Schwingungs- und kernresonanzspektroskopische Untersuchungen am System Antimon(V)-chlorid/Methanol

Investigations of the System Antimony (V) Chloride/Methanol by Vibrational and N.M.R. Spectroscopy The 1 : 1 addition compound I of antimony(V) chloride and methanol reacts with further alcohol. In products with two resp. three methanol molecules these are bonded to I by H bridges (SbCl₅ · n CH₃OH; n = 1–3). More than three methanols yield to ionic products (H⁺(CH₃OH)_nSbCl₅OCH₃^?; n > 3). This can be demonstrated by spectroscopic methods. The vibrational and ¹H-n.m.r. spectra are assigned arid discussed.     

Addukte aus Phosphorylverbindungen und SbCl5 Darstellung und IR-Spektren der 1:1-Addukte aus Chlordimethylamino- bzw. Chlordimethylamino-methoxi-phosphorylverbindungen und Antimon(V)-chlorid

Adducts of Phosphoryl Compounds and SbCl₅ Preparation and IR Spectra of 1:1 Addition Compounds from Chlorodimethylamino- resp. Chlorodimethylaminomethoxiphosphoryl Compounds and Antimony(V) Chloride The addition compounds (CH₃O)₂[(CH₃)₂N]PO · SbCl₅ ( II ), (CH₃O)[(CH₃)₂N]₂PO · SbCl₅ ( III ), [(CH₃)₂N]₃PO · SbCl₅ ( IV ), Cl₂[(CH₃)₂N]PO · SbCl₅ ( VI ), Cl[(CH₃)₂N]₂PO · SbCl₅ ( VII ), and Cl(CH₃O)[(CH₃)₂N]PO · SbCl₅ ( VIII ) are prepared by reaction of the phosphoryl compounds with antimony(V) chloride. The influence of the Lewis acid to the bonds of the phosphoryl compounds is discussed. The ³¹P-n.m.r. data of the adducts are communicated and compared with those of the free phosphoryl compounds.     

Untersuchungen an Wasseraddukten des Antimon(V)-chlorids

Studies on Water Adducts of Antimony(V) Chloride Antimony(V) chloride gives four solid adducts of sbCl₅ · nH₂O I-IV (n = 1, 2, 3, 4) at room temperature. In the solid state I is oligomer by hydrogen bridges. In II, III, and IV are besides the adducts ionic products of the constitution H⁺(H₂O)_n] SbCl₅OH^? (n = 1, 2, 3). I and II reacts with sodium chloride to yield sodium hexachloroantimonate(V) · 1 resp. 2 H₂O. The vibrational spectra were discussed.     

Untersuchungen über das Reaktionsverhalten von Antimonpentachlorid. III [1]. Zur Reaktion von Antimon (V)-chlorid mit Methylisocyanat

Studies on the Reactivity of Antimony Pentachloride. III. The Reaction of Antimony(V) Chloride and Methylisocyanate Methylisocyanate CH₃NCO reacts with SbCl₅ in boiling CCl₄ by an insertion-reaction to a product of the formula C₅H₆Cl₉N₂O₂Sb I, which has the chlorformamidinium-structure (Cl? C(O)? N(CH₃)? CCl? N(CH₃)? C(O)? Cl)⊕SbCl₆?. Hydrolysis of I yields the heterocycle C₅H₆N₂O₄ II. The reaction with methanol gives (CH₃? NH? CCl? NH? CH₃)⊕SbCl₆? III and (CH₃? NH? CCl? N(CH₃)? C(O)? OCH₃)⊕SbCl₆? IV. The i.r. and Raman spectra of the compounds I, III and IV are discussed.     

