cis‐trans‐Isomerie bei (Me4Sb)2[Ph2Sb2I6]

cis‐trans‐Isomerism in (Me₄Sb)₂[Ph₂Sb₂I₆] Crystals of cis‐(Me₄Sb)₂[Ph₂Sb₂I₆] ( 1 a ) are formed by reaction of PhSbI₂ and Me₄SbI in ethanol/petroleum ether at –7 °C. In ethanol/acetone crystals of trans‐(Me₄Sb)₂[Ph₂Sb₂I₆] · acetone ( 1 b ) form. The X‐ray crystal structure analyses reveal that both isomers consist of tetrahedral cations and of dimeric anions with the geometry of two edge sharing tetragonal pyramids. The phenyl groups possess apical cis ( 1 a ) or trans ( 1 b ) positions relative to the I₂SbI₂SbI₂ plane. The acetone molecules in 1 b are non coordinating.     

Neue Synthesen von Me2SbX (X = Cl,I) und Kristallstrukturen von Me2SbI und [(Me3Si)2CH]2SbCl

Novel Syntheses of Me₂SbX (X = Cl, I) and Crystal Structures of Me₂SbI and [(Me₃Si)₂CH]₂SbCl The crystal structures of Me₂SbI (Me = CH₃) and [(Me₃Si)₂CH]₂SbCl have been determined by X‐ray methods. Both molecules are pyramidal. The Me₂SbI molecules are associated to chains through short intermolecular Sb…I distances (366,7(1) pm) with linear I–Sb…I units (171,87(4)°) and bent Sb–I…Sb bridges (116,83(3)°).     

Neutrale Thiolate und ein Iodidthiolat von Antimon(III). Die Kristallstrukturen von Sb(SC6H5)3, Sb(SC6H2Me3-2,4,6)3 und SbI(SC6H2Me3-2,4,6)2

Neutral Thiolates and a Iodothiolate of Antimony(III). Crystal Structures of Sb(SC₆H₅)₃, Sb(SC₆H₂Me₃-2,4,6)₃, and SbI(SC₆H₂Me₃-2,4,6)₂ The crystal structures of Sb(SC₆H₅)₃ ( 1 ), Sb(SC₆ · H₂Me₃-2,4,6)₃ ( 2 ), and the novel compound SbI(SC₆H₂Me₃-2,4,6)₂ ( 3 ) have been determined by X-ray crystallography. In addition to the expected trigonal pyramidal coordination of antimony intermolecular interactions are observed for 1 (Sb … O: 363.3 pm) and 3 (Sb … S: 2 × 369.4 pm) but not for 2 . The reasons for these differences are discussed.     

Mass spectrometry of organic compounds in the group V elements—I: Straight chain aliphatic derivatives

Comparative investigations of the mass spectra of eEH₂, Me₂EH, Et₂EH(E = N, P); Me₃E, Et₃E(E = N, P, As, Sb, Bi). (n-Pr)₃E(E = Sb, Bi); (n-Bu)₃E(E = P, As); (n-C₅H₁₁)₃As and (n-C₆H₁₃)₃As as well as Et₂AsBr have been carried out. Deuteroanalogues, metastable transitions and low voltage spectra were used for elucidation of the fragmentation paths. The mass spectra of MeN(CH₂)₂ and CD₃N(CH₂)₂ were studied to analyse the structure of the fragments. The main degradation path of amines, i.e. α-cleavage, was shown to be untypical for P, As, Sb and Bi derivatives.     

Synthesis and crystal structure of (Et4N)[{μ 3-SbI}Fe3(η 5-C5H5)(CO)10]

Crystal structure of (Et₄N)[{μ ₃-SbI}Fe₃-SbI}Fe₃Cp(CO)₁₀] was determined by X-ray diffraction analysis. The compound was synthesized by the reaction between (Et₄N)₂[Fe₂(CO)₈] and CpFe(CO)₂SbI₂ in a THF solution with cooling in an argon atmosphere. The crystals are monoclinic, a=12.792(2), b=14.152(3), c=17.373(3) Å, β=92.32(1)°, V_cell=3143(1) ų, space group P2₁/n, Z=4, d_calc=1.885 g/cm³, Syntex P2₁, λCuK_α radiation, R(F)=0.0744 for 877 F_hkl>6σ(F_hkl). The data were corrected for crystal decomposition according to the drop in the intensities of control reflections (by 23% during 29 h X-ray exposure). In the cluster anion, the Sb?Fe distances (ave. 2.57(1) Å) and the I?Sb?Fe and Fe?Sb?Fe angles (ave. 102.7(6) and 115.4(4)°) have virtually the same values as in other known complexes containing HalSbFe₃ and SbFe₄ fragments. The Fe...Fe distances of 4.312-4.369 Å indicate that the metal-metal bonds are absent.     

