α, ω-Alkan-bis-dimethylarsansulfide und -selenide,eine neue Klasse von Liganden

α ω-Alkane-bis-dimethylarsine Sulfides and Selenides, a Novel Class of Ligands The reaction of α,ω-alkane-bis-dimethylarsanes (CH₃)₂As? (CH₂)_n? As (CH₃)₂ with sulfur and selenium results in formation of the sulfides and selenides, respectively, (CH₃)₂As(X)? (CH₂)_n? As(CH₃)₂ or (CH₃)₂As(X)? (CH₂)_n? As(X)(CH₃)₂ (X = S, Se), which form chelat-complexes with the salts CoX₂ · 6 H₂O (X = Cl^?, Br^?, I^?, NO₃^?). The UV-spectra of the complexes are presented and discussed.     

Komplexe der Ionen Ni2+ und Co2+ mit Sulfiden (Seleniden) di-, tri- und tetratertiärer Arsane

Complexes of the Ni²⁺ and Co²⁺ Ions with Sulfides and Selenides of di-, tri-, and tetratertiary Arsanes The reaction of the sulfides (selenides) of di-, tri- and tetra-tertiary arsanes with the salts CoCl₂ · 6 H₂O respectively Ni(ClO₄)₂ · 6 H₂O results in the formation of chelat complexes, in which the metal ions are tetrahedrally surrounded by the ligands. The UV spectra of the complexes are discussed.     

Aminomethylierung von Thiophosphorsäuredialkylester-, Phosphon- bzw. Thiophosphonsäurealkylesteramiden,Phosphon- bzw. Thiophosphonsäurediamiden und Diphenylthiophosphinsäureamid

Aminomethylation of Phosphoro-, Phosphono-, Phosphinoamidoates and -amidothioates Dialkylphosphoroamidates, alkyl-phosphonoamidates and phosphonoamidothioates react with C₂H₅O? CH₂? NR₂ and HCOH/HNR₂, respectively, as like as a N-aminomethylation forming the corresponding derivatives of the general formula R₂P(X)? NR′? CH₂? NR″₂? R = alkoxy, alkyl, aryl; R′ = H, alkyl; X = O, S; R″ = alkyl, cycloalkyl —. Under the same conditions phosphonodiamidoates and phosphonodiamidothioates yield RP(X)-[NR′? CH₂? NR″₂]₂ or RP(X)? NHR′? (NR′? CH₂? NR″₂) only. These compounds are not formed by interactions of RP(X)(NR′? CH₂OH)₂ with sec. amines. The aminomethylation of (C₆H₅)₂P(S)NH₂ gives unexceptional [(C₆H₅)₂P(S)]₂N? CH₂? NR′₂. The i.r. and ¹H-n.m.r. data of the prepared compounds, which can't be distilled mostly, are discussed.     

Synthesis of a “Masked” Terminal Nickel(II) Sulfide by Reductive Deprotection and its Reaction with Nitrous Oxide

The addition of 1 equiv of KSCPh₃ to [L^RNiCl] (L^R={(2,6‐iPr₂C₆H₃)NC(R)}₂CH; R=Me, tBu) in C₆H₆ results in the formation of [L^RNi(SCPh₃)] ( 1 : R=Me; 2 : R=tBu) in good yields. Subsequent reduction of 1 and 2 with 2 equiv of KC₈ in cold (?25 °C) Et₂O in the presence of 2 equiv of 18‐crown‐6 results in the formation of “masked” terminal Ni^II sulfides, [K(18‐crown‐6)][L^RNi(S)] ( 3 : R=Me; 4 : R=tBu), also in good yields. An X‐ray crystallographic analysis of these complexes suggests that they feature partial multiple‐bond character in their Ni? S linkages. Addition of N₂O to a toluene solution of 4 provides [K(18‐crown‐6)][L^tBuNi(SN?NO)], which features the first example of a thiohyponitrite (κ²‐[SN?NO]^2?) ligand.     