Über die Reaktion von Trimethylamin mit Antimon(V)-chlorid

Inhaltsübersicht. Trimethylamin und Antimon(V)-chlorid bilden keinen Dornor-Acceptor Komplex. In Abhängigkeit vom Molverhältnis reagieren die Komponenten zu (CH₃)₃NCl⁺SbCl₆^– (I) bzw. zu (CH₃)₃NH+X^– und (CH₃)₂N=CH₃⁺X^– (X^– = SbCl₆^–, SbCI₄^–, Sb₃CI₁₄^3– und CI^–). I kann in (CH₃)₃NH⁺SbCl₆^– und (CH₃)₂N=CH₂+SbCl₆^– zerfallen. The Reaction of Trimethylamine with Antimony (V) Chloride Abstract. Trimethylamine and antimony(V) chloride forms no donor-acceptor-complex. In dependence of the molar ratio the compounds reacts to (CH₃)₃NCl⁺SbCl₆^– (I) resp. to (CH₃)₃NH+X^– and (CH₃)₂N=CH₃⁺X^– (X^– = SbCl₆^–, SbCI₄^–, Sb₃CI₁₄^3– and CI^–). I can decompose into (CH₃)₃NH⁺SbCl₆^– and (CH₃)₂N=CH₂+SbCl₆^–.     

l-Hydroxo/Alkoxo-l-oxo-l-sulfonato-jO:jO'-bis[trichloroantimon(V)]Verbindungen. Zweikernige Antimon(V)-Komplexe mit Sulfonatgruppen als überbrückenden Liganden

l-Hydroxo/alkoxo-l-oxo-l-sulfonato-jO:jO'-bis[trichloroantimony(V)] Compounds. Binuclear Antimony(V) Complexes with Sulfonate Groups as bridging Ligands Sulfonic acids react with antimony(V) chloride and water and water/alcohol resp. dependent of the molar ratios yielding Cl₃SbO(OH)(O₂S(O)CH₃)SbCl₃ ( 1 ), Cl₃SbO(OH)· (O₂S(O)CF₃)SbCl₃ ( 3 ) the monohydrate Cl₃SbO(OH)· (O₂S(O)CH₃)SbCl₃·H₂O ( 2 ) and the compounds Cl₃SbO(OR')(O₂S(O)CF₃)SbCl₃ ( 4 : R'=CH₃; 5 : R'=C₂H₅) and Cl₃SbO(OCH₃)(O₂S(O)C₂H₅)SbCl₃ ( 6 ) resp. The crystal and molecular structures of 1 to 3 , 5 and 6 are determined. 1 and 3 are associated by hydrogen bonds to dimers and crystallize monoclinic ( 1 : P2₁/c; 3 : P2₁/n). 2 is a hydroxonium salt H₃O⁺[Cl₃SbO₂(O₂S(O)CH₃)SbCl₃]^– with strong hydrogen bonds between cations and anions and crystallizes triclinic (P1). 5 and 6 crystallize monoclinic ( 5 : P2₁/m; 6 : P2₁/c). In 1 and 3 to 6 there is an intramolecular reorientation or an intermolecular exchange of protons and R' groups in solution. The NMR spectra are discussed.     

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)°.     

Schwingungsspektroskopische Untersuchungen an Trimethylphosphonium-Kationen (CH3)3PX+ (X = H,D) und Kristallstrukturen von (CH3)3PD+SbCl6− und (CH3)3PCl+SbCl6−

Vibrational Spectra of Trimethylphosphonium Cations (CH₃)₃PX⁺ (X = H, D) and Crystal Structures of (CH₃)₃PD⁺SbCl₆^? and (CH₃)₃PCl⁺SbCl₆^? The trimethylphosphonium salts (CH₃)₃PX⁺SbCl₆^? (X = H, D) and (CH₃)₃PH⁺MF₆^? (M = As, Sb) are prepared and characterized by vibrational and NMR spectroscopy (¹H, ³¹P, ¹³C). In addition the crystal structures of (CH₃)₃PD⁺SbCl₆^? and (CH₃)₃PCl⁺SbCl₆^? are reported. (CH₃)₃PD⁺SbCl₆^? crystallizes in the orthorhombic space group Pnma with a = 1555(1) pm, b = 753.1(8) pm, c = 1166(1) pm Z = 4. (CH₃)₃PCl⁺SbCl₆^? crystallizes triclinic in the space group P1 with a = 704.6(4) pm, b = 729.5(3) pm, c = 1391.1(7) pm, α = 89.57(4)°, b? = 88.04(4)°, γ = 74.98(4)° and Z = 2.     

