Darstellung,spektroskopische und röntgenographische Untersuchung von monomerem Sb(CCCH3)5 und dimerem Sb(OCH3)5

Preparation, Spectroscopic and X-Ray Structure Investigations of Monomeric Sb (CCCH₃)₅ and Dimeric Sb (OCH₃)₅ Prop₃SbCl₂ (Prop ? C?C? CH₃) reacts with NaProp to form SbProp₅. This compound is monomeric in solution and in solid state and has according to the vibrational spectra a trigonal-bipyramidal structure of D_3h symmetry. The X-Ray structure determination shows the monoclinic space group C2/c with 8 formula units per cell. Dimeric Sb(OMe)₅ (Me ? CH₃) is formed by the interaction of SbProp₅ with MeOH in an 1:5 molar ratio. The structure is determined by ¹H, ¹³C-NMR, IR and Raman spectra and the crystal structure of this alkoxide is described.     

Schwingungsspektren und Kraftkonstanten der Übergangsreihen OP (CH3)3–OP(OCH3)3 und SP(CH3)3–SP(OCH3)3

Vibrational Spectra and Force Constants of the Series OP(CH₃)₃? OP(OCH₃)₃ and SP(CH₃)₃? SP(OCH₃)₃ The vibrational spectra of OP(CH₃)₂(OCH₃), OP(CH₃)(OCH₃)₂, SP(CH₃)₂(OCH₃), and SP(CH₃)(OCH₃)₂, are recorded and assigned to the normal vibration. The valence force constants are calculated by a simplified force field. The results are disscussed for both series and compared with former results.     

[Sb(NPPh3)4]+SbF6−: Synthese,Kristallstruktur und 121Sb-Mößbauer-Spektrum

[Sb(NPPh₃)₄]⁺SbF₆^?: Synthesis, Crystal Structure, and ¹²¹Sb Mössbauer Spectrum The title compound as well as the hexachloro antimonate [Sb(NPPh₃)₄]⁺SbCl₆^? have been prepared by the reaction of Me₃SiNPPh₃ with SbF₅ and SbCl₅, respectively, in acetonitrile solutions. The compounds form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy, by ¹²¹Sb Mössbauer spectroscopy, and by crystal structure analyses. A complete crystal structure analysis, however, could be carried out with [Sb(NPPh₃)₄]⁺SbF₆^? only. The compound crystallizes orthorhombically in the space group Pccn with four formula units per unit cell. The structure determination was done with 3 972 observed unique reflections, R = 0.053. Lattice dimensions at 19°C: a = 1 658,6; b = 1 698.9, c = 2 361.9 pm. In the cation [Sb(NPPh₃)₄]⁺ the antimony atom is tetrahedrally coordinated by the four nitrogen atoms of the phosphoraneiminato ligands with extremely short Sb? N bond lengths of 193 pm.     

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)°]     

[Sb(12-Krone-4)2(CH3CN)][SbCl6]3 und [Bi(12-Krone-4)2(CH3CN)][SbCl6]3, die ersten Trikationen von Antimon(III) und Bismut(III)

[Sb(12-Crown-4)₂(CH₃CN)][SbCl₆]₃ and [Bi(12-Crown-4)₂(CH₃CN)][SbCl₆]₃, first Trications of Antimony(III) and Bismuth(III) The crown ether complexes [M(12-crown-4)₂(CH₃CN)][SbCl₆]₃ with M = Sb and Bi are formed by the reaction of antimony trichloride and bismuth trichloride, respectively, with antimony pentachloride in acetonitrile solution in the presence of 12-crown-4. They form colourless, moisture sensitive crystals, which were characterized by X-ray structure determinations and by IR spectroscopy. The complex with M = Sb was also characterized by ¹²¹Sb Mössbauer spectroscopy. Both complexes crystallize isotypically in the orthorhombic space group Pbcn with four formula units per unit cell. M = Sb: 3 483 observed unique reflections, R = 0.038. M = Bi: 2 958 observed unique reflections, R = 0.036. The compounds consist of SbCl₆^? ions and trications [M(12-crown-4)₂(CH₃CN)]³⁺, in which the M³⁺ ions are ninefold coordinated by the eight oxygen atoms of the crown ether molecules and by the nitrogen atom of the acetonitrile molecule. The lone pair of the M³⁺ ions has no steric effect.     