H/D isotope effect on charge‐inverted hydrogen‐bonded systems: Systematic classification of three different types in H3XH…YH3 (X = C,Si, or Ge,and Y = B,Al, or Ga) with multicomponent calculation

Three different H/D isotope effect in nine H₃XH(D)^…YH₃ (X = C, Si, or Ge, and Y = B, Al, or Ga) hydrogen‐bonded (HB) systems are classified using MP2 level of multicomponent molecular orbital method, which can take account of the nuclear quantum nature of proton and deuteron. First, in the case of H₃CH(D)^…YH₃ (Y = B, Al, or Ge) HB systems, the deuterium (D) substitution induces the usual H/D geometrical isotope effect such as the contraction of covalent R(C? H(D)) bonds and the elongation of intermolecular R(H(D)^…Y) and R(C^…Y) distances. Second, in the case of H₃XH(D)^…YH₃ (X = Si or Ge, and Y = Al or Ge) HB systems, where H atom is negatively charged called as charge‐inverted hydrogen‐bonded (CIHB) systems, the D substitution leads to the contraction of intermolecular R(H(D)^…Y) and R(X^…Y) distances. Finally, in the case of H₃XH(D)^…BH₃ (X = Si or Ge) HB systems, these intermolecular R(H(D)^…Y) and R(X^…Y) distances also contract with the D substitution, in which the origin of the contraction is not the same as that in CIHB systems. The H/D isotope effect on interaction energies and spatial distribution of nuclear wavefunctions are also analyzed. © 2015 Wiley Periodicals, Inc.     

Lithiumhydridosilylamide R2(H)SiN(Li)R′ – Darstellung,Eigenschaften und Kristallstrukturen

Lithium Hydridosilylamides R₂(H)SiN(Li)R′ – Preparation, Properties, and Crystal Structures The hydridosilylamines R₂(H)SiNHR′ ( 1 a : R = CHMe₂, R′ = SiMe₃; 1 b : R = Ph, R′ = SiMe₃; 1 c : R = CMe₃, R′ = SiMe₃; 1 d : R = R′ = CMe₃) were prepared by coammonolysis of chlorosilanes R₂(H)SiCl with Me₃SiCl ( 1 a , 1 b ) as well as by reaction of (Me₃C)₂(H)SiNHLi with Me₃SiCl ( 1 c ) and Me₃CNHLi with (Me₃C)₂(H)SiCl ( 1 d ). Treatment of 1 a–1 d with n-butyllithium in equimolar ratio in n-hexane resulted in the corresponding lithiumhydridosilylamides R₂(H)SiN(Li)R′ 2 a–2 d , stable in boiling m-xylene. The amines and amides were characterized spectroscopically, and the crystal structures of 2 b–2 d were determined. The comparison of the Si–H stretching vibrations and ²⁹Si–¹H coupling constants indicates that the hydrogen atom of the Si–H group in the amides has a high hydride character. The amides are dimeric in the solid state, forming a planar four-membered Li₂N₂ ring. Strong (Si)H … Li interactions exist in 2 c and 2 d , may be considered as quasi tricyclic dimers. The ‘‘NSiHLi rings”︁”︁ are located on the same side of the central Li₂N₂ ring. In 2 b significant interactions occurs between one lithium atom and the phenyl substituents. Furthermore all three amides show CH₃ … Li contacts.     

Steering of Configuration by (2‐Phosphanyl)phenolato Ligands in Trimethylphosphane Iron Complexes

(Diphenylphosphanyl)phenols C₆H₃(1‐OH)(2‐PPh₂)(4‐R¹)(6‐R²), abbreviated as (P^∧OH), oxidatively add to Fe(PMe₃)₄ affording hydridoiron(II) compounds fac‐FeH(P^∧O)(PMe₃)₃ ( 1 : R¹=R²=H; 2 : R¹=Me, R²=H; 3 : R¹=OMe, R²=H; 4 : R¹=Me, R²=CMe₃; 5 : R¹=R²=CMe₃) with high stereoselectivity. (2‐diphenylphosphanyl)thiophenol (P^∧SH) reacts accordingly forming fac‐FeH(P^∧S)(PMe₃)₃ ( 9 ). Complete assignment of ¹H, ¹³C, and ³¹P signals is achieved by 2D heteronuclear shift correlations. 4,6‐Di‐tert‐butyl‐(2‐diphenylphosphanyl)phenol reacts with FeI(Me)(PMe₃)₄ to form FeI(P^∧O)(PMe₃)₂ ( 6 ). 4 , 5 and 9 under 1 bar of CO are converted to monocarbonyl derivatives FeH(P^∧X)(CO)(PMe₃)₂ ( 7 , 8 : X = O; 10 : X = S) which in solution form mixtures of two isomers A and B . 4 and 5 react with their parent phosphanylphenols, respectively, to give diamagnetic complexes Fe(P^∧O)₂(PMe₃) ( 11 , 12 ) which dissociate trimethylphosphane to give paramagnetic compounds Fe(P^∧O)₂. The same phosphanylphenols react with FeCl₃ to afford racemic mixtures of complexes Fe(P^∧O)₃ ( 13 , 14 ). Structural data were also obtained from single crystals of compounds 1 , 5 , and 11 .     

