Reactions of Bis(chloromethyl)phosphinic(-Phosphinothioic) Chlorides with Silylated Carbamates and Trimethylsilyl N-Trimethylsilylacetimidoate

Bis(chloromethyl)phosphinic chloride reacts with trimethylsilyl methylcarbamate in benzene in the presence of a base to give trimethylsilyl bis(chloromethyl)phosphinate. The same reaction performed without a solvent and in the absence of a base yields trimethylsilyl bis(chloromethyl)phosphinate and bis(chloromethyl)phosphinic anhydride. Reaction of bis(chloromethyl)phosphinic chloride with trimethylsilyl diethylcarbamate yields N,N-diethylbis(chloromethyl)phosphinic amide. The reaction of bis(chloromethyl)phosphinic (-phosphinothioic) chlorides with trimethylsilyl N-trimethylsilylacetimidoate was studied.     

Reaction of ytterbium(II) and praseodymium(III) phenylethynyl cuprates with trimethylsilyl iodide

Russian Journal of General Chemistry -     

Synthesis and Crystal Structure of Bis（tetra－hydrofurfurylcyclopentadienyl）ytterbium Chloride

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＢｉｓ（ｔｅｔｒａ－ｈｙｄｒｏｆｕｒｆｕｒｙｌｃｙｃｌｏｐｅｎｔａｄｉｅｎｙｌ）ｙｔｔｅｒｂｉｕｍＣｈｌｏｒｉｄｅＺＨＵＡＮＧＸｉｕ－ｌｉ;ＺＨＡＮＧＳｕｏ－ｂｏ;ＨＵＮｉｎｇ－ｈａｉａｎｄ...     

二(四氢糠基茚)稀土氯化物的合成及晶体结构

将四氢糠基茚锂分别与无水三氯化钇和无水三氯化钆以摩尔比2;1反应,除去不溶物和溶剂后,将产物在甲苯/THF中冷冻得到晶体(C₄H₇OCH₂C₉H₆)₂LnCl[Ln=Y(1);Ln=Gd(2)].这两种配合物都是单分子无溶剂化合物,在空气中稳定.配合物1和2的晶体结构都属于正交晶系,P2₁2₁2₁空间群,晶胞参数分别为a=1.04252(9)nm,b=1.47455(12)nm,c=1.49799(13)nm,Z=4,Dc=1.508g/cm³;a=1.03701(10)nm,b=1.47233(12)nm,c=1.51354(14)nm,Z=4,Dc=1.699g/cm³.它们的结构相似,但空间构象不同.稀土中心离子分别与两个茚中的五元环和两个氧原子及氯原子成键,形成九配位结构.     

Bis(di-tert-butylcyclopentadienyl)ytterbium(ii). Synthesis and catalytic properties

Polymeric (Cp₂Yb·THF) _n (1), ionicate-complex Cp₃YbNa (2), and mono-adduct (Bu^t ₂C₅H₃)₂Yb·THF (3) were prepared through a reaction of CpNa (Cp = C₅H₅ or C₅H₃Bu^t ₂) with Ybl₂ in THF. Cooling complex (3) in THF at –100 °C gives a bis-adduct, which reversibly dissociates to give the mono-adduct, The (Bu^t ₂C H , Yb·THF complex shows catalytic activity in the homogeneous hydrogenation of hex-l-ene and in the polymerization of styrene.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No, 7, pp. 1833–1837, July, 1996.     

Reactions of Tin and Lead with Tricarbonylcyclopentadienylmolybdenum(II) and Tricarbonylcyclopentadienyltungsten(II) Chlorides

Tin was oxidized with tricarbonylcyclopentadienylmolybdenum and tricarbonylcyclopentadienyltungsten chlorides to obtain polynuclear organometallic compounds [⁵-C₅H₅M(CO)₃]₂SnCl₂ (M = Mo, W). The reactions of the above-mentioned oxidants with lead gave lead chloride and [⁵-C₅H₅M(CO)₃]₂ dimers. Formal-kinetic regularities of tin oxidation with tricarbonylcyclopentadienylmolybdenum chloride in N,N-dimethylformamide were found. Thermodynamic parameters of adsorption of the reagent on the metal surface were determined.     

Reactions of Triarylbismuth Bis(arenesulfonates)

Reactions of triphenylbismuth with sodium salts, acids, alkalies, and zinc are studied. In the first three cases Bi-O bond cleavage takes place, while zinc reduces the starting bismuth compounds to triphenylbismuth.     