Zweikernige Antimon(V)-Komplexe mit Diphenylphosphato-Brückenliganden

Binuclear Antimony(V) Complexes with Bridging Diphenylphosphato Ligands The binuclear antimony(V) complexes Cl₃Sb(O)[(C₆H₅O)₂PO₂]₂SbCl₃ ( 1 ), Cl₃Sb(O)[(C₆H₅O)₂PO₂](OCH₃)SbCl₃ ( 2 ), Cl₃Sb(O)[(C₆H₅O)₂PO₂](OH)SbCl₃ ( 3 ) and Cl₄Sb[(C₆H₅O)₂PO₂]₂SbCl₄ ( 4 ) are prepared by reaction of diphenylphosphoric acid with antimony(V) chloride, water and methanol in different molar ratios. The progress of the reactions was controlled by the ³¹P-NMR signals. 1 crystallizes triclinic in the space group P1 with a = 918.8, b = 1312.9, c = 1395.8 pm, α = 91.91, β = 101.36, γ = 95.90° and Z = 2. 2 to 4 crystallize in monoclinic space groups: 2 : C2/c, a = 2753.4, b = 1156.1, c = 1476.7 pm, β = 98.01° and Z = 8; 3 : P2₁/c, a = 1234.8, b = 1471.8, c = 1263.4 pm, β = 107.15° and Z = 4; 4 : P2₁/n, a = 1943.8, b = 940.8, c = 2015.6 pm, β = 109.87° and Z = 4 resp. The NMR spectra are discussed and some IR data are communicated.     

Die Kristallstruktur des 1 : 1-Adduktes zwischen Antimontrichlorid und Diphenylammoniumchlorid,SbCl3 · (C6H5)2NH2+Cl−

The Crystal Structure of the 1:1 Addition Compound between Antimony Trichloride and Diphenylammonium Chloride, SbCl₃ · (C₆H₅)₂NH₂⁺Cl^? The 1:1 addition compound between antimony trichloride and diphenylammoniumchloride SbCl₃ · (C₆H₅)₂NH₂⁺Cl^? crystallizes in the monoclinic space group P2₁/n with a = 5.668(8), b = 20.480(12), c = 14.448(17) Å, β = 110.4(1)° and Z = 4 formula units. Chains of SbCl₃ molecules and anion cation chains are bridged by Cl ions and form square tubes. The coordination of the Sb atoms by Cl atoms by Cl atoms and Cl ions is distorted octahedral. Mean distances are Sb? Cl = 2.37 Å for Sb? Cl (3×), 3.09 Å for Sb…Cl^? (2×) and 3.42 Å for Sb…Cl (1×). The Sb…Cl^? contacts and hydrogen bonds NH…Cl^? at 3.15 Å generate tetrahedral coordination of the Cl ions.     

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.     

Über Antimon(V)-bromchloride und ihre Stabilisierung durch Elektronendonatoren

SbCl₃Br₂ may be stabilized by electron donors. Crystalline 1:1 adducts with diethyl ether, tetrahydrofurane, triphenylphosphine oxide and -sulphide were isolated. Their bonding properties, regarding the donor strengths, are discussed. The tetrahydrofurane adduct takes up three molecules of CCl₄ in the presences of CCl₄ · SbCl₃Br₂ · OP(C₆H₅)₃ is converted in introbenzene into SbCl₃Br₂ · O₂NC₆H₅ which, at room temperature, transforms in the course of 15 hours to heteropolar compounds of the general formula [SbCl_nBr_4?n · (O₂NC₆H₅)₂]+[SbCl_mBr_6?m]^?, with m + n = 6 and n = 1, 2, 3, 4.     

