Electron transfer reactions of nickel(III) and nickel(IV) complexes

This review narrates the electron transfer reactions of various nickel(III) and nickel(IV) complexes reported during the period 1981 until today. The reactions have been categorized mainly with respect to the type of nickel complexes. The reactivity of nickel(III) complexes of macrocycles, 2,2′-bipyridyl and 1,10-phenanthroline, peptides and oxime–imine, and of nickel(IV) complexes derived from oxime–imine, oxime and miscellaneous ligands with various organic and inorganic electron donors have been included. Kinetic and mechanistic features associated with such interactions have been duly analyzed. The relevance of Marcus cross-relation equations in the delineation of the electron transfer paths has also been critically discussed.     

1,3-diallyl-5-[ω-(diphenylphosphino)alkyl] isocyanurates in reactions of complex formation with palladium(ii) dichloride

The reactions of phosphine derivatives of diallyl isocyanurates with palladium(ii) dichloride lead to the formation of complexes, whose structure, composition, and stability depend on the length of the methylene chain between the isocyanurate and diphenylphosphine fragments in the ligand. 1,3-Diallyl-5-[5′-(diphenylphosphino)pentyl and 10′-(diphenyl-phosphino)decyl] isocyanurates with PdCl₂ form monomeric L₂PdCl₂ trans-complexes in which P atoms of the ligands participate in coordination with the metal. 1,3-Diallyl-5-[2′-(diphenylphosphino)ethyl] isocyanurate with PdCl₂ forms a dimeric (LPdCl₂)₂ complex, which decomposes in a solution to the monomer including solvent molecule into the coordination sphere of the metal. The reactions of 1,3-diallyl-5-[4′-(diphenylphosphino)butyl] isocyanurate and 1,3-diallyl-5-[6′-(diphenylphosphino)hexyl] isocyanurate with PdCl₂ give monomeric chelate LPdCl₂ complexes in which one of the allyl groups of the isocyanurate cycle participates in coordination with the central ion along with the phosphorus atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1859–1865, September, 1998.     

Antimicorbial effects of newly synthesized organotin(IV) and organolead(IV) derivatives

Triorganotin(IV) and triorganolead(IV) derivatives of the types Me₃Sn(SCZ) and Ph₃Pb(SCZ) (where SCZ^? is the anion of a semicarbanzone ligand) have been synthesized by substitution reactions of trimethyltin chloride and triphenyl-lead chloride with semicarbazones derived from heterocyclic ketones. The resulting complexes have been characterized by elemental analyses, molecualr weight determinations and conductivity measurements. The mode of bonding has been established on the basis of infrared and ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopic studies. Some respresentative complexes have also been evaluated for their antimicrobial effects on different species of pathogenic fungi and bacteria; the results of these investigations have been reported in the present paper.     

Strukturelle Charakterisierung der Dicyanamid-Komplexe von Kupfer(II), Nickel(II) bzw. Kobalt(II) mit Aminopyridinen

Summary New dicyanamide complexes of the typeM[N(CN)₂]₂ L ₂ (M=Cu or Ni;L=2-, 3-, 4-aminopyridine, 2-amino-5-nitropyridine) and Co[N(CN)₂]₂ (2-amino-5-nitropyridine)₂ were prepared and studied by spectroscopic methods as well as by room-temperature magnetic moments. The results show that the Cu(II) complexes have elongated pseudooctahedral structures while the Ni(II) and Co(II) complexes are octahedral. In most cases the N(CN)₂ groups are in bridging function and through their cyanide nitrogens, or-more rarely-amide and cyanide nitrogens connect the basic structure units into polymeric conglomerates. In the Cu(II) systems exchange coupling is seen from the _eff value or ESR spectrum.

Professor Viktor Gutmann zum 70. Geburtstag gewidmet     

Rh(Ⅰ),Co(Ⅰ)和Ru(Ⅱ)双齿磷氢化物的合成.结构表征和催化加氢活性

膦配位的过渡金属氢化物被看作是烯烃及其他一些不饱含有机化合物催化加氢反应及氢甲酰化反应的催化活性物种,关于它们的结构与催化活性关系的研究,有着重要的理论意义和实际意义,通常单齿膦配位表现出较高的催化活性,而不同的金属中心在催化活性和选择性上也表现出明显的差别,反映了催化功能与催化活性物种的电子结构和空间结构之间存在着依存关系.膦配体过渡金属氢化物,通常是以它们的相应卤化物经氢化锂铝或硼氢化钠或肼还原得     

[Co(2,3-tri)(ibn)Cl][ZnCl4]体系一经式异构体的晶体结构及体系异构体的理论计算研究

用单晶X-射线衍射分析方法解析了[Co(2,3-tri)(ibn)Cl]²⁺(2,3-tri=N-(2-氨基乙基)-1,3-丙二胺,ibn=1,2-二氨基-2-甲基丙烷)体系中一经式异构体(m2-[Co(2,3-tri)(ibn)Cl][ZnCl₄])。该晶体属单斜晶系,空间群P2₁/c,a=11.317(3)?,b=14.931(4)?,c=11.646(3)?,β=1     

聚苯并咪唑金属复合物的X-射线光电子能谱(XPS)研究

本文报道以聚苯并咪唑(PBI)与某些过渡金属卤化物所形成的金属复合物的XPS研究,由反映在金属复合物N_(1s)和C_(1s)振起(Shake-up)伴峰的消失,反映在PBI中N_(1s)双峰变为复合物中的具有高结合能的单峰以及与其复合金属离子结合能的降低,这就从施受两个侧面确证金属复合物的形成。XPS结果也说明在金属复合物的制备中,不同溶剂条件所制得的复合物在硅氢加成中活性丧失归结於溶剂导致的金属离子的还原。     

Asymmetric Baeyer—Villiger oxidation: control of stereoelectronic demand

The recent development of asymmetric Baeyer—Villiger oxidation of prochiral and racemic ketones is briefly summarized, focusing on the regio- and stereocontrol of the oxidation attained by regulating the stereoelectronic demand in the step of rearrangement of the Criegee intermediate.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1784–1794, September, 2004.     

异核双金属有机化合物的合成方法与反应性能研究

本文对近年来异核双金属有机化学的发展作了简要的介绍和回顾, 文中对含金属-金属键和不含金属-金属键的d/d和d/f异核双金属有机化合物的合成方法及反应性能作了归纳。     

糖蛋白/胆红素钙水溶性复合物的形成及光谱研究

采用傅立叶变换红外光谱(FT-IR)，结合减法、二阶导、退卷积和曲线拟合等先进光谱技术，紫外可见光谱，ICP-AES分析方法，对不同质量比的α-酸性糖蛋白(AGP)和胆红素钙(CaBR)反应后的滤液进行了研究。结果表明，AGP和CaBR之间存在着较强的相互作用，导致AGP二级结构的有序性增加，CaBR的水溶性增大，两者形成了可溶性的AGP/CaBR复合物。