Oxidation of Zinc and Cadmium with Tricarbonylcyclopentadienylmolybdenum Chloride and Tricarbonylcyclopentadienyltungsten Chloride

The rate of the reaction of zinc and cadmium with tricarbonylcyclopentadienylmolybdenum chloride and tricarbonylcyclopentadienyltungsten chloride and the yield of the final products of these reactions were studied as influenced by the solvent nature. Kinetic features of oxidation of zinc and cadmium with tricarbonylcyclopentadienylmolybdenum chloride in the presence of dimethylformamide were determined. The thermodynamic parameters of adsorption of the oxidizing agent and the ligand on the metal surface were determined.     

Reactions of Tin(II) Fluoride with Halogens

By oxidative-addition of X₂ (X = Cl, Br) to SnF₂ in acetonitrile, monomeric SnF₂Cl₂(MeCN)₂ and polymeric or oligomeric SnF₂Br₂(MeCN)₂ are obtained. The corrected v CN IR frequencies provide a good indication of the Sn–N bond strength. The reactions of SnF₂ with Br₂ and I₂ in the presence of DMSO, and with I₂ in the presence of pyridine yield the disproportionation products rather than the mixed-halide compounds. That suggests that the stability of the mixedhalide compounds decreases when the difference between the halides increases. The reaction of SnF₂ with I₂ in acetonitrile gives rise to SnF₄(MeCN)₂, and provides a simple and inexpensive route to SnF₄ and its complexes, as MeCN is lost under mild conditions or substituted by other ligands. In this way we have prepared SnF₄L₂ (L = DMF, DMSO, THF, Py). The structure of the compounds is discussed in terms of the IR and ¹¹⁹Sn Mössbauer spectra and, in the case of SnF₄L₂, the Mössbauer isomer shift and the IR v Sn–F compared to the corresponding SnCl₄L₂ compounds.     

Tin(II) Halide Insertion or Halogen Exchange in the Reactions of Dihaloplatinum(II) Complexes with Tin(II) Halide

Reactions of SnCl₂ with the complexes cis‐[PtCl₂(P₂)] (P₂=dppf (1,1′‐bis(diphenylphosphino)ferrocene), dppp (1,3‐bis(diphenylphosphino)propane=1,1′‐(propane‐1,3‐diyl)bis[1,1‐diphenylphosphine]), dppb (1,4‐bis(diphenylphosphino)butane=1,1′‐(butane‐1,4‐diyl)bis[1,1‐diphenylphosphine]), and dpppe (1,5‐bis(diphenylphosphino)pentane=1,1′‐(pentane‐1,5‐diyl)bis[1,1‐diphenylphosphine])) resulted in the insertion of SnCl₂ into the Pt? Cl bond to afford the cis‐[PtCl(SnCl₃)(P₂)] complexes. However, the reaction of the complexes cis‐[PtCl₂(P₂)] (P₂=dppf, dppm (bis(diphenylphosphino)methane=1,1′‐methylenebis[1,1‐diphenylphosphine]), dppe (1,2‐bis(diphenylphosphino)ethane=1,1′‐(ethane‐1,2‐diyl)bis[1,1‐diphenylphosphine]), dppp, dppb, and dpppe; P=Ph₃P and (MeO)₃P) with SnX₂ (X=Br or I) resulted in the halogen exchange to yield the complexes [PtX₂(P₂)]. In contrast, treatment of cis‐[PtBr₂(dppm)] with SnBr₂ resulted in the insertion of SnBr₂ into the Pt? Br bond to form cis‐[Pt(SnBr₃)₂(dppm)], and this product was in equilibrium with the starting complex cis‐[PtBr₂(dppm)]. Moreover, the reaction of cis‐[PtCl₂(dppb)] with a mixture SnCl₂/SnI₂ in a 2 : 1 mol ratio resulted in the formation of cis‐[PtI₂(dppb)] as a consequence of the selective halogen‐exchange reaction. ³¹P‐NMR Data for all complexes are reported, and a correlation between the chemical shifts and the coupling constants was established for mono‐ and bis(trichlorostannyl)platinum complexes. The effect of the alkane chain length of the ligand and Sn^II halide is described.     

NMR Study of the Interaction of Tin(II) and Antimony(III) Fluorides with Phosphorus Chlorides

Reactions of SnF₂ and SbF₃ with POCl₃ and PCl₅ in acetonitrile were studied by ¹⁹F, ³¹P, and ¹¹⁹Sn NMR. Tetrahedral compounds POF₂Cl and POF₃ form in the reaction with POCl₃. Interaction of SnF₂ and SbF₃ with PCl₅ yields higher (in terms of fluorine) octahedral complexes [PF₅ · MeCN] and [PF₆]^–. In all cases, fluorine-free phosphorus compounds are found in the acetonitrile solution.     

Peculiarities of Chemical Binding in Anhydrous Lead(II) and Tin(II) Hexacyanoferrates(II,III)

The electronic structure and chemical binding of anhydrous lead and tin hexacyanoferrates(II,III) Pb₂Fe(CN)₆, Pb_1.5Fe(CN)₆, and Sn₂Fe(CN)₆ were studied by the linear muffm-tin orbital (tight binding approximation) and extended Hückel theory methods. The general tendencies of variation for the stability of the Pb–N, Sn–N, Fe–C, and C–N bonds were determined for Pb₂Fe(CN)₆, Pb_1.5Fe(CN)₆, and Sn₂Fe(CN)₆ crystals. Peculiarities of Pb(Sn)–N chemical interactions in the structure of the phases have been found.     