Diaquahydrogenium hexachloroantimonate (V). Observed and calculated infrared spectra

The diaquahydrogenium hexachloroantimonates(V) H₅O₂⁺SbCl₆^-(I) and D₅O₂⁺SbCl₆^-(II) were prepared by the reaction of SbCl₅ · 2H₂O and SbCl₅ · 2D₂O with HCl or DCl respectively. The infrared spectra were assigned. In addition ab initio calculations were performed on the system H₅O₂⁺, for which frequencies and IR absorbances of three mutually perpendicular modes of the H-bonded proton and D-bonded deuteron were calculated.     

Nitrosolate und Nitrosolatokomplexe. III. Darstellung und Struktur von Nitrosolsäurederivaten organosubstituierter Antimon(V)-, Tellur(IV)- und Jod(III)-Verbindungen

Nitrosolates and Nitrosolatocompounds. III. Synthesis and Structures of Nitrosolate Derivatives of Organosubstituted Compounds of Antimony(V(, Tellurium(IV), and Iodine(III) In solution the derivatives of the nitrosolates of acetic and benzoic acids and of the ions (C₆H₅)₄Sb⁺, (CH₃),Sb⁺, (C₆H₅)₃Te⁺, and the derivative of the nitrosolate of acetic acid and of the ion C₁₂H₈I⁺ show ionic or covalent structures, depending on the polarity of the solvent. In the solid state only the derivatives of (C₁₂H₅)₄Sb⁺ unequivocally do not display salt character. The structure of (C₆H₅)₄Sb · O₂N₂C–CH₃ was determined by X-ray methods. The compound consists of separated molecules with slightly distorted trigonal-bipyramidonal environment of the antimony atom. The nitrosolato ligand is oxygen bonded to one of the apical positions. According to the electronic spectra of the solutions of the nitrosolate derivatives the nitrosolate ions react in the covalent forms either as uni-dentate ligands with O-coordination or as bidentate chelating or bridging ligands with O,O′-coordination.     

dh-μ-Carboxilato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimone(V)] Struktur und spektroskopsiche Untersuchungen

dh-μ-Carboxilato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimonies(V)] Structure and Spectroscopic Investigations The title compounds can be prepared by reaction of SbCl₅ · H₂O and RCOOH (R ? CF₃, CCl₃, CHCl₂, CH₂Cl, CH₃, CH₃CH₂, (CH₃)₂CH, H) or by reaction of H₅O₂⁺SbCl₆^? and RCO₂SbCl₄ in good yields. ¹H-NMR investigations proove that there is a rapid exchange between the components in the reaction mixture. The vibrational spectra are discussed in view of the CO₂ vibrations and hydrogen bonding. The crystal and molecular structure of dh-μ-Trichloroacetato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimony(V)] is determined by X-ray analysis.     

Chloroantimon(V)-phosphate

Chloroantimony(V) Phosphates The 1:1 adducts of alkoxiphosphoryl compounds and antimony(V) chloride eliminate alkylchloride to yield the dimere tetrachloroantimony(V) phosphates [Cl₄SbO₂PCl₂]₂ I, [Cl₄SbO₂P(OCH₃)Cl]₂ II, [Cl₄SbO₂P(OCH₃)₂]₂ III, [Cl₄SbO₂P(OC₂H₅)Cl]₂ IV, [Cl₄SbO₂P(OC₂H₅)₂]₂ V and the tetramere trichloroantimony(V) phosphates [Cl₃SbO₃POCH₃]₄ VI resp. [Cl₃SbO₃POC₂H₅]₄ VII. III can also be prepared by reaction of K⁺O₂P(OCH₃)₂^? with SbCl₅. The vibrational spectra, the ¹H- and the ³¹P-n.m.r. data of II, IV, V, VI and VII are communicated.     