Übergangsmetall-substituierte phosphane,arsane und stibane : XXIX. Metallierte arsane und stibane mit chiralem eisen-substituenten

The reaction of Cp(CO)₂FeEMe₂ (E  As, Sb, Bi) with Me₃P, Et₃P, Me₂PhP and (MeO)₃P leads to a CO/R₃P exchange and formation of the chiral derivatives Cp(CO)(R₃P)FeEMe₂. Cp(CO)[(MeO)₃P]FeEMe₂ rearranges already at room temperature to Cp(CO)[(Me₃E]FeP(O)(OMe)₂ which is transformed by (MeO)₃P to Cp(CO)[(MeO)₃P]FeP(O)(OMe)₂. The high nucleophilicity of the new organometallic Lewis bases is established by the easy conversion of Cp(CO)(Me₃P)FeSbMe₂ to [Cp(CO)(Me₃P)Fe(SbMe₃)]I with MeI, or to [Cp(CO)(Me₃P)FeSbMe₂Fe(CO)LCp]Hal (L  CO, Hal  Cl; L  Me₃P, Hal  Br) with Cp(CO)LFe-Hal, respectively. The new compounds are characterized by spectroscopy and elementary analyses.     

Stoichiometry-dependent oxidation of tris(2-methoxyphenyl)antimony with diiodine

The reaction of 2-methoxyphenyllithium with SbCl₃ affords tris(2-methoxyphenyl)antimony. Its treatment with equimolar amount of I₂ results in stiborane (2-MeOC₆H₄)₃SbI₂, while heating with 2 equivalents of I₂ leads to iodotris(2-methoxyphenyl)stibonium triiodide [(2-MeOC₆H₄)₃SbI]⁺ [I₃]^– featuring halogen bonding in solid state.     

Influence of electrolyte characteristics on the electrochemical parameters of electrical double layer capacitors

Electrical double layer capacitors based on ideally polarizable nanoporous carbon electrodes in propylene carbonate with the addition of different 1 M Me₃EtNBF₄, Me₂Et₂NBF₄, MeEt₃NBF₄, Et₄NBF₄, Et₃PrNBF₄ and Et₃BuNBF₄ electrolytes have been tested by cyclic voltammetry, chronoamperometry and electrochemical impedance methods. The limits of ideal polarizability, low-frequency limiting capacitance and series resistance, time constant, Ragone plots (energy density vs. power density dependencies) and other characteristics have been discussed. The influence of the electrolyte molar mass on the electrochemical characteristics of the nanoporous carbon electrode cells has been established. The applicability limits of the Srinivasan and Weidner model have been tested.     

The synthesis and characterization of isobutylantimony compounds

Six new isobutyl derivatives of antimony have been synthesized in good yields, including the five-coordinate i-Bu₃SbI₂ and the three-coordinate i-Bu₂SbI, i-Bu₂SbBr, i-BuSbBr₂, i-Bu₂SbH, and i-BuSbH₂. The iodides were made from addition of iodine to i-Bu₃Sb and subsequent thermal decomposition of i-Bu₃SbI₂. The bromides were synthesized by thermal exchange reactions of i-Bu₃Sb with SbBr₃, and the hydrides from reduction of the bromides with LiAlH₄. All compounds have been characterized by elemental analysis, IR, and NMR spectroscopy.     

