Umsetzung von 2-Dimethylamino-(1,3,2)-diox-, oxathi- und dithi-arsolanen mit Alkoholen und Thiolen

Reaction of 2-Dimethylamino-(1,3,2)-diox-, oxathi-, and dithi-arsolanes with Alcohols or Thiols The reactions of 2-dimethylamino-(l, 3,2)-diox-, oxathi- and dithi-arsolanes (CH₂)₂XYAs? N(CH₃)₂ (X = Y = O or S; X = S, Y = O) with alcohols and thiols yield by cleavage of the As? N bond in the formation of alkoxy and alkylmercaptoarsolanes (CH₂)₂XYAs? ZR (X = Y = Z = O or S; X = Y: O, Z = S; X = Y = S, Z = O; X = S, Y = O, Z = O or S), respectively. Some of these arsolanes are not stable but rearrange under formation of 1,2-Bis-(arsolanyl)ethane and arsinous acid esters.     

A convenient way of making arsoxanes (RAsO)n,X‐ray crystal structure of (m‐F3CC6H4AsO)4

The reactions of RLi (R = t‐Bu, m‐F₃CC₆H₄) with bis(dimethylamino)chloroarsine in diethyl ether at room temperature result in the formation of t‐butyl‐bis(dimethylamino)arsine ( 1 ) and m‐trifluromethylphenyl‐bis(dimethylamino)arsine ( 2 ). Compounds 1 and 2 were hydrolysed in water solution in the presence of sodium carbonate to give the oxides (t‐BuAsO)_n ( 3 ) and (m‐F₃CC₆H₄AsO)_n ( 4 ) respectively. The X‐ray crystal structure of 4 shows the molecule to be cyclotetrameric with pyramidal arsenic. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthese von methyldihalogenarsinen CH3AsXY mit verschiedenen halogenen XY

The reactions of the methylhalogenodimethylaminoarsines CH₃As-[N(CH₃)₂]X (X  F, Cl, Br, I) with HY (Y = Cl, Br) yield the methyldihalogenoarsines CH₃AsXY. The compounds CH₃As[N(CH₃)₂]X are prepared by the reactions of CH₃AsCl₂ with HN(CH₃)₂, CH₃As[N(CH₃)₂]₂ with HX (X = Cl, Br) and by exchange reactions between CH₃As[N(CH₃)₂]₂ and CH₃AsX₂ (X = F, Cl, Br, I).     

Synthesis,Complexes and Metal Extraction Ability of R1R2NC(X)NHP(Y)(0Ph)2

Abstract

The new 1,1-disubstituted 3-diphenoxy(thio)phosphoryl-(thio)ureas, R¹R²NC(X)NHP(0Ph)₂, HA, with X,Y = O,S, were synthesized by addition of secondary mines to the corresponding P-iso(thio)cyanates. This reaction is reversible if X,Y = S. (PhO)₂P(Y)Cl reacts with H₂NC(X)NR₂ in the presence of an HCl acceptor only if X,Y a 0. Side reactions are observed. Phosphorylated derivatives of biuret were isolated from such a reaction mixture.     

Bis(trimethylsilyl)-hypophosphit und Alkoxycarbonylphosphonigsäure-bis(trimethylsilyl)ester als Schlüsselsubstanzen für die Synthese von Organophosphorverbindungen