Reaktionen von ClS[OCH(CF3)2]3 und S[OCH(CF3)2]2 mit Phosphor(III)-Verbindungen

Reactions of ClS[OCH(CF₃)₂]₃ and S[OCH(CF₃)₂]₂ with Phosphorus(III) Derivatives The sulfurane ClS[OCH(CF₃)₂]₃ reacts with Me₃P to give the phosphonium salt [Me₃POCH(CF₃)₂]⁺Cl^?, in the case of (MeO)₃P products of an Arbuzov reaction are found: (MeO)₂P-(:O)OCH(CF₃)₂ and MeCl; the sulfurane is reduced to the sulfoxylate S[OCH(CF₃)₂]₂. The cyclic phosphite FP[OC(CF₃)₂C(CF₃)₂O] and P[OCH(CF₃)₂]₃ furnish derivatives of pentacoordinated phosphorus upon reaction with ClS[OCH(CF₃)₂]₃. The sulfoxylate S[OCH(CF₃)₂]₂ oxidises Me₃P, (MeO)₃P and P[OCH(CF₃)₂]₃ to form R₃P? O and R₃P? S (R = Me, OMe, OCH(CF₃)₂). The ether (CF₃)₂CHOCH(CF₃)₂ is isolated, too.     

Oxidative Addition von N‐Chlortriphenylphosphanimin an Phosphortrichlorid und Antimontrichlorid. Kristallstrukturen von (Cl3PNPPh3)2[PCl6][ClHCl],[SbCl4(HNPPh3)2][SbCl6] und [Sb(NPPh3)4][SbCl6]

Oxidative Addition of N‐chlorotriphenylphosphoraneimine onto Phosphorus(III) Chloride and Antimony(III) Chloride. Crystal Structures of (Cl₃PNPPh₃)₂[PCl₆][ClHCl], [SbCl₄(HNPPh₃)₂][SbCl₆], and [Sb(NPPh₃)₄][SbCl₆] Phosphorus(III) chloride reacts with N‐chlorotriphenylphosphoraneimine, ClNPPh₃, in CH₂Cl₂ solution strongly exothermically via oxidative addition to give (Cl₃PNPPh₃)₂[PCl₆][ClHCl] ( 1 ). As a by‐product, Ph₃PNP(O)Cl₂ can be obtained, which is formed from PCl₃ and ClNPPh₃ in the presence of POCl₃. In contrast to these results, antimony(III) chloride reacts with ClNPPh₃ in CH₂Cl₂ solution to give a mixture of the phosphoraneimine complex [SbCl₄(HNPPh₃)₂][SbCl₆] ( 2 ) and the phosphoraneiminato complex [Sb(NPPh₃)₄][SbCl₆] ( 3 ). The complexes 1 ‐ 3 were characterized by IR spectroscopy and by single crystal X‐ray determinations. 1 : Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 3282.0(2), b = 798.7(1), c = 1926.1(2) pm, β = 107.96(1)°, R₁ = 0.0302. 1 contains [Cl₃PNPPh₃]⁺ cations with PN bond lengths of 152.5(2) and 160.9(2) pm, and a PNP bond angle of 140.5(1)°. 2 ·CH₂Cl₂: Space group , Z = 2, lattice dimensions at 193 K: a = 1031.2(1), b = 1448.3(2), c = 1811,4(2) pm, α = 70.96(1)°, β = 87.67(1)°, γ = 75.37(1)°, R₁ = 0.0713. 2 ·CH₂Cl₂ contains cations [SbCl₄(HNPPh₃)₂]⁺ with octahedrally coordinated Sb atom and the HNPPh₃ ligand molecules being in trans‐position. Sb–N bond lengths are 207.6(6) and 209.3(6) pm, PN bond lengths 162.3(7) and 160.8(7), which approximately corresponds with double bonds. 3 ·0.5CH₂Cl₂: Space group P4/n, Z = 2, lattice dimensions at 193 K: a = b = 1678.8(1), c = 1244.3(1) pm, R₁ = 0.0618. 3 ·0.5CH₂Cl₂ contains [Sb(NPPh₃)₄]⁺ cations with tetrahedrally coordinated Sb atom and short Sb–N bond lengths of 193.7(6) pm. The PN distances of the phosphoraneiminato ligands, (NPPh₃)^? with 156.5(6) pm, correspond with double bonds, the SbNP bond angles are 130.6(3)°.     

Kraftkonstanten von Verbindungen des Typs (CH3)3ElCl+X− (El = N,P, As,Sb; X− = SbCl6−)

Force Constants of Compounds of the Type (CH₃)₃ElCl⁺X^?(El = N, P, As, Sb; X^? = SbCl₆^?) For the cations (CH₃)₃NCl⁺ ( 1 ), (CH₃)₃PCl⁺ ( 2 ), (CH₃)₃AsCl⁺ ( 3 ), and (CH₃)₃SbCl⁺ ( 4 ) a normal coordinate analysis using a general valence force field is performed by the method of Fadini. The force constants are discussed. Calculations of the potential energy distribution show, that the skeletal vibrations in 4 are all characteristic vibrations, but there is a strong coupling of vibrations in 1 .     