The Reaction of Bunsen's Cacodyl Disulfide,Me2As(S)‐S‐AsMe2, with Iodine: Preparation and Properties of Dimethylarsinosulfenyl Iodide,Me2As‐S‐I

Bunsen's cacodyl disulfide, Me₂As(S)‐S‐AsMe₂ ( 1 ), reacted with iodine giving the novel dimethylarsinosulfenyl iodide, Me₂As‐S‐I ( 3 ) although theoretical calculations indicated that the As^V compound Me₂As(S)‐I ( 4 ) was more stable in the gas phase. The oily product was stable neat and as a solution in CDCl₃ at +4 °C and –20 °C for at least 15 d. Light, H₂O, H₂O₂, and Zn dust, but not NaI or Ag, decomposed it. Compound 3 did not interact with Ph₃N, with Ph₂NH and PhNH₂ it interacted but not reacted. 3 was decomposed by piperidine, with pyridine and 4‐dimethylaminopyridine it interacted and produced Me₂As‐SS‐AsMe₂ ( 2 ) and I₂ that formed charge transfer complexes Base · I₂, whereas Et₃N decomposed 3 , and 3Et₃N · 2I₂ was isolated. 3 was desulfurized by Ph₃P and (Me₂N)₃P completely, and by (PhO)₃P and (PhS)₃P partially. The reactions of 3 with (Me₂N)₃P, (PhS)₃P, and (EtO)₃P were complicated. From the As^III nucleophiles, only Ph₃As was bound, while (PhS)₃As reacted slowly in a complicated manner with 3 . No interaction of 3 with MeOH or PhOH was observed but NaOH, Ag₂O, and PhONa decomposed it. Thiophenol produced traces of Me₂As‐SPh ( 10 ) and sodium thiophenolate attacked mainly at As^III of 3 . Thus, externally stabilized sulfenium ions of the type Me₂As‐S‐Nu⁺I^– were not obtained.     

Synthesen und Kristallstrukturanalysen von [SbI3(SbMe3)(THF)]2 und [Li(THF)4]2[Bi2Cl8(THF)2]

Syntheses and Crystal Structure Analyses of [SbI₃(SbMe₃)(THF)]₂ and [Li(THF)₄]₂[Bi₂Cl₈(THF)₂] The reaction of Me₃Sb with SbI₃ in tetrahydrofuran (THF) gives [SbI₃(SbMe₃)(THF)]₂ ( 1 ). [Li(THF)₄]₂[Bi₂Cl₈(THF)₂] ( 2 ) is formed by reaction of LiCl and BiCl₃ in tetrahydrofuran. The structures of ( 1 ) and ( 2 ) have been determined by X-ray diffractometry. Both structures contain centrosymmetric dimers with the geometry of edge sharing octahedra.     

Substitutionsreaktionen der Bis(trimethylelement)carbodiimide des Siliciums und Germaniums mit Metallchloriden und Dimethylmetallchloriden des Sb,Al, Ga und In

Substitution Reactions of Bis(trimethylelement)carbodiimides of Silicon and Germanium with Metal Chlorides and Dimethylmetalchlorides of Sb, Al, Ga, and In The reaction of Me₃Ge? N?C?N? GeMe₃ (Me?CH₃) with SbCl₅ in a 1 : 1 molar ratio forms dimeric Cl₄SbNCNGeMe₃ in high yields. The corresponding compounds (X₂MNCNSiMe₃)_2–3 (with X?Cl, Me and M = Al, Ga), formed by reactions of X₂MCl and Me₃SiNCNSiMe₃, are less stable and tend to condensations, eliminating Me₃SiX. The carbodiimide derivates (Me₂MNCNEMe₃)_2–3 (with E = Si, Ge) are also available in aprotic solvents from polymeric LiNCNEMe₃ and Me₂MCl (M = Al, Ga, In). According to the IR and Raman spectra the low associated substitution products consists of cyclic ring skeletons and asymmetric > N? C?N? EMe₃ units with cyanamide conformation.     

Gemischtligandkomplexe des Technetiums. XV. Zur Reaktion von [TcNCl2(Me2PhP)3] mit Dialkyldithiocarbamaten und N,N-Dialkylthiocarbamoylbenzamidinen