Die Darstellung der Methylthio(trihalogen)phosphonium-Salze ClnBr3−nPSCH3+MF6−(n = 0–3; M = As,Sb) und Hal3PSCH3+SbCl6−(Hal = Br,Cl)

The Preparation of Methylthio(trihalogeno)phosphonium Salts Cl_nBr_3?nPSCH₃⁺MF₆^?(n = 0–3; M = As, Sb) and Hal₃PSCH₃⁺SbCl₆^?(Hal = Br, Cl) The methylthio(trihalogeno) phosphonium salts Br_nCl_3?nPSCH₃⁺MF₆^? (n = 0–3; M = As, Sb) are prepared by methylation of the corresponding thiophosphorylhalides Br_nCl_3?nPS in the system SO₂/CH₃F/MF₅. The hexachloroantimonates Hal₃PSCH₃⁺SbCl₆^?(Hal = Br, Cl) are synthesized by thiomethylation of PBr₃ and PCl₃ with CH₃SCl/SbCl₅. All salts are characterized by vibrational and NMR spectroscopy.     

Stabilitäten von As(V) in Chlorokomplexen

The temperature dependent behaviour of PCl₄AsCl₆, PCl₄SbCl₆ and AsCl₄SbCl₆ has been investigated byRaman spectroscopy. The As(V) containing complexes decompose into homogeneous molecular melts consisting of AsCl₃, Cl₂ and PCl₅, respectively. In PCl₄SbCl₆ PCl₄ ⁺ and SbCl₆ ^– complex ions were found in the solid as well as in the molten state.

     

Element-Element-Bindungen. II. Synthese und Struktur eines anellierten Tetrastibaadamantans,dargestellt aus Antimon(III)-chlorid und Natrium-cyclopentadienid

Element-Element Bonds. II. Synthesis and Structure of an Anellated Tetrastibaadamantane, Formed by Antimony(III) Chloride and Sodium Cyclopentadienide Revising the reaction between antimony(III) chloride and sodium cyclopentadienide in tetrahydrofuran (THF), originally published by FISCHER und SCHREINER [3], we could not verify the stated formation of tetra(cyclopentadienyl)distibane being red both in the solid and in solution. The pale yellow compound isolated instead is sodium [18-cyclopenta-2,4-dienyl-4,8,12-cyclopenta-2,4-diene-1,1,2-triyl-3a,8a-epistibino-tricyclopenta[1,4,7]tristiboninide] = 3 tetrahydrofuran 1 . Shown by an x-ray crystal structure determination (?45°C; monoclinic; Cc; a = 1882.7(9); b = 1183.5(5); c = 1733.8(13) pm; β = 93.38(5)°; Z = 4; R = 0.043) three (μ₃-C₅H₃) units together with four antimony atoms build up a tetrastibaadamantane framework with a (σ-C₅H₅) and a (μ₂-C₅H₃^?) group as additional substituents. Nearly centric above the anionic ring a sodium cation coordinated by three THF molecules is placed. Characteristic bond lengths and angles lie in the following ranges: Sb? C(sp²) 212–216; Sb? C(sp³) 216–228; Na? C 270–284; Na? O 226–235 pm; C? Sb? C 91–97; Sb? C? Sb 109–110°. ¹H and ¹³C-{¹H} n.m.r. spectra are discussed; the ion pair 1 shows a degenerate valency tautomerism in solution.     

Additionsverbindungen zwischen Antimon(III)-Halogeniden und 1,4-Dithiacycloheptan

Addition Compounds between Antimony(III)-Halides and 1,4-Dithiacycloheptane SbCl₃, SbBr₃, and SbI₃ do form the addition compounds SbCl₃ · 1,4-Dithiacycloheptane, SbBr₃ · 1,4-Dithiaheptane and 2 SbI₃ · 1,4-Dithiacycloheptane from benzene solutions. The new compounds are only stable in the solid form. FIR spectra of the SbCl₃ and SbBr₃ complexes are recorded as well as the X-ray structure of the SbCl₃ compound.