Bis(trimethylsilyl)hypophosphite und Alkoxycarbonylphosphonous Acid Bis(trimethylsilyl) esters as Building Blocks in Organophosphorus Chemistry The oxidation of pure bis(trimethylsilyl)hypophosphite ( BTH ) with chalcogenides forming (Me₃SiO)₂P(X)H (X = O, S, Se, Te) is described as well as its reactions with alkylhalides RX (X = Cl, Br, I) and Cl? C(O)OR (R = Me, Et, Bzl). By reaction with oxygen, sulfur, and selenium the alkoxycarbonylphosphonous acid bis(trimethylsilyl)esters form RO? C(O)? P(X)(OSiMe₃)₂ (X = O, S, Se) whereas with Cl? C(O)OR the bis(alkoxycarbonyl)-phosphinic acid trimethylsilylesters are obtained. After partial hydrolysis the resulting instable RO? C(O)? P(O)H(OSiMe₃) gives RO? C(O)? P(O)(OSiMe₃)? CH₂? NH? A? COOR′ (A = CH₂, CH₂CH₂, CHCH₃, CH₂CH₂SH, CHCH(CH₃)₂,…) when allowed to react with hexahydro-s-triazines of the aminoacid esters. Reactions of the alkoxycarbonyl-P-silylesters with NaOR or NaOH result in the corresponding mono-, di-, or trisodium salts. With mineral acids decarboxylation occurs, but H? P(O)(OH)? CH₂? NH? A? COOH can be obtained, too. The structure of the compounds described are discussed by their n.m.r. data.     

A theoretical study of the activation of methane by Gold(III) homoleptic complexes

The density functional theory method with the PBE functional, SBK pseudopotential, and extended basis sets was used to study the reaction between methane and gold(III) homoleptic complexes, namely, [AuX₄]^? (X = Cl, Br, I, H, CN, NH₂, OH, CH₃, and SH), [Au(X(CY)₂X)₂]^? (X = S, Y = H; X = Y = O), Au₂Cl₆, [Au(X₂(CY))₂]⁺ (X = S, Y = NH₂; X = O, Y = H), and [Au(acac)₂]⁺, with the formation of electrophic substitution products. The activation of methane under mild conditions was found to be uncharacteristic of anionic and neutral complexes. According to calculations of cationic oxygen-containing complexes, the formation of methane complexes is possible in their reactions with methane. The energy barrier to this reaction noticeably decreases because of the activation of the C-H bond in this complex. The heat effects vary widely depending on the nature of the ligand. There is, however, no obvious correlation between their values and the activation energy of the reaction.     

The use of chloroalkyldichloroarsines in hybrid ligand synthesis. The preparation of but-3-enylbis(3-dimethylarsinopropyl)arsine and 3-dimethylarsinopropylbis(but-3-enyl)arsine,and their reaction with nickel(II) salts to form pentacoordinate complexes. Novel nickel(II)—olefin bonds

Routes have been developed to the hitherto unobtainable arsine-olefin ligands (CH₂CHCH₂CH₂)_nAs(CH₂CH₂CH₂AsMe₂)_3-n (n = 1, tasol, but-3-enylbis(3-dimethylarsinopropyl)arsine; n = 2, dasdol, 3-dimethylarsinopropylbis(but-3-enyl)arsine) by making use of the difference in reactivity between the ClC and AsCl bonds in the precursor Cl(CH₂)_mAsCl₂ (m = 2,3) molecules. Thus, the triarsine obtained by reaction of 2-chloroethyldichloroarsine with the Grignard reagent of 3-chloropropyldimethylarsine yields 2-chloroethylbis(3-dimethylarsinopropyl)arsine, from which tasol is obtainable by subsequent reaction with either the Grignard reagent of vinyl bromide or, preferably, with vinyllithium. Similarly, 3-chloropropyldichloroarsine reacts with the Grignard reagent of 4-chlorobut-1-ene to form 3-chloropropylbis(but-3-enyl)arsine which, on reaction with sodium dimethylarsenide yields dasdol. The tasol ligand reacts with nickel(II) salts to form [NiX(tasol)]⁺ (X = Cl, Br) and [NiI₂(tasol)], the former are trigonal bipyramidal and contain a nickel(II)—olefin bond, and the latter are square pyramidal containing a [NiI₂As₃] coordination sphere. In addition, tasol forms a number of polynuclear complexes with nickel(II). The dasdol ligand acts as a bidentate arsine to form only [NiX(dasdol)₂)]⁺ The formation of novel nickel(II)—olefin bonds in the [NiX(tasol)]⁺ cations is discussed.     