Mixed-ligand Complexes of Technetium. XV. The Reaction of [TcNCl₂(Me₂PhP)₃] with Dialkyldithiocarbamates and N,N-Dialkylthio-carbamoylbenzamidines [TcN(Cl)(Me₂PhP)₂(Et₂dtc)], [TcN(Me₂PhP)(Et₂dtc)₂], and [TcN(Et₂dtc)₂] can be prepared by stepwise ligand exchange reactions starting from dichlorotris(dimethylphenylphosphine)nitridotechnetium(V), [TcNCl₂(Me₂PhP)₃], and diethyldithiocarbamate. In contrast to this, only one intermediate, [TcN(Cl)(Me₂PhP)₂(HEt₂tcb)], could be isolated during the reaction with N,N-Diethlthiocarbamoylbenzamidine, which yields the bis chelate [TcN(HEt₂tcb)₂]. [TcN(Me₂PhP)(Et₂dtc)₂] crystallizes in the monoclinic space group P2₁/c; a = 17.369(5) Å, b = 15.024(1) Å, c = 9.906(3) Å, β = 76.47(1)º, Z = 4. The phosphine is coordinated equatorially. The multiply bonded nitrogen ligand (Tc? N(1) 1.624(3) Å) strongly labilizes the trans positioned donor atom (distance Tc? S(4) 2.826(1) Å). [TcN(HEt₂tcb)₂] crystallizes in the triclinic space group P1 with a = 9.749(4) Å, b = 11.264(4) Å, c = 12.359(4) Å, α = 75.34(2)º, β = 79.69(2)º, γ = 87.55(2)º, Z = 2. The metal is five-coordinate with the nitrido donor atom occupying the apex of a square pyramid. It's basal plane is formed by the cis-coordinated chelate ligands. The technetium is situated over the basal plane by about 0.6 Å. The Tc?N distane was found to be 1.610(5) Å.     

Reaktion von N-Alkyl-bis(difluorophosphoryl)amiden,RN(POF2)2, mit silylierten Nukleophilen und Et2NSF3

Reaction of N-Alkyl-bis(difluorophosphoryl)amides, RN(POF₂)₂, with Silylated Nucleophiles and Et₂NSF₃ N-Alkyl-bis(difluorophosphoryl)amides, RN(POF₂)₂ (R = Me, Et), react in any case with silylated nucleophiles such as Me₃SiOMe and Me₃SiNEt₂ under cleavage of the PNP bridge forming derivatives of di- and monofluorophosphoric acid. In their reaction with Et₂NSF₃ (RNPF₃)₂ and OPF₃ or PF₅, resp., are obtained. The compounds F₂P(O)? NR? PF₄ and RN(PF₄)₂ postulated as intermediates are not stable.     

Gemischtligandkomplexe des Rheniums. IX. Reaktionen am Nitridoliganden von [ReN(Me2PhP)(Et2dtc)2]. Synthese,Charakterisierung und Kristallstrukturen von [Re(NBCl3)(Me2PhP)(Et2dtc)2], [Re(NGaCl3)(Me2PhP)(Et2dtc)2] und [Re(NS)Cl(Me2PhP)2(Et2dtc)]

Mixed-ligand Complexes of Rhenium. IX. Reactions on the Nitrido Ligand of [ReN(Me₂PhP)(Et₂dtc)₂]. Synthesis, Characterization, and Structures of [Re(NBCl₃)(Me₂PhP)(Et₂dtc)₂], [Re(NGaCl₃)(Me₂PhP)(Et₂dtc)₂], and [Re(NS)Cl(Me₂PhP)₂(Et₂dtc)] BCl₃, GaCl₃ and S₂Cl₂ react with the well-known [ReN(Me₂PhP)(Et₂dtc)₂] by attack of the nucleophilic nitrido ligand. Final products of these reactions are [Re(NBCl₃)-(Me₂PhP)(Et₂dtc)₂], [Re(NGaCl₃)(Me₂PhP)(Et₂dtc)₂], and [Re(NS)Cl(Me₂PhP)₂Et₂dtc)] which have been studied by mass spectrometry, IR spectroscopy and X-ray diffraction. [Re(NBCl₃)(Me₂PhP)(Et₂dtc)₂] crystallizes in the triclinic space group P1 , Z = 2, a = 8.151(6), b = 9.935(8), c = 18.67(1) Å; α = 94.42(4), β = 97.09(1), γ = 101.35(4)°. The coordination geometry is a distorted octahedron. The equatorial coordination sphere is occupied by one phosphorus and three sulphur atoms. The fourth sulphur atom is in trans position to the Re?N? B moiety. The almost linear Re?N? B unit has an Re?N? B angle of 170.5(3)° with a Re? N bond length of 1.704(3) Å. The analogous [Re(NGaCl₃)(Me₂PhP)(Et₂dtc)₂] crystallizes in P2₁/c with a = 8.138(3), b = 18.279(2), c = 19.880(6) Å; β = 99.81(2)°; Z = 4. Rhenium has a distorted octahedral environment. The Re? N? Ga bond is slightly bent with an angle of 154.5(4)° and a Re? N bond length of 1.695(6) Å. [Re(NS)Cl(Me₂PhP)₂(Et₂dtc)] crystallizes in the triclinic space group P1 , Z = 4, a = 9.514(2); b = 16.266(5); c = 18.388(3) Å; α = 88.75(2), β = 76.59(2), γ = 85.50(2)° with two crystallographically independent molecules in the asymmetric unit. Rhenium has a distorted octahedral environment with the chloro ligand in trans position to the almost linear thionitrosyl group. The Re?N bond lengths are 1.795(6) and 1.72(1) Å, respectively, and the N?S distances are 1.55(1) and 1.59(1) Å, respectively.     

