(μ-巯基)(μ-烃硫)六羰基二铁Michael型反应的研究(Ⅱ)——(μ-β-腈乙基硫)(μ-烃硫)六羰基二铁的合成及Michael反应机量

Studies on Michael-Type Reaction of(μ-Mercapto)(μ-Alkylthio)Bis(Tricarbonyliron)(Ⅱ)--Synthesis of(μ-β-Cyanoethylthio)(μ-Alkylthio)-bisTricarbonyliron and Mechanism of the Michael-type Reaction

一系列(μ-巯基)(μ-烃硫)六羰基二铁(μ-HS)(μ-RS)Fe_(2)(CO)_(6),在六氢吡啶、三氟醋酸或中性条件下同丙烯腈能发生Michael型反应,生成非对称型含μ-β-腈乙基新颖铁硫原子簇络合物,(μ-RS)(μ-NCCH_(2)CH_(2)S)Fe_(2)(CO)_(6)。确定了所有络合物的结构及某些络合物的构象体种类和比例。并对该反应的自诱导、碱诱导和三氟醋酸抑制反应的机理进行了初步讨论。

A Michael-type reaction of a series of-(μ-mercapto)(μ-alkylthio)bis(tricar-bonyliron)s,(μ-HS)(μ-RS)Fe_(2)(CO)_(6),with acrylonitrile can occur under piperi-dine,trifluoroacetic acid or neutral conditions to afford unsymmetrically novel Fe-S cluster complexes,(μ-NCCH_(2)CH_(2)S)(μ-RS)Fe_(2)(CO)_(6).By elemental analysis,IR and ^(1)HNMR spectroscopy structures of all the complexes were confirmed and the numbers and ratios of the conformers of some complexes were also determined.In addition,mechanisms of the Michaeltype reaction,being base-induced,self-induced and CF_(3)CO_(2)H-repressed,have been preliminarily discussed.