Polysulfonylamine. LXXII [1]. Triphenylcarbenium- und Triphenylphosphonium-di(fluorsulfonyl)amid: Zwei Kristallstrukturen mit geordneten (FSO2)2N⊖-Lagen

Polysulfonyl Amines. LXXII. Triphenylcarbenium and Triphenylphosphonium Di(fluorosulfonyl)amides: Two Crystal Structures with Ordered (FSO₂)₂N^? Sites Treatment of HN(SO₂F)₂ in CH₂Cl₂ with Ph₃P, Ph₃PO or collidine (=B) affords the compounds Ph₃PH^⊕[(FSO₂)₂N]^? ( 3 ), Ph₃PO · HN(SO₂F)₂, and BH^⊕[(FSO₂)₂N]^? ( 7 ). The carbenium salt Ph₃C^⊕[(FSO₂)₂N]^? ( 5 ), obtained by metathesis of Ph₃CBr with [(C₆H₆)AgN(SO₂F)₂] in CH₂Cl₂, crystallizes from chloroform/petroleum ether as a monosolvate Ph₃C^⊕[(FSO₂)₂N]^? · CHCl₃ ( 6 ). In presence of a sterically hindered base, viz. collidine, 5 is a suitable reagent for the tritylation of molecules containing weakly activated H atoms (e. g.: MeCN → Ph₃CCH₂CN, acetone → tritylacetone; co-product: 7 ). The crystal structures of the ionic solids 3 (monoclinic, space group P2₁/n) and 6 (monoclinic, P2₁/c) were determined by X-ray diffraction at ?130°C; the structure refinements were not impaired by the notorious tendency of the (FSO₂)₂N moiety towards crystallographic disorder. As in the known structure of the tetraphenylarsonium salt, the anion of 3 and 6 adopts a staggered conformation of approximately C₂ symmetry (averages of all values: S? N? S 121.4°, N? S 156.2, S? O 141.6, S? F 156.6 pm). The crystal packing of 6 displays a three-centre C? H(…?O)₂ hydrogen bond between the CHCl₃ molecule and two oxygen atoms of a single anion, resulting in a six-membered ring [R₁²(6) pattern; H …? O 234 and 262 pm]. The crystal of 3 contains one-dimensional arrays of alternating cations and anions connected by a three-centre P? H(…?O)₂ bond [C(6) pattern; H …? O 237 and 254 pm]. The Ph₃C^⊕ cation of 6 is propeller-shaped, with three coplanar central bonds (mean C? C 144.5 pm) and interplanar angles of 52.7, 56.4 and 60.1° between the phenyl groups.     

Richtlinien und Bemerkungen der Redaktion und des Verlages für Abfassung von Manuskripten für die Zeitschrift für anorganische und allgemeine Chemie

Reaction of Trimethylsilylethers of Unsaturated Alcohols with Schwartz Reagent – Stabilisation of Cyclic Zirconiumorganic Compounds by the Moiety Cp₂ZrH₂ Besides the normal product of hydrozirconation the reaction of allyltrimethylsilylethers CH₂? CHC(R¹R²)OSi(CH₃)₃ ( I : R¹ = R² = H, VIII : R¹ = R² = CH₃, X : R¹ = H, R² = CH₃) with Cp₂Zr(H)Cl yields, as a result of a hydrogenation of the Si? O bond, trimethylsilane and a series of compounds with a Zr? O bond. Depending on the substitution of the α-C atom either dimeric chelates ( III ) or binuclear complexes of the type Cp₂Zr(Cl)CH₂CH₂C(R¹R²)OZr(Cl)Cp₂ ( IX : R¹ = R² = CH₃; XII : R¹ = H, R² = CH₃) are formed. Starting with X and excess Cp₂Zr(H)Cl the binuclear compound XIII is obtained which may be considered as an adduct of Cp₂ZrH₂ to the unsaturated chelate Compound XVII with a structure analogous to XIII is synthesized by the reaction of IX with Cp₂ZrH₂. The ¹H-NMR spectrum is in accordance with the existence of cis-trans-isomers of this complex.     