Reactions of Unsaturated Ketones with Bis(trimethylsilyl) Hypophosphite

Bis(trimethylsilyl) hypophosphite reacts with unsaturated ketones (methyl vinyl ketone and mesityl oxide) to give, depending on the reaction conditions, 1: 1 or 1: 2 adducts after hydrolysis. It was found that the intramolecular cyclization of the 1: 2 reaction product with mesityl oxide, trimethylsilyl bis(2-methyl-4- oxopentan-2-yl)phosphinate, yields, after hydrolysis, a phosphorinane with exocyclic carbonyl and hydroxyl groups.     

Mechanism of Reactions of P(III) Amidoesters with Carboxylic Acid Chlorides

Russian Journal of General Chemistry -     

Reactions of styryl and phenylethynyl sulfones with some CH-acids

Reactions of methyl and p-tolyl phenylethynyl sulfones with enolated of dimethyl malonate and malononitrile lead to the formation of sulfonyl-substituted derivatives of ethylidenemalonic acid. Methyl (E)-β-styryl sulfone reacts with sodium enolates of dimethyl malonate, malononitrile, and methyl cyanoacetate to give common Michael adducts.     

Transmetallation of Bis(6-diphenylphosphinoacenaphth-5-yl)-Mercury and -Tributyltin with Precious Metal Chlorides

The reaction of bis(6-diphenylphosphinoacenapht-5yl)mercury, (6-Ph₂P-Ace-5-)₂Hg, with [(CO)₂RhCl]₂ and PtCl₂ proceeded with extrusion of mercury / mercury(I) chloride and provided the octahedral rhodium and platinum complexes (6-Ph₂P-Ace-5-)₂Rh(CO)Cl and (6-Ph₂P-Ace-5-)₂PtCl₂, respectively. The reaction of the (6-diphenylphosphinoacenapht-5yl)stannane 6-Ph₂P-Ace-5-SnBu₃ with PdCl₂ gave rise to tributyltin chloride and a dimeric arylpalladium chloride [(6-Ph₂P-Ace-5-)PdCl]₂ with a planar Pd₂Cl₂ core. Together with the previously known gold(III) complex cis- and trans-[R₂Au][Cl], the newly prepared compounds were investigated by DFT calculations. The fully optimized gas-phase structure of [(6-Ph₂P-Ace-5-)PdCl]₂ gives rise to a bend Pd₂Cl₂ core featuring a Pd ··· Pd palladophilic interaction. The bonding situation was studied using a set of real-space bonding indicators (RSBIs) derived from the methods Atoms-In-Molecules (AIM), Electron Localizability Indicator (ELI-D) and Non-Covalent Interaction (NCI) index.     

Reactions of Pentaphenylantimony and Pentaphehylphosphorus with Arylmercury Chlorides

Russian Journal of General Chemistry -     

Syntheses and Diel-Alder Reactions of Bis(Alkylidene)Cyclohexanes

Substituted cyclohexene-fused 3-sulfolenes have been prepared by the direct deprotonation/alkylation reactions of a readily available starting material. These fused 3-sulfolenes undergo inter- and intramolecular Diels-Alder reactions at high temperatures to give properly substituted bi- and tricyclic molecules.     

A Doubly Bridged Bis(phenylethynyl)benzene: Different from a Twisted Tolan

The synthesis of a doubly bridged 1,4-bis(phenylethynyl)benzene is reported. The target displays photophysical properties, distinctly different from that of its congeners, the singly bridged tolans. Quantum-chemical calculations suggest a lack of planarization of the bridged bis(phenylethynyl)benzene in the first excited state.     

Reactions of p-Hydroxyphenylphosphine and Functionally Substituted Bis(hydroxymethyl)phosphines with Heterocumulenes

Reactions of p-hydroxyphenylphosphine, bis(hydroxymethyl)(p-hydroxyphenyl)phosphine, and bis(hydroxymethyl)(5-allyl-2-ethoxybenzyl)phosphine with nitrogen-containing heterocumulenes were studied. The competitive reactivity of the phenol, phosphine, and hydroxymethyl groups in these reactions was examined.     

Reactions of Bis(p-methoxyphenyl)trisulfane and Its Oxides with Dimethyldioxirane and (Trifluoromethyl)methyldioxirane

The reactions of dimethyldioxirane and (trifluoromethyl)methyldioxirane with bis(p-methoxyphenyl)trisulfane, its 1-oxide, its 2-oxide, and its 1,1-dioxide derivatives have been investigated. The reactions were followed by careful monitoring of the methoxy region of the (1)H NMR spectra and where possible by doping with authentic samples of the products. The decomposition of labile intermediates and products was investigated. A new mechanism for the rearrangement of a trisulfane 1,3-dioxide to a trisulfane 1,1-dioxide is proposed.