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

金属-卡宾配合物的合成及其反应活性的研究已被广泛开展。研究了镍基环丁烷生成的镍-卡宾配合物与不同取代烯烃的反应活性。由铂(II)络合物与双环[1.1.0]丁烷反应生成了新的烯丙基卡宾-铂配合物，表明这些络合物是过渡金属催化双环[1.1.0]丁烷分子内和分子间反应的重要中间体。用茂钛-乙烯配合物与6、7族金属羰基反应，合成了一系列钛氧基卡宾-金属羰基配合物，阐明了这些配合物的结构-活性关系，研究了生成卡宾、硅烯和锗的新方法，并利用这些活性物种进行了有机合成。…生成的1-卤代环丙基锌酸锂的制备及反应对较多的1，1-二溴环丙烷进行了研究。利用该试剂实现了GEM-二取代环丙烷的立体选择性合成。研究了在CS_2存在下，O-(重氮乙酰基)苯甲酸酯的催化分解反应，得到了独特的2：1-加合物。α，α-氯氟烷基亚砜与格氏试剂进行亲核脱氢反应，得到烷基氟碳化合物，在碘化铜(I)存在下，烷基氟碳化合物坍塌为顺式氟烯烃。二氮杂环丙烷或氮杂二氮杂三氮杂环丙烷是由二氢化二氢呋喃与重氮甲烷或β-苯叠氮化物反应生成的。通过重氮化合物的光化学分解发现了芳基卡宾的一些新的有趣的性质。邻位含甲氧基的二苯基卡宾的反应模式对支撑甲氧基的间烷基团悬在卡宾中心上非常敏感。通过9-(2-重氮甲基-1-萘基)菲的光解反应研究了芳基卡宾的构象对反应活性的影响，并对卡宾的反应进行了理论研究。用分子轨道计算方法研究了单线态卡宾与烯烃的加成反应及取代基对反应的影响。较少

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