Reaction of Indium with Tricarbonylcyclopentadienyl-molybdenum(II) and -tungsten(II) Chlorides

The reactions of indium with tricarbonylcyclopentadienyl-molybdenum(II) and -tungsten(II) chlorides in donor solvents result in formation of compounds containing Mo-In and W-In bonds. The formalkinetic features of the metal oxidation with ⁵-C₅H₅Mo(CO)₃Cl in dimethylformamide were studied.     

Novel Dinuclear Tin(II) and Lead(II) Compounds with 2‐Pyridyl Functionalized Silylamido Ligands

Treatment of R₂SiCl₂ (R = Me, Ph) with 2‐aminopyridine in the presence of NEt₃ led to the formation of the bis(N‐2‐pyridylamino)silanes R₂Si{NH(2‐Py)}₂, which were isolated as pale yellow solids. Crystal structure analyses revealed that both compounds exhibit tetrahedrally coordinated silicon atoms which are linked to two 2‐pyridylamido moieties and two organyl groups (Me or Ph). As a result of intermolecular hydrogen bonding between the NH groups and the pyridyl N atoms the R₂Si{NH(2‐Py)}₂ molecules are catenated in the solid state. Treatment of R₂Si{NH(2‐Py)}₂ with nBuLi afforded the corresponding amides R₂Si{NLi(2‐Py)}₂, which were subsequently reacted with MCl₂ (M = Sn, Pb) to give the dinuclear silylamides [{R₂Si(N‐2‐Py)₂M}₂]. Both the tin and the lead derivatives exhibit closely related molecular structures, in which the tin (or lead) atoms are linked to two amido N atoms and a pyridyl N atom in a distorted trigonal bipyramidal coordination mode.     

NMR Study of the Reactions of Tin(II) Difluoride and Antimony(III) Trifluoride with Niobium Pentachloride

The reactions of SnF₂and SbF₃with NbCl₅in acetonitrile or dimethyl sulfoxide were studied by ¹⁹F, ⁹³Nb, and ¹¹⁹Sn NMR spectroscopy. The products of reaction in acetonitrile are anionic, while those in di-methyl sulfoxide are neutral octahedral niobium chlorofluoride complexes. Tin(II) difluoride and antimony(III) trifluoride are powerful sources of fluoride ions in the preparation of metal chlorofluoride and fluoro complexes.     

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.     

Flow-Injection Study and Analytical Applications of the Reactions of Palladium(II) and Platinum(IV) with Tin(II) Chloride in Hydrochloric Acid Solutions

The interaction of palladium(II) and platinum(II) with tin(II) chloride in hydrochloric acid solutions was studied by flow-injection (FI) spectrophotometry. It was found using kinetic measurements in the stopped flow mode that the composition of detected products and the rate of their formation depend on the concentrations of tin(II) and chloride ions in the reaction zone and on the acidity of the solution. Optimal FI conditions were found, and the selectivity of interaction of palladium(II) with tin(II) chloride was estimated for the detection of the signal at 407 nm (yellow form) and 646 nm (green form). It was demonstrated that the reaction of the formation of yellow platinum(IV) complexes is slower than that for palladium(II), especially at rather low concentrations of hydrochloric acid in the reaction flow. Based on the detection of green complexes of palladium(II) with tin(II) chloride, a flow injection method was proposed for the selective spectrophotometric determination of palladium(II) in the presence of other platinum-group metals. The height of the recorded peak is directly proportional to the concentration of palladium(II) in the injected solution in the range of 0.028–0.300 mM. The method was used for the analysis of pharmaceuticals and industrial catalysts.     

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

Russian Journal of General Chemistry -     

Reactions of Bis(phenylethynyl)ytterbium with Trimethylsilicon,Triphenylgermanium, and Triphenyltin Chlorides

The ytterbium phenylethynyl compound (PhCC)₂Yb(THF)₄ reacts with trimethylsilicon, triphenylgermanium, and triphenyltin chloride in tetrahydrofuran (THF) at room temperature to give the corresponding cross-coupling products: phenylethynylytterbium chloride PhCCYbCl(THF)₂ and ytterbium chloride YbCl₂(THF)₂.     

Reactions of Pentaphenylantimony and Pentaphehylphosphorus with Arylmercury Chlorides

Russian Journal of General Chemistry -     

Tin(II) Difluoride and Antimony(III) Trifluoride as Fluorine Donors in Reactions with Tantalum Halides in Various Solvents

Reactions of SnF₂and SbF₃with TaF₅and TaCl₅in acetonitrile and dimethyl sulfoxide were studied by ¹⁹F and ¹¹⁹Sn NMR. It was found that SnF₂and SbF₃behave as fluorine donors for tantalum(V). The anionic and cationic tantalum fluorochloride complexes form in acetonitrile, while [TaF₆]^–predominates in dimethyl sulfoxide. Tin(II) occurs in solution in the form of fluorine-containing polymeric cations.     

Reactions of Lower Titanium Chlorides with Molten Magnesium-containing Chlorides of Alkaline Metals

Conditional equilibrium constants K _n ^* of reactions between titanium chlorides and molten magnesium were calculated.     

Reaction of Gelatin-immobilized Lead(II) Hexacyanoferrate(II) with Dithioxamide

Russian Journal of General Chemistry -     

Reactions of Benzylidene Chlorides with S -Methyl Diethylphosphinothioate

S-Methyl diethylphosphinothioate reacted with benzylidene chlorides to give the corresponding aryl(chloro)methyl methyl sulfide and diethylphosphinoyl chloride. The product structure suggests initial attack of the methylsulfanyl group on the CH carbon atom of dichloromethylarene. Arenecarbothialdehyde dithioacetals and trimers and O,O-dialkyl[aryl(methylsulfanyl)methyl]phosphonates were synthesized.