(μ-巯基)(μ-烃硫)六羰基二铁Michael型反应的研究(Ⅰ)——(μ-β-酯乙基硫)(μ-烃硫)六羰基二铁的合成和鉴定

Studies on Michael-Type Reaction of(μ-Mercapto)-(μ-Alkylthio)Bis(Tricarbonyliron)(Ⅰ)——Synthesis and Characterization of(μ-β-Alkoxycarbonylethylthio)(μ-Alkylthio)-Bis(Tricar bonyliron)

合成了非对称型合μ-β-酯乙基的12个新铁硫原子簇络合物(H-RS)·(μ-P′OCCH_(2)CH_(2)S)Fe_(2)(CO)_(6)。此外还根据硫桥上所连基因,尤其是乙撑基—CH_(2)CH_(2)—的化学位移和积分值,进一步确定了某些络合物的构象休种类及比例。并对反应的某些特点和机理进行了初步讨论。

(μ-Mcrcapto)(μ-alkylthio)bis(trjcarbonyliron),(μ-HS)(μ-RS)Fe_(2)(CO)_(6),pmay be prepared by reaction ofμ-S2Fe_(2)(CO)_(6)with RMgX,followed by F_(2)CCOOHacidolysis of the intermediates,(μ-XMgS)(μ-RS)Fe_(2)(CO)_(6).A piperidine-induced Michad-type reaction of(μ-HS)(μ-RS)Fe_(2)(CO)_(6)can occur withα,β-unsaturated esters,CH_(2)=CHC-OR',to give 12 new Fe-S cluster complexes of unsvm metrical type(μ-R’0CCH_(2)CH_(2)S)(μ-RS)Fe_(2)(CO)_(6),which containμ-β-alk-oxycarbonylethyl group.The data of C/H analysis,IR and ^(1)HNMR for the comlexes are in good agreement with the structures as shown.Conformers and their ratios of some complexes were determined according to the 3 and integrated values of the groups(particularly the ethylene group)bound to sulfur bridges.In addition,some features and mechanism of the reaction have been preliminarily discussed.