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

含有硫、硒和碲供体原子的金属配合物的合成和反应。

• 批准号: 06640727
• 负责人: KITA Masakazu
• 金额: $ 1.41万
• 依托单位: Naruto University of Education
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06640727/
• 关键词: Cobalt (III) Complexes; Rhodium (III) Complexes; Palladium (II) Complexes; Trans influence; Selenolate Lingnd; Solid State Pyrolysis; Ligand Coupling Reaction; コバルト(lll)錯体; 熱重量・熱示差測定; ロジウム(lll)錯体; パラジウム(ll)錯体; 硫黄; セレン; テルル; 金属錯体; 結晶構造; 酸化反

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.

合成了含2-吡啶硒（pySe）、[Co（pySe）（en）_2]^~（2+）、[Co（pySe）（bpy）_2]^~（2+）、[Co（pySe）_2（bpy）]^~+、fac- [Co（pySe）_3]的新型混配钴（III）配合物，通过电子光谱、圆二色谱、核磁共振谱进行了表征。[Co（pySe）（en）_2]（ClO_4）_2的空间群为P2_1 2_1 2_1，a=12.316（3），B=13.012（2），c=11.728（3）A，Z=4。2845次反射（Mo Ka辐射）的细化导致R=0.056。与pySe硒原子反式的Co-N键比顺式的长0.045 A。类似的2-吡啶硫醇盐（pyS）的硫醇盐引起的反式影响小于现有的pySe。三（pySe）配合物中位于fac几何构型的硒代基团的几何配位位置偏好。合成了新的铑（Ⅲ）配合物[Rh（pySe）_2（PPh_3）_2]^+，fac- [Rh（pySe）_3]，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）苄基硒醚和（2-吡啶基）苄基硫醚）。[PdCl_2（Me_2S）]在固态下的热分解是通过PdCl（SMe）作为中间体生成PdS。而[PdCl_2（pySeBz）_2]和[PdCl_2（pySBz）_2]在固态下的热分解分别为[Pd（pySe）_2]和[Pd（pyS）_2]。而[PdCl_2（pySeBz）_2]在室温下从CHCl_3溶液中重结晶得到[PdCl_2（pySepy-N，N '）]（pySepy表示2，2'-二吡啶硒醚）。这种新型的过渡金属配合物配体偶联反应为有机合成提供了一条新的途径。

项目成果

K.kashiwabara, M.Kita, H.Masauda, S.Kurachi, and S.Ohba: "Crystal Structures of Cobalt (III)-Methyldiphenylphosphine Complexes. Co (III)-P Bond Length and Their Cleavages" Bull.Chem.Soc.Jpn.68. 883-888 (1995)

K.kashiwabara、M.Kita、H.Masauda、S.Kurachi 和 S.Ohba：“钴 (III)-甲基二苯基膦配合物的晶体结构。Co (III)-P 键长及其裂解” Bull.Chem.Soc

K.Kashiwabara et al.,: "Crystal Structure of Cobalt (III)-Methyldiphenylphosphine Complexes. Co (III)-P Bond Length and Cleavages" Bull.Chem.Soc.Jpn.68. 883-888 (1995)

K.Kashiwabara 等人，“钴 (III)-甲基二苯基膦配合物的晶体结构。Co (III)-P 键长和裂解”Bull.Chem.Soc.Jpn.68。

K.Kashiwabara: "Syuthesis and Crystal Structure of Bis (l.l.l-tris (dimethy lphos phino methyl) ethane) iron (II) Tetrafluoro borate" Bull.Chem.Soc.Jpn.68. 3453-3457 (1995)

K.Kashiwabara：“双(1.1.1-三(二甲基膦甲基)乙烷)铁(II)四氟硼酸的合成和晶体结构”Bull.Chem.Soc.Jpn.68。

喜多 他4名: "Crystal Structures of Cobalt(III)-Methyldiphenylphosphine Complexes.Co(III)-P Bond Lengths and Their Cleavages" Bull.Chem,Soc.Jpn.,. 68(3月号に掲載予定). (1995)

Kita 等 4 人：“Crystal Structures of Cobalt(III)-Mmethyldiphenyphosphine Complexes.Co(III)-P Bond Lengths and Their Cleavages”Bull.Chem,Soc.Jpn., 68（计划于 3 月号出版）。 (1995)

K.Kashiwabara et al.,: "Synethesis and Clystal Structure of Bis (1,1,1-tris (dimethylphosphinomethyl) ethane) iron (II) Tetrafluoroborate" Bull.Chem.Soc.Jpn.68. 3453-3457 (1995)

K.Kashiwabara 等人：“双（1,1,1-三（二甲基膦甲基）乙烷）四氟硼酸铁（II）的合成和晶体结构”Bull.Chem.Soc.Jpn.68。