[μ‐(Me3SiCH2Sb)5–Sb1,Sb3–{W(CO)5}2] und [{(Me3Si)2CHSb}3Fe(CO)4] – zwei cyclische Komplexe mit Antimon‐Liganden

Syntheses and Crystal Structures of [μ‐(Me₃SiCH₂Sb)₅–Sb¹,Sb³–{W(CO)₅}₂] and [{(Me₃Si)₂CHSb}₃Fe(CO)₄] – Two Cyclic Complexes with Antimony Ligands cyclo‐(Me₃SiCH₂Sb)₅ reacts with [(THF)W(CO)₅] (THF = tetrahydrofuran) to form cyclo‐[μ‐(Me₃SiCH₂Sb)₅–Sb¹,Sb³–{W(CO)₅}₂] ( 1 ). The heterocycle cyclo‐ [{(Me₃Si)₂CHSb}₃Fe(CO)₄] ( 2 ) is formed by an insertion reaction of cyclo‐[(Me₃Si)₂CHSb]₃ and [Fe₂(CO)₉]. The crystal structures of 1 and 2 are reported.     

Phosphaniminato-Komplexe des Antimons. Die Kristallstrukturen von [Sb2Cl5(NPMe3)2][SbCl6] · CH3CN und [SbCl(NPPh3)]2[SbCl6]2 · 6 CH3CN

Phosphorane Iminato Complexes of Antimony. The Crystal Structures of [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN and [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN The title compounds are formed by reaction of antimony pentachloride in acetonitrile solution with the phosphorane iminato complexes SbCl₂(NPMe₃) and SbCl₂(NPPh₃), respectively, which themselves are synthesized by reaction of antimony trichloride with Me₃SiNPR₃ (R = Me, Ph). The complexionic compounds are characterized by ¹²¹Sb Mössbauer spectroscopy and by crystal structure determinations. [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN: Space group P4₁, Z = 4, 3 698 observed unique reflections, R = 0.022. Lattice dimensions at ?60°C: a = b = 1 056.0(1), c = 2 709.6(2) pm. The structure consists of SbCl₆^? ions and cations [Sb₂Cl₅(NPMe₃)₂(CH₃CN)]⁺, in which one Sb^III atom and one Sb^V atom are bridged by the N atoms of the phosphorane iminato ligands. [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN: Space group P1 , Z = 2, 5 958 observed unique reflections, R = 0.033. Lattice dimensions at ?60°C: a = 989.4(11), b = 1 273(1), c = 1 396(1) pm, α = 78.33(7), β = 77.27(8)°, γ = 86.62(8)°. The structure consists of SbCl₆^? ions and centrosymmetric cations [SbCl(NPPh₃)(CH₃CN)₂]₂²⁺, in which the antimony atoms are bridged by the N atoms of the phosphorane iminato ligands.     

Attempted Abstraction of the Halogenides in (HNEt3)[Re(CH3CN)2Cl4] and Crystal Structures of cis‐[Re(CH3CN)2Cl4]·CH3CN and cis‐[Re(NHC(OCH3)CH3)2Cl4]

The abstraction of the halogenide ligands in [Re(CH₃CN)₂Cl₄]^? should result in a solvent‐only stabilized Re^III complex. The reactions of salts of [Re(CH₃CN)₂Cl₄]^? with silver(I) and thallium(I) salts were investigated and the solid‐state structures of cis‐[Re(CH₃CN)₂Cl₄]·CH₃CN and cis‐[Re(NHC(OCH₃)CH₃)₂Cl₄] are described.     

Die Antimonid–Triantimonidometallate(III) Cs6K3Sb[AlSb3] und Cs6K3Sb[GaSb3]

The Antimonide Triantimonidometallates(III) Cs₆K₃Sb[AlSb₃] and Cs₆K₃Sb[GaSb₃] The novel compounds Cs₆K₃Sb[AlSb₃] and Cs₆K₃Sb[GaSb₃] are formed from stoichiometric mixtures of Cs, AlSb (GaSb) and KSb in sealed niobium ampoules at 950 K. The hexagonal structures are especially characterized by one-dimensional rod packings ¹∞[Cs₆K₃Sb] which are formed from columns of condensed (Cs₆K_6/2) icosahedra. The icosahedra are centered by Sb^3-? anions. The trigonal planar anions [AlSb₃]^6-? and [GaSb₃]^6-? are embedded between the icosahedra columns, and they are coordinated by alkali metal atoms. The FIR spectra were assigned to the vibrations of the [MSb₃]^6-? anions, with respect to the 6 m2-D_3h symmetry. (P6₃/mmc, No. 194; a = 1101.7 and 1097.2 pm; c = 1158.9 and 1150.1 pm; Z = 2; Single crystal data: 574 and 546 reflections; R = 0.073 and 0.029. Distances:d(Al? Sb) = 265.4 pm; d(Ga? Sb) = 265.1 pm; d(Sb? Cs) = 401.6–423.0 pm; d(Sb? K) = 358.6–367.3 pm).     

