Synthesis and Reaction of Metal Complexes Containing Sulfur, Selenium, and Tellurium donor atoms.

制备了含有2-吡啶烯酸酯（pySe）、[Co(pySe) (en)_2]^<2+>、[Co(pySe) (bpy)_2]^<2+>、[Co(pySe) _2 (bpy)]^+、fac- [Co(pySe) _3]的新型混合钴（III）配合物，并用电子能谱、圆二色光谱、核磁共振谱对其进行了表征。自发分解的[Co (pySe) (en)_2] (CIO_4)_2配合物具有正交空间群P2_1 - 2_1 - 2_1， a=12.316 (3), b=13.012 (2), c=11.728 (3) a， Z=4。2845反射（Mo Kalpha辐射）的细化得到R=0.056。Co-N反式键比顺式键长0.045 A。类似的2-吡啶硫代酸盐（pyS）的硫代酸盐诱导的反式影响小于目前的pySe。三（pySe）配合物表面硒酸盐基团的几何配位偏好。同时，还制备了新的铑（III）配合物[Rh(pySe) _2(PPh_3)_2]^+和[Rh(pySe)_3]。制备了新的钯（II）配合物[PdCl_2(pySeBz)_2]和[PdCl_2(pySBz)_2] （pySeBz和pySBe分别表示（2-吡啶基）苄基硒化物和（2-吡啶基）苄基硫化物）。[PdCl_2(Me_2S)]在固体状态下通过PdCl （SMe）作为中间体热解生成PdS。另一方面，配合物[PdCl_2(pySeBz)_2]和[PdCl_2(pySBz)_2]在固态下热解生成[Pd(pySe)_2]和[Pd(pyS)_2]。而[PdCl_2(pySeBz)_2]在CHCl_3溶液中室温再结晶得到[PdCl_2(pySepy-N，N')] （pySepy为2,2'-二吡啶基硒化物），X射线结构分析证实了这一点。这种新型的配体偶联过渡金属配合物将为有机合成提供一条有用的途径。

The new mixed cobalt (III) complexes containing 2-pyridineselenolate (pySe), [Co(pySe) (en)_2]^<2+>, [Co (pySe) (bpy)_2]^<2+>, [Co (pySe)_2 (bpy)]^+, fac- [Co (pySe)_3] were prepared and characterized by their electronic spectra, circular dichroism spectra, NMR spectra. The [Co (pySe) (en)_2] (CIO_4)_2 complex, which was spontaneously resolved, had an orthorhombic space group of P2_1 2_1 2_1, with a=12.316 (3), b=13.012 (2), c=11.728 (3) A,and Z=4. The refinement of 2845 reflections (Mo Kalpha radiation) led to R=0.056. The Co-N bond trans to the pySe selenium atom was longer by 0.045 A than the cis one. The trans influence induced by the thiolate of the similar 2-pyridinethiolate (pyS) is less than the present pySe's one. The geometrical ligand site preference of selenolate groups which are located at fac geometry in the tris (pySe) complex. Also, the new rhodium (III) complexes, [Rh (pySe)_2(PPh_3)_2]^+, fac- [Rh(pySe)_3] were prepared.The new palladium (II) complexes [PdCl_2(pySeBz)_2] and [PdCl_2(pySBz)_2] were prepared (pySeBz and pySBe denote (2-pyridyl) benzylselenide and (2-pyridyl) benzylsulfide). The pyrolysis of [PdCl_2(Me_2S)] in the solid state was resulted in PdS through the PdCl (SMe) as an intermediate. On the other hand, the pyrolyses of the complexes [PdCl_2(pySeBz)_2] and [PdCl_2(pySBz)_2] in the solid state were resulted in [Pd (pySe)_2] and [Pd(pyS)_2], respectively. The recrystalization from CHCl_3 solution of [PdCl_2(pySeBz)_2] at the room temperature was, however, resulted in [PdCl_2(pySepy-N,N')] (pySepy denotes 2,2'-dipyridylselenide), which was confirmed by X ray structural analysis. This novel ligand-coupling in the transition metal complex will give a useful organic synthesis route.