Darstellung und Eigenschaften von Dibromotrachloro-u-methylen- diantimonaten(III) and Hexabromotetrachloro-u-methylen-diantimonaten(V)

Preparation and Properties of Dibromotetrachloro-u-methylene-diantimonates(III) and Hexabromotetrachloro-u-methylene-diantimonates(V) The complex salts (R₄E)₂ [Br₃Cl₂Sb]₂ CH₂ (R₄E = Et₄N, Ph₄P, Ph₄As, Ph₄Sb) are obtained by the reaction of [Cl₂Sb]₂ with R₄ EBr in dichloromethane. The oxidation of the new compounds with Br₂ at ?78°C, in dichloromethane, leads to the corresponding complex salts of pentavalent antimony (R₄E)₂[Br₃Cl₂Sb]₂CH₂.     

Untersuchungen an Polyhalogeniden. XVII. Darstellung und Kristallstruktur von Urotropiniumtriiodid,UrHI3

Studies on Polyhalides. 17. Preparation and Crystal Structure of Urotropinium Triiodide, UrHI₃ Urotropinium triiodide C₆H₁₃N₄I₃ is formed by the reaction of equimolar amounts of urotropinium iodide and iodine in ^tBuOH as red-brown cube-like crystals melting at 402 K under decomposition. The compound crystallizes monoclinically in the space group P2₁/c with a = 952.0(3) pm, b = 1 160.2(6) pm, c = 1 149.9(4) pm, β = 92.22(3)° and Z = 4. The till now not described crystal structure (R = 0.027 for 1 860 observed reflexes) contains urotropinium ions UrH⁺ and slightly distorted triiodide ions I₃^?(d(I—I) = 292.3(1), 294.1(1) pm, φ(I—I—I) = 178.27(2)°) which are linked to ion pairs by a rather short contact (d(I …? I) = 389.0(1) pm, φ(I—I …? I) = 149.12(2)°).     

Übergangsmetall-substituierte phosphane,arsane und stibane: XXXVI. Diastereomere dreikernkomplexe mit verbrückenden dimethylarsino-, dimethylstibino- oder dimethylbismutino-einheiten

Interaction of the chiral organometallic Lewis bases Cp(CO)(Me₃P)Fe—EMe₂ (E = As, Sb, Bi) (1a–1c) with the norbornadiene metal complex (C₇H₈)Mo(CO)₄ yields the first examples of trinuclear complexes [Cp(CO)(Me₃P)Fe—EMe₂]₂Mo(CO)₄ (2a–2c), bearing two chiral metal atoms separated by a E—Mo—E-linkage. 2a–2c are generated as a mixture of two diastereomers (RS/SR, RR/SS), which gives rise to a resonance doubling in their ¹H and ³¹P NMR spectra. This phenomenon is not observed for the achiral, in part sterically more crowded derivatives [Cp(CO)₂Fe—SbMe₂]₂Mo(CO)₄ (4) and [Cp(CO)₂(Me₃P)Mo—EMe₂]₂Mo(CO)₄ (E = As, Sb (6a, 6b)), which excludes the existence of conformers resulting from restricted rotation about the FeE or MoE bond in the case of 2a–2c.     