INORGANIC RINGS WITH GALLIUM ORGANYLS AND IMINODIPHOSPHINECHALCHOGENIDES

The organometallic complexes of general formula [Me ₂ Ga{(XPR ₂ ) (YPR′ ₂ )N}] (R, R′ = Ph, X, Y = O, (1); R, R′ = Ph, X, Y = S (2); R, R′ = Ph, X = O, Y = S (3); R = Me, R′ = Ph, X = O, Y = S (4)) were obtained by alkane eliminations from Me ₃ Ga and the free acidic ligands, LH, in toluene solutions. Complexes 1– 4 seem to be potential precursors to cationic gallium species.     

2,6—二乙酰吡啶类双希夫碱配合物的研究——Ⅲ.Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Pb(Ⅱ)和Cd(Ⅱ)配合物的合成和表征

制备了由2,6—二乙酰吡啶和肼基硫代甲酸酯衍生的希夫碱C₅H₃N[CH=NNHC(S)XR]₂(X=S,R=CH₃、C₆H₅CH₂;X=O,R=C₆H₅CH₂).离析出类型为MC₅H₃N[CH=NN=C(S)XR]₂(M=Co²⁺、Ni²⁺、Zn²⁺、Pb²⁺和Cd²⁺)的希夫碱配合物.配合物为元素分析、红外、可见—紫外光谱以及磁化率测量所表征.结果指出:上述希夫碱均为N₃S₂型五齿配体.     

Mass spectra of organometallic compounds—XIII: Metal carbonyl complexes of tris(dimethylamino)arsine

The mass spectra of the tris(dimethylamino)arsine metal carbonyl complexes [(CH₃)₂N]₃-AsM(CO)₅ (M = Cr, Mo and W), trans-[(CH₃)₂N]₃AsCr(CO)₄As[N(CH₃)₂]₃ and [(CH₃)₂N]₃-AsFe(CO)₄ were examined and compared with those of the corresponding tris(dimethylamino)-phosphine complexes. The molecular ions in the mass spectra of the tris(dimethylamino)arsine complexes have a greater tendency to eliminate a (CH₃)₂N fragment than the molecular ions in the mass spectra of the corresponding tris(dimethylamino)phosphine complexes. The mass spectrum of the tungsten derivative [(CH₃)₂N]₃AsW(CO)₅ exhibits not only the usual series of ions [(CH₃)₂N]₃-AsW(CO)n+ and [(CH₃)₂N]₂AsW(CO)n[+ but also the series of ions (CH₃)₂NAsW(CO)n]+ (n = 5, 4, 3, 2, 1 and 0) and even the nitrogen-free ions [AsW(CO)_n]+ (n = 2, 1 and 0). Metastable ion evidence was obtained for arsine (AsH₃) elimination from the [(CH₃)₂N]₂AsFeH⁺ ion in the mass spectrum of [(CH₃)₂N]₃AsFe(CO)₄.     

Yttrium Complexes of Arsine,Arsenide, and Arsinidene Ligands

Deprotonation of the yttrium–arsine complex [Cp′₃Y{As(H)₂Mes}] ( 1 ) (Cp′=η⁵‐C₅H₄Me, Mes=mesityl) by nBuLi produces the μ‐arsenide complex [{Cp′₂Y[μ‐As(H)Mes]}₃] ( 2 ). Deprotonation of the As H bonds in 2 by nBuLi produces [Li(thf)₄]₂[{Cp′₂Y(μ₃‐AsMes)}₃Li], [Li(thf)₄]₂[ 3 ], in which the dianion 3 contains the first example of an arsinidene ligand in rare‐earth metal chemistry. The molecular structures of the arsine, arsenide, and arsinidene complexes are described, and the yttrium–arsenic bonding is analyzed by density functional theory.     

