Electrosynthesis and Reactions of Platinum Triad Metal Cluster Containing Bidentate Phosphine

含双齿膦三元组铂金属簇的电合成及反应

• 批准号: 02640484
• 负责人: YAMAMOTO Yasuhiro
• 金额: $ 1.22万
• 依托单位: Toho University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02640484/
• 关键词: EHMO calculations of dinuclear and trinuclear platinum complexes; Naked platinum complex; A-frame complex; 配位不飽和白金錯体; Aーframe錯体; 白金錯体のESCA; 白金二核錯体の分子軌道; 裸の白金錯体; Aーframe 錯体; “裸"の白金3核錯体; 白金多核錯体

Electrochemical reductionsof isocyanide. complexes of platinum and palladium [M(RNC)_2(diphos)]^<2+> (1) (M = Pt, Pd ; diphos = PP_2P(CH_2)_nPPh_2, n = 1, 2, 3, 4) containing bidentate phosphine ligands were carried out. One electron reduction of (1) gave [M_2(RNC)_2(diphos)_2]^<2+>. The dppm (n = 1) complex has a trans-dppm structure, containing a mu-coordination to two metals and other diphosphine complexes (n = 2, 3, 4) have a chelate structure. A 1.5 electron reduction of (1) gave tri-nuclear complexes, [M_3(RNC)_4(diphos)_2]^<2+> (M = pt. Pd ; ri = 1, 2, 4) (2) and [Pt_3(RNC)_2(diphos)_2]^<2+> (n = 3) (3), depending on diphosphine ligands. In the complex (2), the dppm (n = 1) complex has a A-frame structure and other ones have a linear structure which two diphosphines chelated to two outer metals. The remarkable feature of (3) is the central platinum atom, which is bound only to other Pt atoms. To our knowledge, this is the first example of an electron-deficient tri-platinum compound. The electronic structure of the naked platinum of (3) was estimated by EHMO calculations of the model complexes, in which the charge separation of outer and central atoms was observed. This was confirmed by ESCA of (3). Reactions of dinuclear complexes with d^<10> ML_2 fragments led to an insertion of ML_2 one into a metal-metal bond to give homo-, heteronuclear or A-frame complexes. Reaction with RNC was also carried out.

异氰化物的电化学还原。合成了含双齿膦配体的铂和钯[M(Rnc)_2(Diphos)]^&lt；2+&gt；(1)(M=Pt，Pd；diphos=PP_2P(CH_2)_nPPh_2，n=1，2，3，4)的配合物。(1)的一个电子还原得到[M_2(Rnc)_2(Diphos)_2]^&lt；2+&gt；Dppm(n=1)配合物具有反式dppm结构，与两种金属配位，其他双膦配合物(n=2，3，4)具有螯合结构。(1)经1.5电子还原得到三核配合物[M_3(Rnc)_4(Diphos)_2]^&lt；Pd；ri=1，2，4)(2)和[Pt_3(Rnc)_2(Diphos)_2]^&lt；2+&gt；(n=3)(3)，取决于双膦配体。在配合物(2)中，dppm(n=1)配合物具有A-骨架结构，其他配合物具有两个双膦配体与两个外部金属络合的线形结构。(3)的显著特征是中心铂原子，它只与其他铂原子结合。据我们所知，这是第一个缺电子的三铂化合物的例子。通过对模型化合物的EHMO计算，估算了(3)的裸铂的电子结构，其中观察到外层原子和中心原子的电荷分离。(3)的ESCA证实了这一点。双核配合物与d^&lt；10&gt；ML_2片段反应，将ML_2插入金属-金属键，得到同核、异核或A-骨架配合物。并与RNC进行了反应。

项目成果

T. Tanase, Y. Kudo, M. Ohno, K. Kobayashi, Y. Yamamoto: "A tri-platinum complex containing a coordinatively naked paltinum atom" Nature. 344. 526-528 (1990)

T. Tanase、Y. Kudo、M. Ohno、K. Kobayashi、Y. Yamamoto：“含有配位裸铂原子的三铂复合物”《自然》。

T.Tamase,Y.Kudo,M.Ohno,K.Kobayashi,Y.Yamamoto: "A tirーplatinum complex contairing a condinatively naked platinum atom" hature. 344. 526-528 (1990)

T. Tamase、Y. Kudo、M. Ohno、K. Kobayashi、Y. Yamamoto：“含有条件裸露铂原子的钛铂络合物”344. 526-528 (1990)。

山本 育宏: "A triーplatinum complex containing a coordinatively naked platirum atom" Nature. 344. 526-528 (1990)

Ikuhiro Yamamoto：“含有配位裸铂原子的三铂络合物”《自然》344. 526-528 (1990)。

T.Tanase,K.Kobayashi Y.Yamamoto: "An EXAFS study on bi-and tri-nuclear palladiunr and platinum complexes containing isocyanide and diphosphine ligands" Photon Factory Activity Report. 8. 183 (1990)

T.Tanase、K.Kobayashi Y.Yamamoto：“关于含有异氰化物和二膦配体的双核和三核钯和铂配合物的 EXAFS 研究”光子工厂活动报告。

T.Tanase,Y.Kudo,M.Ohno,K.Kobayashi,Y.Yamamoto: "A tri-platinum complex containing a coodinatively naked platinum atom" hatue. 344. 526-528 (1990)

T.Tanase，Y.Kudo，M.Ohno，K.Kobayashi，Y.Yamamoto：“含有配位裸铂原子的三铂络合物”帽子。