Synthesis, Properties and Chemical Functions of Group 8 Transition Metal Nitrosyl Complexes

对标题主题进行了研究，目的是利用新合成的配合物的特征化学性质来开发新的合成反应。特别强调的是eta^3-烯丙基亚硝基腈配合物的化学性质。本研究的主要成果可以总结如下：1。（eta^3-烯丙基）Fe(CO)_2NO配合物1可由烯丙基卤化物高效合成，（eta^3-1-三甲基硅氧基）Fe(CO)_2NO配合物2可由α， β -不饱和羰基化合物合成，（eta^3-2-三甲基硅氧基）Fe(CO)_2NO配合物3可由α -卤羰基化合物合成，[eta^3-1-（酰基甲基）-烯丙基]Fe(CO)_2NO配合物4可由1,3 -二烯合成，（eta^3-1-乙酰氧基）Fe(CO)_2NO配合物5可用Bu_4N^+[Fe(CO)_3NO]^-作为试剂可由alkenyloxiranes合成。2. 所有这些配合物都与碳亲电试剂和亲核试剂反应，具有很高的区域选择性。3. 这些配合物表现出有趣的反应性特征。的详细研究表明,配合物1可以作为综合利用等效合成纤维的allylcations allylanions,配合物2作为beta-acylcarbocations beta-acylcarbanions,这些复合物3作为alpha-acylcarbocations alpha-acylcarbanions,这些配合物4作为中间体1,4-functionalization 3-dienes,复合物的5作为multifunctionalized醇的合成中间体。4. 1,2,3和4的烯丙基配体与α， β -不饱和羰基化合物进行共轭加成，形成多种具有高选择性的多功能化化合物。5. 铁配合物与碳亲电试剂和亲核试剂的反应是通过两种不同的立体化学过程进行的，这两种反应的区域选择性和立体选择性通常都很高。

The title subjects have been studied with the intention of developing new synthetic reactions by utilizing characteristic chemical properties of newly synthesized complexes. The special emphasis has been placed on the chemistry of eta^3-allylnitrosyliron complexes. The major outcomes of this research can be summarized as follows :1. (eta^3-Allyl)Fe(CO)_2NO complexes 1 can be synthesized efficiently from allylic halides, (eta^3-1-trimethylsiloxyallyl)Fe(CO)_2NO complexes 2 from alpha, beta-unsaturated carbonyl compounds, (eta^3-2-trimethylsiloxyallyl)Fe(CO)_2NO complexes 3 from alpha-halocarbonyl compounds, [eta^3-1-(acylmethyl)-allyl]Fe(CO)_2NO complexes 4 from 1, 3-dienes, and (eta^3-1-acetoxyallyl)Fe(CO)_2NO complexes 5 from alkenyloxiranes by using Bu_4N^+[Fe(CO)_3NO]^- as a reagent. 2. All these complexes react with both of carbon electrophiles and carbon nucleophiles with a high regio-selectivity. 3. These complexes exhibit interesting reactivity features. The detailed studies have shown that the complexes 1 can be utilized as synthetically equivalent synthons for both of allylcations and allylanions, the complexes 2 as those for both of beta-acylcarbocations and beta-acylcarbanions, the complexes 3 as those for both of alpha-acylcarbocations and alpha-acylcarbanions, the complexes 4 as intermediates for 1, 4-functionalization of 1, 3-dienes, and the complexes 5 as intermediates for the synthesis of multifunctionalized alcohols. 4. The allylic ligands of 1, 2, 3, and 4 undergo a conjugate addition to alpha, beta-unsaturated carbonyl compounds, affording a variety of multifunctionalized compounds with a high selectivity. 5. The reactions of the iron complexes with carbon electrophiles and carbon nucleophiles proceed via two different, distinctive stereochemical courses, and the regio- and stereo-selectivities of both the reactions are generally high.