Synthese und Kristallstrukturen der Thiochloroantimonate(III) PPh4[Sb2SCl5] und (PPh4)2[Sb2SCl6] · CH3CN

Syntheses and Crystal Structures of the Thiochloroantimonates(III) PPh₄[Sb₂SCl₅] and (PPh₄)₂[Sb₂SCl₆]. CH₃CN (PPh₄)₂Sb₃Cl₁₁, obtained from Sb₂S₃, PPh₄Cl and HCl, reacts with Na₂S₄ in acetonitrile forming PPh₄[Sb₂SCl₅]. From this and Na₂S₄ or from (PPh₄)₂[Sb₂Cl₈] and Na₂S₄ or K₂S₅ in acetonitrile (PPh₄)₂[Sb₂SCl₆] · CH₃CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh₄[Sb₂SCl₅], monoclinic, space group P2₁/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, β = 99.12(2)°, Z = 4, R = 0.068 for 1283 reflextions; (PPh₄)₂[Sb₂SCl₆] · CH₃CN, triclinic, space group P1 , a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, α = 69.82(5), β = 85.08(4), γ = 71.54(6)°, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl₅]^? ions are associated via Sb …? S and Sb …? Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting.     

Dimethyl(methansulfinyl)sulfoniumhexafluorometallate (CH3)2SS(O)CH3+MF6− (M = As,Sb) und Kristallstruktur von Methansulfinylchlorid [1]

Dimethyl(methanesulfinyl)sulfonium Hexafluorometallates (CH₃)₂SS(O)CH₃⁺MF₆^? (M = As, Sb) and the Crystal Structure of Methanesulfinylchloride CH₃S(O)Cl [1] The preparation of dimethyl(methanesulfinyl)sulfoniumhexafluorometallates (CH₃)₂SS(O)CH₃⁺MF₆^? (M = As, Sb) and the spectroscopic characterization of the new thiosulfonium salts are described. Alternatively they can be obtained from methylmethanethiosulfinate by methylation. In addition the crystal structure of methanesulfinylchloride CH₃S(O)Cl at 113 K is reported. The compound crystallizes in the monoclinic space group P2₁/n with a = 528.2(1), b = 829.2(2), c = 880.9(2) pm, β = 90.48(2)° and Z = 4.     

Über Sn[OCH(CF3)2]2 und Sn (OCH2CF3)2 (n = 1, 2)

On S_n[OCH(CF₃)₂]₂ and S_n(OCH₂CF₃)₂ (n = 1, 2) The sulfoxylates S[OCH(R)CF₃]₂, 1 and 2 and the disulfides S₂[OCH(R)CF₃]₂, 5 and 6 (R = CF₃, H) are obtained by reacting SCl₂ or S₂Cl₂, respectively, and the lithium alcoxides LiOCH(R)CF₃. Chlorine and compound 2 give ClS(O)OCH₂F₃ and CF₃CH₂Cl, whereas the sulfur-sulfur bound is cleaved in 5 and 6 furnishing SCI₂, 1 and 2 , respectively. The ¹⁹F n.m.r. spectrum of 5 and the ¹H n.m.r. spectrum of 6 are interpreted in terms of hindered rotation about the sulfur-sulfur axis.     

The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N3)3], [MoO(N3)3⋅2 CH3CN], [(bipy)MoO(N3)3], [MoO(N3)5]2−, [WO(N3)4], and [WO(N3)4⋅CH3CN]

A series of novel molybdenum(V) and tungsten(VI) oxoazides was prepared starting from [MOF₄] (M=Mo, W) and Me₃SiN₃. While [WO(N₃)₄] was formed through fluoride–azide exchange in the reaction of Me₃SiN₃ with WOF₄ in SO₂ solution, the reaction with MoOF₄ resulted in a reduction of Mo^VI to Mo^V and formation of [MoO(N₃)₃]. Carried out in acetonitrile solution, these reactions resulted in the isolation of the corresponding adducts [MoO(N₃)₃?2 CH₃CN] and [WO(N₃)₄?CH₃CN]. Subsequent reactions of [MoO(N₃)₃] with 2,2′‐bipyridine and [PPh₄][N₃] resulted in the formation and isolation of [(bipy)MoO(N₃)₃] and [PPh₄]₂[MoO(N₃)₅], respectively. Most molybdenum(V) and tungsten(VI) oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [WO(N₃)₄?CH₃CN], [(bipy)MoO(N₃)₃], and [PPh₄]₂[MoO(N₃)₅], by their X‐ray crystal structures.     

