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

研究了低价态过渡金属络合物与吡喃类化合物的反应。结果如下：1.10-S-3四氮杂戊烯衍生物分别与Pd(PPh_3)_4、Pt(PPh_3)_4和RhCl(PPh_3)_3反应生成[N-M-S]和/或[S-M-S]型(M=Pd、Pt、Rh)的卡宾络合物，同时生成与卡宾络合物相同摩尔比的三苯基膦硫化物。通过X-射线分析确定了卡宾配合物的结构。[S-Pd-S]型钯原子具有两个硫配体、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-钯-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。铂(II)卡宾络合物的结构与Pd(II)卡宾络合物的结构相似。[N-Pd-S]型卡宾络合物在室温下对空气稳定，在有机溶剂中不稳定。即在回流苯中，[N-Pd-S]型卡宾络合物完全转化为[S-Pd-S]型卡宾络合物。Rh(III)卡宾配合物的X-射线单晶分析显示出以下结构特征。(I)Rh原子为八面体配位。(Ii)六个配位位被一个氯配体、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。(3)C(1)-Rh键长与已知的Rh(III)卡宾络合物的键长非常相似。(4)该卡宾络合物在空气中是稳定的。三氧化二铁和硫杂硒-重氮戊烯衍生物还分别与Pd(PPh_3)_4、Pt(PPh_3)_4和RhCl(PPh_3)_3反应，得到了[Y-M-Y]型(Y=S或Se，M=Pd，Pt，Rh)的卡宾配合物，S=PPh_3。

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.