Synthesis of New Transition Metal Carbene Complexes Using the Caracteristics of Hypervalent Sulfur and Its applications

研究了π-硫烷类化合物与低价过渡金属配合物的反应。1.10-S-3四氮杂并环戊二烯衍生物与Pd（PPh_3）_4、Pt（PPh_3）_4和RhCl（PPh_3）_3反应，分别得到[N-M-S]和/或[S-M-S]型（M=Pd、Pt、Rh）的卡宾配合物，同时生成与卡宾配合物等量的三苯基硫化膦.通过X射线衍射分析确定了配合物的结构。[S-Pd-S]型的Pd原子具有由两个硫配体、一个磷配体和一个卡宾配体包围的正方形平面配位结构。通过与[S-Pd-S]型卡宾配合物的光谱数据比较，确定了[N-Pd-S]型卡宾配合物的结构。Pt（II）卡宾配合物的结构与Pd（II）卡宾配合物的结构相似. [N-Pd-S]型卡宾配合物在室温下对空气稳定，但在有机溶剂中不稳定。即[N-Pd-S]型卡宾配合物在回流苯中完全转化为[S-Pd-S]型卡宾配合物. Rh（III）卡宾配合物的X-射线晶体学分析显示了以下结构特征。(i)Rh原子是八面体配位的。(ii)六个配位点被一个氯配体、两个反式膦配体和一个由高价硫释放形成的三齿配体占据。(iii)C（1）-Rh键长与已知的Rh（III）碳烯配合物非常相似。(iv)这种卡宾配合物在空气气氛下是稳定的.三硫杂和硫杂二硒杂二氮戊二烯衍生物还分别与Pd（PPh_3）_4、Pt（PPh_3）_4和RhCl（PPh_3）_3反应，与S=PPh_3一起生成[Y-M-Y]型卡宾配合物（Y=S或Se，M=Pd、Pt、Rh）。

The reactions of pi-sulfurane compounds with low valence transition metal complexes were in investigated. The results obtained are summarized below.1.10-S-3 Tetraazapentalene derivatives reacted with Pd (PPh_3)_4, Pt (PPh_3)_4, and RhCl (PPh_3)_3 to give the carbene complexes of the [N-M-S] and/or [S-M-S] types (M=Pd, Pt, Rh) , respectively, accompanying the formation of triphenyl phosphine sulfide in the same ammount as that of the carbene complexes.2. The structure of carbene complexes was determined by X-ray analysis. The Pd atom of [S-Pd-S] type has a square planar-coordinated structure surrounded by two sulfur ligands, one phosphorus ligand, and one carbene ligand. The structure of carbene complex of [N-Pd-S] type was determined by comparison of its spectral data with those of the carbene complexes of [S-Pd-S] type. The structure of Pt (II) carbene complex was similar to the structure of Pd (II) carbene complex.3. The [N-Pd-S] type-carbene complex is stable to air in solid state but unstable in organic solvents at room temperature. Namely, the [N-Pd-S] type-carbene complex was completely converted into [S-Pd-S] type-carbene complex in refluxed benzene.4. The X-ray crystallographic analysis of Rh (III) carbene complex showed the following structural features. (i) The Rh atom is octahedrally coordinated. (ii) The six coordinated-sites are occupied by one chloro ligand, two trans phosphine ligands, and one tridentate ligand formed by release of hypervalent sulfur. (iii) The C (1)-Rh bond length is very similar to that of known Rh (III) carbene complexes. (iv) This carbene complex is stable under air atmosphere.5. Trithia-and thiadiselena-diazapentalene derivatives also reacted with Pd (PPh_3) _4, Pt (PPh_3) _4, and RhCl (PPh_3) _3 to give the carbene complexes of [Y-M-Y] types (Y=S or Se, M=Pd, Pt, Rh) , respectively, together with S=PPh_3.