钴原子簇化学研究Ⅵ．含2，4－二硫代乙内酰脲分子片卡宾的三核钴羰基硫簇合物的合成

Syntheses of New Trinuclear Cobalt Carbonyl-Sulfur Clusters Containing Carbene Ligands from Cleavage of 2,4-Dithiohydantoins

用Ｃｏ＿２（ＣＯ）＿８与２，４－二硫代乙内酰脲Ｓ＝ＣＮＨＣ（Ｒ＿１）（Ｒ＿２）Ｃ（Ｓ）ＮＨ反应，得到两类６个新的可能具有手征性的三核钴羰基硫簇合物ＣＯ＿３（ＣＯ）＿７（μ＿３－Ｓ）［μ，η￣２－，对它们进行了元素分析、ＩＲ和￣１ＨＮＭＲ谱表征，证明它们的分子骨架为四面体构型，前期配体２，４－二硫代乙内酰脲在反应过程中至少破碎成四种不同分子片，通过Ｃ、Ｎ、Ｓ原子与簇骨架Ｃｏ原子键合。

he syntheses of two kinds including six of the new Co_3-carbonyl clusters,with chiral Co_3Sframework,containing fragmentary heterocyclic 2,4-dithiohydantoins are described.The reactionof Co_2(CO)_8 with 2,4-dithiohydantoin in THF at 20℃ for ca 30 hunder argon gives products Co_3(CO)7(μ_3-S)(1)and Co_3(CO)_6(μ_3-S)[μ,η￣2- (Ⅱ)in which μ,η￣2-S=is a bridging bidentate ligand linked by N and S atom to two cobalts oftriangular Co_3,and:is a heterocyclic terminal earbene ligand linked bycarbon to the third cobalt atom. These clusters have been characterized by elemental analysis,IRand HNMR spectra. The molecule of Ⅱ has a triangular pyramidal Co_3S sleleton and four kinds ofligands namely μ_3-S(4e donor),:(2e donor),μ,η￣2-S=(3e donor)and CO(2e donor).The former three ligands are fragmentsfrom the same reactants 2,4-dithiohydantoin.This ligand precursor was cleaved to afford threekinds of fragments during the reaction with Co_2(CO)_8 and all the fragments are linked to the sameCo_3 by the atom C,N and S atom.