and the structures and thier chemical behavior was studied in order to elucidate reasonable mechanism. Ruthenium (II) carbenoid species derived from (C_5M_<e5>) Ru fragments were found to be efficient catalyst for metathesis polymerization of norbornene.(3) The complex, Ru (COD) (COT), COT=1,3,5-cyclooctatriene ; COD=1,5-cyclooctadiene, induced new double cycloaddition towards two melecules of alkyl propiolates. One alkyne added to the COT ligand in a [6+2] cycloaddition mode, whereas the other to the COD ligand in a [2+2+2] one, to result in the final formation of bicyclo [4.2.2] decadiene framework.(4) Hydrogenation of acenephtylene or aceanthrylene ligands facially coordinarted to the trinuclear rethenium carbonyl cluster followed by treatment with carbon monoxide furnished new 4,5-dihydro derivatives with a fulven partial structure.(5) New C_<60> complexes of transition metal fragments were prepared in order to develop new ligand fields for selective C-C bond formation. Less