Kinetics of gas‐phase reactions of CH3OCH2CF3, CH3OCH3, CH3OCH2CH3, CH3CH2OCH2CH3, and CHF2CF2OCH2CF3 with NO3 radicals at 298 K

Rate constants for the gas‐phase reactions of CH₃OCH₂CF₃ (k₁), CH₃OCH₃ (k₂), CH₃OCH₂CH₃ (k₃), and CH₃CH₂OCH₂CH₃ (k₄) with NO₃ radicals were determined by means of a relative rate method at 298 K. NO₃ radicals were prepared by thermal decomposition of N₂O₅ in a 700–750 Torr N₂O₅/NO₂/NO₃/air gas mixture in a 1‐m³ temperature‐controlled chamber. The measured rate constants at 298 K were k₁ = (5.3 ± 0.9) × 10^?18, k₂ = (1.07 ± 0.10) × 10^?16, k₃ = (7.81 ± 0.36) × 10^?16, and k₄ = (2.80 ± 0.10) × 10^?15 cm³ molecule^?1 s^?1. Potential energy surfaces for the NO₃ radical reactions were computationally explored, and the rate constants of k₁–k₅ were calculated according to the transition state theory. The calculated values of rate constants k₁–k₄ were in reasonable agreement with the experimentally determined values. The calculated value of k₅ was compared with the estimate (k₅ < 5.3 × 10^?21 cm³ molecule^?1 s^?1) derived from the correlation between the rate constants for reactions with NO₃ radicals (k₁–k₄) and the corresponding rate constants for reactions with OH radicals. We estimated the tropospheric lifetimes of CH₃OCH₂CF₃ and CHF₂CF₂OCH₂CF₃ to be 240 and >2.4 × 10⁵ years, respectively, with respect to reaction with NO₃ radicals. The tropospheric lifetimes of these compounds are much shorter with respect to the OH reaction. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 490–497, 2009     

Benzene carbon-hydrogen bond activation using Ru(C6Me6)[PH(C6H11(2]H2

The dihydride Ru(C₆Me₆)[PH(C₆H₁₁)₂]H₂ is synthesized in high yield by reducing Ru(C₆Me₆)[PH(C₆H₁₁)₂]Cl₂ with Na[AlH₂(OCH₂CH₂OMe)₂]. In benzene it loses hydrogen under UV irradiation to give Ru(C₆Me₆)[PH(C₆H₁₁(₂]H(C₆H₅).     

Über die Darstellung der N-Chlor-N-Methylammoniumsalze (CH3)nNCl4–n+MF6− (n = 1–3; M = As,Sb) und (CH3)2NCIX+MF6− (X = F,Br)

About the Preparation of N-Chloro-N-Methylammonium Salts (CH₃)_nNCl_4–n⁺MF₆^? (n = 1–3; M = As, Sb) and (CH₃)₂NClX⁺MF₆^? (X = F, Br) Simple one-step methods for the preparation of the methylated chloroammonium salts (CH₃)_nNCl_4–n⁺MF₆^? (n = 1–3; M = As, Sb) and for (CH₃)₂NClX⁺MF₆^? (X = F, Br) are reported. Their vibrational and NMR-spectroscopical data are discussed in comparison.     

Synthese und Struktur eines Pentaalkylchlorohexastibans Sb6R5Cl [R = (Me3Si)2CH]

Synthesis and Structure of Pentaalkylchlorohexastibane Sb₆R₅Cl [R = (Me₃Si)₂CH] The reaction of RSbCl₂ [R = (Me₃Si)₂CH] with Na‐K alloy in tetrahydrofuran gives besides the known rings Sb_nR_n (n = 3, 4), (Me₃Si)₂CH₂ and the pentaalkylchlorohexastibane Sb₆R₅Cl ( 1 ). 1 was characterized by spectroscopic methods (MS, ¹H‐, ¹³C‐NMR, X‐ray diffraction). The structure of 1 consists of a folded four membered antimony ring in the all‐trans configuration with three alkyl groups and one Sb(R)—Sb(R)Cl fragment as substituents.