Tridentate Schiff base complexes of ruthenium(III) containing ONS/ONO donor atoms and their biocidal activities

New ruthenium(III) complexes of the [RuY(LL)(E)₂] type (Y = Cl or Br; LL = tridentate Schiff bases; E = PPh₃ or AsPh₃) have been synthesised by reacting [RuX₃(EPh₃)₃] (X = Cl, E = P; X = Cl or Br, E = As) or [RuBr₃(EPh₃)₂(MeOH)] with Schiff bases having the donor groups (O, N, X) viz., salicylaldehydethiosemicarbazone (X = S), salicylaldehydesemicarbazone (X = O), o-hydroxyacetophenonethiosemicarbazone (X = S) and o-hydroxyacetophenonesemicarbazone (X = O). The new complexes were characterised by elemental analysis, spectral (i.r., electronic spectra, e.p.r.), magnetic moment and cyclic voltammetry data. Biocidal activity studies were also carried out for the new complexes.     

Yttrium Complexes of Arsine,Arsenide, and Arsinidene Ligands

Deprotonation of the yttrium–arsine complex [Cp′₃Y{As(H)₂Mes}] ( 1 ) (Cp′=η⁵‐C₅H₄Me, Mes=mesityl) by nBuLi produces the μ‐arsenide complex [{Cp′₂Y[μ‐As(H)Mes]}₃] ( 2 ). Deprotonation of the As? H bonds in 2 by nBuLi produces [Li(thf)₄]₂[{Cp′₂Y(μ₃‐AsMes)}₃Li], [Li(thf)₄]₂[ 3 ], in which the dianion 3 contains the first example of an arsinidene ligand in rare‐earth metal chemistry. The molecular structures of the arsine, arsenide, and arsinidene complexes are described, and the yttrium–arsenic bonding is analyzed by density functional theory.     

Some chemistry of mixed ligand complexes of platinum

Simple synthetic routes to the mixed ligand complexes PtLL'X₂ and PtLL'XY (L' = PEt₃; L = phosphine, arsine, etc.; X = Cl and Y = Cl, H or Me) are described; unexpectedly, these display an extensive chemistry without disproportionation, although in some cases ligand scrambling does occur.     

Darstellung,Eigenschaften und Molekülstrukturen von Alkylaluminiumaminoalkoxidchloriden

Synthesis, Properties, and Molecular Structures of Alkylaluminium Aminoalkoxide Chlorides Alkylaluminium aminoalkoxide chlorides [R(Cl)AlOR*] 1 – 3 have been obtained from the reaction of dialkyl aluminium chlorides R₂AlCl with the respective aminoalkohol HOR* ( 1 : R = Et, OR* = dimethylamino‐1‐propanol; 2 : R = Me, OR* = (+);(–)‐dimethylamino‐2‐propanol; 3 : R = Me, OR* = (S)‐N‐methyl‐2‐pyrrolidinyl‐methanol). The reaction between dimethylaluminium chloride and (S)‐α, α‐diphenyl‐2‐pyrrolidinyl‐methanol (OR* = Dpm) yielded, by contrast, the ionic {[MeAl(OR*)₂AlMe₂]⁺ [MeAlCl₃]^–} complex ( 4 ). 1 – 4 have been characterised by ¹H, ¹³C and ²⁷Al‐NMR spectroscopy. Crystal structures of 1 and of the 1 : 1 solvate of 4 with Et₂O have been determined by X‐ray methods and the absolute structure of 4 was confirmed by refinement of the Flack‐parameter. The dimeric molecules of 1 are composed of two chelating rings linked via an almost planar Al₂O₂ unit and pentacoordination is observed about aluminium. In contrast, each of the two crystallographically independent cation molecules of 4 contains one four‐ and and one five‐coordinate metal centre.     