Unsymmetrische Triorganobismutane mit β-funktionalisierten Alkylsubstituenten

Unsymmetrical Triorganobismuthanes Containing β-Functionalized Alkylsubstituents Sodium diorganobismuthide, was treated with strained ring systems such as propyleneoxide, styreneoxide, ethylene-sulfide or propyleneimine to produce unsymmetrical triorganobismuthanes R₂BiCH₂CH(R′)XH (R = Me, Et, Ph, pTol; R′ = H, Me, Ph; X = O, S, NH) in good yields.     

Salze von Halogenophosphorsäuren. XV. Sulfan-α,ω-diyl-bis(fluorodithiophosphate), Reaktionsprodukte des Fluoridabbaus schwefelreicher Phosphorsulfide

Salts of Halogenophosphoric Acids. XV. Sulfane-α,ω-diyl-bis(fluorodithiophosphates). Products of the Fluoride Degradation of Sulfur-rich Phosphorus Sulfides By the reaction of sulfur-rich phosphorus sulfides ?P₄S_10+m”? (m = 0,5 to 6) with fluorides MF (M = Na, K, NH₄) in acetonitrile or 1,2-dimethoxy-ethane mixtures of sulfane-α,ω-diyl-bis(fluorodithiophosphates) [(PFS₂)₂S_n]^2? (n = 1 to 8) are formed. The average chain length n of the sulfane derivatives depends on the S:P ratio of the starting phosphorus sulfides. The compounds are identified by ¹⁹F and ³¹P n.m.r. spectroscopy.     

Schwefeldioxid als Ligand und Synthon. XII. Synthese und Reaktivität von Nickel(II)-Komplexen dreizähniger anionischer Liganden des Typs (C6H3{CH2NR1R2}2-2,6)−

Sulfur Dioxide as Ligand and Synthon. XII. Synthesis and Reaction Behaviour of Nickel(II) Complexes with Terdendate Anionic Ligands of the Type (C₆H₃{CH₂NR¹R²}₂?2,6)^? Organonickel(II) complexes of the type [NiX{C₆H₃(CH₂NR¹R²)₂?2,6}] (X = halide OH₂⁺/CF₃SO₃^?; R¹?R²?Et 1 ; R¹?R²?i? Pr 2 ; R¹ = Me, R² = Cy 3 ; (NR¹R²) = piperidino 4 ; (NR¹R²) = pyrrolidino 5 ) are described. ¹H and ¹³C NMR and UV/Vis spectra were recorded, and the X-ray crystal structure of 1 a (X = Br) was determined. This complex crystallizes orthorhombically in the space group Pbca with a = 1 335.8(2) pm, b = 1 903.3(3) pm, c = 1 365.4(3) pm and Z = 8, and has an approximately square-planar geometry. 4 and 5 show a reversible binding of SO₂ which has been detected by means of IR photoacoustic spectroscopy. The reactions of 1 – 5 with CS₂ and PhNSO are discussed.     

Ein neuartiges Diorganylzinn(IV)-Komplexkation als Gastspezies in einer ionischen Harnstoff-Einschlußverbindung: Bildung und Struktur von [trans-Me2Sn{OC(NH2)2}4]2+ · 2 (MeSO2)2N7 · 6 (NH2)2CO

