钴原子簇化学研究 Ⅷ.含桥基2-硫代乙内酰脲分子片配位及杂环卡宾的三核钴羰基硫簇合物的合成和结构

Synthese and Structure of Sulfuro --Trinuclear Cobalt Carbonyl Cluster Containing Bridging 2 Thiohydantoin and Heterocyclic Carbene

用乙酸、硫氰化铵与氨基酸反应，得到４个２－硫代乙内酰脲配体Ｓ＝ＣＮＨＣ（Ｏ）ＣＨ（Ｒ）Ｎ↓Ｈ，它们分别与Ｃｏ２（ＣＯ）８反应，合成出两类４个三核钴羰基硫簇合衍生物：Ｃｏ３（ＣＯ）７（μ３－Ｓ）〔μ－η２－ＳＣ＝ＮＣ（Ｏ）ＣＨ（Ｒ）Ｎ↓Ｈ（Ｉａ，Ｉｂ）和Ｃｏ３（ＣＯ）６（μ３－Ｓ）（μ－η２－ＳＣ＝ＮＣ（Ｏ）ＣＨ（Ｒ）Ｎ↓Ｈ）（：ＣＮＨＣ（Ｏ）ＣＨ（Ｒ）Ｎ↓Ｈ）（Ⅱｃ，Ⅱｄ）．对４个族合物进行了元素分析、ＩＲ谱、１ＨＮＭＲ和ＭＳ表征，并推测出它们的分子结构．

The former ligand 2 thiohydantoins were synthesized from acetic acid,NH 4SCD and α aminoacid.The reaction of Co 2(CO) 8 with four 2 thiohydantoins gives two kinds of four sulfuro trinuclear cobalt carbonyl clusters:Co 3(CO) 7( μ 3 S) μ-η 2 SCNC(O)CH(R)NH(I) and Co 3(CO) 6( μ 3 -S)( μ-η 2- SC=NC(O)CH(R)NH)(:CNHC(O)CH(R)NH)(Ⅱ),in which μ-η 2- SC=NC(O)CH(R)NH) is a three electron bridging ligand linked by S and N to two cobalts,and :CNHC(O)CH(R)NH is a two electrons heterocyclic carbene ligand.The structure of the molecular framework Co 3S of the clusters is trigonal pyramid.These four clusters have been characterized by IR, 1HNMR、MS and elementary analysis.