Some reactions and spectroscopic studies of tris(pentafluorophenyl)arsenic and -antimony(III and V) derivatives

The reactions of tris(pentafluorophenyl)arsenic(III) with iodine monochloride, iodine monoazide, and dithiocyanogen yielded corresponding oxidative-addition products of the type (C₆F₅)₃As(V)XY (X=I, Y=Cl, N₃; X=Y=NCS). The elemental sulphur also added oxidatively with tris(pentafluorophenyl)arsenic(III) yielding tris(pentafluorophenyl)arsine(V) sulphide. Some displacement reactions were also carried out to synthesize mixed pseudohalide derivatives of the type (C₆F₅)₃M(N₃)NCS (M=As and Sb) and their insertion reactions were studied with phenyl isothiocyanate which yielded the corresponding 1,2-cycloaddition products, i.e. tetrazole-5-thiones. The compounds were characterized by elemental analysis, molar conductance, UV, IR and NMR spectroscopic studies.     

Komplexe des Chroms,Molybdäns und Wolframs mit Aminoarsan-Liganden

Complexes of Chromium, Molybdenum, and Tungsten with Aminoarsanes as Ligands The aminoarsanes Me₂As? NMe₂, MeAs(NMe₂)₂, and As(NMe₂)₃ form with the carbonyles of the sub-group VI metals complexes of the general formula (CO)₅M? L (L = aminoarsane; M ? Cr, Mo, W). The cleavage of the As? N bond by reactions with acids HX results in the formation of complexes of the general formula (CO)₅M? As(Me₂)? X, (CO)₅M? As(Me)X₂, and (CO)₅M? AsX₃.     

Fluoridolyse von N-Phosphorylphosphazenen

Fluoridolysis of N-Phosphoryl Phosphazenes In the reaction of the N-phosphoryl phosphazenes X₃P?N? P(Y)X₂ (X = Cl, PhO, Et₂N, CF₃CH₂O, PrS, Ph; Y = O, S) ( 1 – 18 ) with Et₃N · nHF (n ≈? 3 or 0.6) fluoro derivatives of N-phosphoryl phosphazenes (see table 2) as well as N-phosphorylated imiddotetrafluorophosphates, [F₄P?N? P(Y)Cl₂]^? (Y = O, S), and imidopentafluorophosphates, [F₅P? N? P(Y)X₂]^2? or [F₅P? NH? P(O)X₂]^? (see table 3), are formed. t-BuNHPCl₂?N? POCl₂ reacts in acetonitrile with Et₃N or i-Pr₂EtN to form a product, representing probably the diazadiphosphetine ( 5 b ).     

Complexes of Crown Ether‐Containing N‐Phosphorylated Thioamides and Thioureas with CoII,ZnII and PdII Cations

The reaction of the potassium salts of N‐phosphorylated thioureas [4′‐benzo‐15‐crown‐5]NHC(S)NHP(Y)(OiPr)₂ (Y = S, HL^I ; Y = O, HL^II ) with Zn^II and Co^II cations in aqueous EtOH leads to complexes of formulae Zn(L^I,II‐S,Y)₂ (Y = S, 1 ; Y = O, 2 ) and Co(L^I‐S,S′)₂ ( 3 ), while interaction of the potassium salt of N‐phosphorylated thioamide [4′‐benzo‐15‐crown‐5]C(S)NHP(O)(OiPr)₂ ( HL^III ) with Zn^II in the same conditions leads to the complex Zn(HL^III)(L^III‐S,O)₂ ( 4 ). The reaction of the potassium salt of crown ether‐containing N‐phosphorylated bis‐thiourea N,N′‐[C(S)NHP(O)(OiPr)₂]₂‐1,10‐diaza‐18‐crown‐6 ( H₂L ) with Co^II, Zn^II and Pd^II cations in anhydrous CH₃OH leads to complexes M₂(L‐O,S)₂ (M = Co, 5 ; Zn, 6 ; M = Pd, 7 ). Thioamide HL^III was investigated by single‐crystal X‐ray diffraction.