Polysulfonylamines. CVIII. A Novel Diorganyltin(IV) Complex Cation as Guest Species in an Ionic Urea Inclusion Compound: Formation and Structure of [ trans -Me₂Sn{OC(NH₂)₂}₄]²⁺ · 2 (MeSO₂)₂N⁷ · 6 (NH₂)₂CO The title compound (triclinic, space group P 1, Z = 1, X-ray analysis at –130 °C) was fortuitously obtained during an attempt to complex the known dimeric hydroxide [Me₂Sn(A)(μ-OH)]₂, where A⁷ = (MeSO₂)₂N⁷, with four equivalents of urea. The trans-octahedral and crystallographically centrosymmetric [Me₂Sn(urea)₄]²⁺ cation (Sn–O 221.6 and 223.7 pm, cis-angles in the range 90 ± 1.5°) is the first structurally authenticated [R₂Sn(L)₄]²⁺ complex featuring a urea-type ligand L. In the crystal, these cations are sandwiched between and hydrogen-bonded to puckered layers corresponding to the [011] family of planes. Each layer is constructed from rows of A⁷ anions, which extend parallel to the x axis and are alternatingly cross-linked by a planar zig-zag tape of urea molecules or by a pair of inversion-related urea zig-zag tapes displaying a non-planar roof profile. The structure contains 23 crystallographically independent hydrogen bonds N–H…O/N, comprising two intracationic N–H…O bonds, two and four N–H…O bonds leading to the two respective types of urea tapes, eight N–H…O bonds and one N–H…N⁷ bond connecting the urea tapes to the electronegative atoms of the anions, and six N–H…O interactions between the ligands of the complex guest cation and C=O or S=O acceptors within the layers of the host lattice. The anion A⁷ accepts a total of twelve H bonds and adopts a previously unreported conformation.     

DFT/TDDFT studies of the ancillary ligand effects on structures and photophysical properties of rhenium (I) tricarbonyl complexes with the imidazo[4,5‐f]‐1,10‐phenanthroline ligand

The seven rhenium (I) tricarbonyl complexes having a general formula fac‐[ReBr(CO)₃(R₁,R₂,R₃‐N^{^}N)] (N^{^}N = imidazo[4,5‐f]‐1,10‐phenanthroline; R₁ = ? ^tBu, R₂ = R₃ = ? H, 1 ; R₁ = ? C?CH, R₂ = R₃ = ? H, 2 ; R₁ = ? ^tBu, R₂ = ? C?CH, R₃ = ? H, 3 ; R₁ = ? ^tBu, R₂ = R₃ = ? C?CH, 4 ; R₁ = ? ^tBu, R₂ = ? CH₃, R₃ = ? H, 5 ; R₁ = ? ^tBu, R₂ = R₃ = ? CH₃, 6 ; R₁ = ? ^tBu, R₂ = ? OCH₃, R₃ = ? H, 7 ) have been investigated theoretically by density functional theory (DFT) and time‐dependent density functional theory (TDDFT) methods. The different substituted groups on N^{^}N ligand induce changes on the electronic structures and photophysical properties for these complexes. It is found that the introduction of ? C?C decreases the energy level of lowest unoccupied molecular orbital (LUMO) while the introduction of ? CH₃ or ? OCH₃ lead to increase the energy level of LUMO. The order of LUMO energy level rising is in line with the increasing of donating abilities of substituted groups; and the influence of R₂ position is greater than that of R₁ position on LUMO energy level. The lowest energy absorption bands have changes in the order of 7 < 6 < 5 < 1 < 2 < 3 < 4 . These results of electronic affinity (EA), ionization potential (IP), and reorganization energy (λ) indicate that all of these complexes can be used as electron transporting materials. Moreover, the smallest difference between λ_electron and λ_hole of 4 indicates that it is better to be used as an emitter in the organic light‐emitting diodes. © 2015 Wiley Periodicals, Inc.     

Erdalkali-Fluoromanganate(III): BaMnF5 · H2O und SrMnF5 · H2O

Alkaline Earth Fluoromanganates(III): BaMnF₅ · H₂O and SrMnF₅ · H₂O Solid BaF₂ or SrF₂ forms with solutions of Mn³⁺ in aqueous hydrofluoric acid precipitates of hitherto unknown BaMnF₅ · H₂ and SrMnF₅ · H₂O respectively. X-ray structure determination on single crystals of both isotypic compounds (space group P2₁/m, Z = 2; BaMnF₅ · H₂O: a = 537.0(3), b = 817.2(2), c = 628.0(4) pm β = 111.17(5)°, R_w = 0.035 for 1403 reflections; SrMnF₅ · H₂O: a = 510.8(1), b = 792.0(2), c = 610.6(1) pm, β = 110.24(1)° R_w = 0.068 for 539 reflections) reveal pure [MnF₆]^3? octahedra connected with each other to infinite chains by sharing trans corners. The H₂O molecules are coordinated to the alkaline earth ions only and form weak O? H…F hydrogen bonds. The pronounced weakening of the Mn? F bonds within the chain direction (Mn? F 2X 212.7(1)/210.8(5) pm, 2X 183.8(3)/181.8(9) pm, 2X 186.9(2)/187.2(8) pm) may be due by halves to the Jahn-Teller-effect as can be deduced by bond valence calculations.     