Bildung und Reaktionen silylierter Diphosphane

Preparation and Reactions of Silylated Diphosphanes The preparation of previously not available silylated diphosphanes is reported, i. e. the compounds (Me₃Si)₂P? P(SiMe₃)(CMe₃) 1 , (Me₃Si)₂P? P(CMe₃)₂ 2 and (CMe₃)₂P? P(SiMe₃)(CMe₃) 4 as well as of the respective PH containing derivatives and Li phosphides thereof. The reaction of 1 with MeOH leads to (Me₃Si)₂P? P(CMe₃) H 6 , while 4 generates (Me₃C)₂P? P(CMe₃) H 7 , and finally 3 gives access to (Me₃C)(Me₃Si)P? P(CMe₃) H 8 . LiBu on the other hand forms the Li phosphides Li(Me₃Si)P? P(SiMe₃)(CMe₃) 10 (through 1 ), Li(Me₃Si)P? P(CMe₃)₂ 11 (through 2 ), Li(Me₃C)P? P(SiMe₃)(CMe₃) 12 (through 3 ), and Li(Me₃C)P? P(CMe₃)₂ 13 (through 4 ), the latter being more easily accessible through the reaction of H(Me₃C)P? P(CMe₃)₂ with LiBu. The introduction of one single CMe₃ substituent into 1 is sufficient to obtain the Li phosphide 10 , which is stable in ethers, as opposed to the corresponding Li Phosphide of the persilylated diphosphane.     

Triorganoantimon- und Triorganobismutdisulfonate Kristall- und Molekülstrukturen von (C6H5)3M(O3SC6H5)2 (M = Sb,Bi)

Triorganoantimony and Triorganobismuth Disulfonates. Crystal and Molecular Structure of (C₆H₅)₃M(O₃SC₆H₅)₂(M = Sb, Bi) Triorganoantimony disulfonates R₃Sb(O₃SR′)₂ [R = CH₃ = Me, C₆H₅ = Ph; R′ = Me, CH₂CH₂OH, Ph, 4-CH₃C₆H₄. R = Ph; R′ = 2,4-(NO₂)₂C₆H₃], Me₃Sb(O₃SCF₃)₂ · 2 H₂O and triphenylbismuth disulfonates Ph₃Bi(O₃SR′)₂ [R = Me, CF₃, CH₂CH₂OH, Ph, 4-CH₃C₆H₄, 2,4-(NO₂)₂C₆H₃] have been prepared by reaction of Me₃Sb(OH)₂, (Ph₃SbO)₂, and Ph₃BiCO₃, respectively, with the appropriate sulfonic acids. From vibrational data an ionic structure is inferred for Me₃Sb(O₃SCF₃)₂ · 2 H₂O and Me₃Sb(O₃SCH₂CH₂OH)₂, and a covalent structure for the other compounds with a penta-coordinated central atom with trigonal bipyramidal surrounding (Ph or Me in equatorial, unidentate sulfonate ligands in apical positions). Ph₃M(O₃SPh)₂ (M = Sb, Bi) crystallize monoclinic [space group P2₁/c; M = Sb/Bi: a = 1 611.5(8)/1 557.4(9), b = 987.5(6)/1 072,5(8), c = 1 859.9(9)/1 696.5(9) pm, β = 105.71(5)/96.62(5)°; Z = 4; d(calc.) 1.556/1.781 Mg · m^?3; V_cell = 2 849.2 · 10⁶/2 814.8 · 10⁶ pm³; structure determination from 3 438/3 078 independent reflexions (I ≥ 3σ(I)), R(unweighted) = 0.030/0.029]. M is bonding to three Ph groups in the equational plane [mean distances Sb/Bi? C:210.1(4)/219.1(7) pm] and two sulfonate ligands with O in apical positions [distances Sb? O: 210.6(3), 212.8(2); Bi? O: 227.6(5), 228.0(4) pm]. Weak interaction of M with a second O atom of one sulfonate ligand is inferred from a rather short M? O contact distance [Sb? O: 327.4(4), Bi? O: 312.9(5) pm], and from the distortion of equatorial angles [C? Sb? C: 128.4(2), 119.2(2), 112.2(2); C? Bi? C: 135.9(3), 117.8(3), 106.3(3)°]