Chemical Behaviors and Synthetic Applications of Hypovalent Organic Metastable Species Under WellーControlled Conditions

金属-碳配合物的合成及其反应性的研究得到了广泛的开展。研究了由镍环丁烷生成的镍卡宾配合物对不同取代烯烃的反应性。Pt （II）配合物与双环[1.1.0]丁烷反应生成了新的烯丙基碳铂配合物，表明这些配合物是过渡金属催化的双环[1.1.0]丁烷分子内和分子间反应的重要中间体。用6、7基团的金属羰基对二茂钛-乙烯配合物进行处理，制备了一类钛氧羰基-金属羰基配合物，并对这些配合物的结构-反应性关系进行了研究。合成碳烯、硅烯和革烯的新方法得到了广泛的研究，这些活性物质已被用于有机合成。研究了以1,1 -二溴环丙烷为原料合成1-卤代环丙基锌酸锂的制备及反应。利用该试剂实现了宝石二取代环丙烷的立体选择性合成。研究了烷基O-（重氮乙酸）苯甲酸酯在CS_2存在下的催化分解反应，得到了独特的2:1加合物。α， α -氯氟烷基亚砜用格氏试剂亲核脱硫，得到烷基氟化苯，在碘化铜(I)存在下分解成顺式氟烯烃。由双双烯与重氮甲烷或^-苯基叠氮化物反应生成双双烯烷或氮杂双烯嘧啶。研究了这些化合物的分子结构和反应性。通过重氮化合物的光化学分解，发现了芳基碳烯的一些新的有趣性质。邻位含甲氧基取代基的二苯基羰基的反应模式对支撑甲氧基悬于羰基中心的间位烷基非常敏感。通过对9-（2-重氮甲基-1-萘基）芴的光解反应，研究了芳烃构象对反应活性的影响。对碳烯的反应也进行了理论研究。用MO计算方法研究了单线态碳烯在烯烃中的加成反应及取代基对这类反应的影响。少

Researches on syntheses and reactivities of metal-carbene complexes have been carried out extensively. Reactivities of Ni-Carbene complexes generated from nickellacyclobutane toward various substituted olefins have been investigated. New allylcarbene-Pt complexes have been generated by the reaction of Pt (II) complexes and bicyclo [1.1.0] butanes and showed that these complexes are important intermediates in the intra- and intermolecular reaction of bicyclo [1.1.0] butanes catalyzed by transition metals. A family of titanoxycarbene-metal carbonyl complexes has been prepared by the treatment of titanocene-ethylene complex with metal carbonyls of group 6 and 7, and structure-reactivity relationship of these complexes has been elucidated.New methodologies for the generation of carbenes, silylenes, and germylenes have been widely studied and these reactive species have been utilized for organic syntheses. Preparation and reaction of lithium 1-halocyclopropylzincates which are generated fro … More m 1, 1-dibromocyclopropanes were studied. Stereoselective synthesis of gem-disubstituted cyclopropanes was realized by utilizing the above reagent. The catalytic decomposition of alkyl O- (diazoacety) benzoates in the presence of CS_2 was studied and unique 2 : 1-adducts were obtained. alpha, alpha-Chlorofluoroalkyl sulfoxides undergo nucleophilic desulfinylation with a Grignard reagent to give alkylfluorocarbenoids which collapse into cis-fluoroalkenes in the presence of copper (I) iodide. Digermiranes or azadegermiridines were produced from the reaction of digermene with diazomethane or^- phenyl azide. Molecular structures and reactivities of these compounds were also investigated.Several new interesting properties of arylcarbenes have been discovered by the photochemical decomposition of diazo compounds. The reaction modes of diphenylcarbenes bearing methoxy substituents at ortho position are shown to be very sensitive to the meta-alkyl groups which buttress the methoxy group to hang over he carbenic center. Effect of the conformations of the arylcarbenes on the reactivity was shown by the photolysis of rotameric 9- (2-diazomethyl-1-naphthyl) fluorenes.Theoretical studies on the reactions of carbenes have also been done. Addition of singlet carbenes to olefins and effects of substituents on this type of reaction were studied by means of MO calculation. Less