Chiral Phosphine Ligands from Amino Acids. II. A Facile Synthesis of Phosphinoserines by Nucleophilic Phosphination Reactions – X‐Ray Structure Analyses of Ar2P–CH2–CH(NHBOC)(COOMe) (Ar = Ph,m‐xylyl)

Phosphino derivatives of serine R₂P–CH₂–CH(NHBOC)(COOMe) ( 2 a – 2 d ) have been obtained in high yield by nucleophilic phosphination of N‐(tert.butoxycarbonyl)‐3‐iodo‐L‐alanine methylester with secondary phosphines R₂PH (R = Ph, 2‐tolyl, 3,5‐xylyl, cyclohexyl) in DMF using potassium carbonate as the base. Deprotection of 2 b with HCl affords the amino acid ester hydrochloride [2‐Tol₂P–CH₂–CH(NH₃)(COOMe)]⁺Cl^– ( 3 a ). The X‐ray structures of 2 a (space group P2₁/n) and 2 c (space group P 1) have been determined. The two enantiomers of 2 a or 2 c are interconnected by N–H…O hydrogen bridges forming dimers in the solid state.     

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.     

M3NS3, die ersten Nitridsulfide der Lanthanide (M = La?Nd,Sm)

M₃NS₃, the First Nitride Sulfides of the Lanthanides (M = La? Nd, Sm) . The oxidation of the “light” lanthanides (M = La? Nd, Sm) with equimolar amounts of sulfur in the presence of NaN₃ as nitrogen source results in the formation of the first lanthanide nitride sulfides: M₃NS₃ (evacuated silica vessels, some NaCl as flux, 850°C, 7 d). NaCl is afterwards removed from the not moisture sensitive crude product (faint- or orange-yellow to amber-co- loured transparent needles, oftenly intergrown to feltlike bunches) upon rinsing with water. The crystal structure was determined from X-ray single crystal data for the example of Sm₃NS₃ (orthorhombic, Pnma (no. 62), a = 1 201.18(7), b = 394.32(3), c = 1 285.27(6) pm, Z = 4, R = 0.027, R_w = 0.024), and M₃NS₃ (M = La? Nd) proved to be isostructural from Guinier powder data. There are three crystallographically different M³⁺ cations in six- (1 X) and sevenfold (2 X) coordination of the N^3? and S^2? anions. [(N^3?)(M³⁺)₄] tetrahedra connected via two corners forming linear chains [N(M1)_1/1(M2)_1/1(M3)_2/2] ⁶⁺ build up the main structural feature. Arranged in the manner of a closest packing of rods, they are held together by three crystallographically different S^2? which take care for charge neutrality and three-dimensional interconnection.     

Polysulfonylamine. LXIX. Neuartige Pniktogendisulfonylamide: Synthese von Bismutdimesylamiden und Kristallstrukturen des zwölfgliedrigen Cyclodimers [Ph2BiN(SO2Me)2]2 und des ionischen Komplexes [H(OAsPh3)2]⊕(MeSO2)2N⊖

Polysulfonyl Amines. LXIX. Novel Pnictogen Disulfonylamides: Synthesis of Bismuth Dimesylamides and Crystal Structures of the Twelve-Membered Cyclodimer [Ph₂BiN(SO₂Me)₂]₂ and of the Ionic Complex [H(OAsPh₃)₂]^⊕(MeSO₂)₂N^? The novel bismuth(III or V) disulfonylamides Ph₂BiN(SO₂Me)₂ ( 1 ), PhBi[N(SO₂Me)₂]₂ ( 2 ), PhBi[N(SO₂Me)₂]Br ( 3 ), Bi[N(SO₂Me)₂]₂Cl ( 4 ), Bi[N(SO₂Me)₂]Cl₂ · 12-crown-4 ( 5 ) and Ph₃Bi[N(SO₂Me)₂]Cl ( 6 ) were obtained by acidolysis of Ph₃Bi with HN(SO₂Me)₂ (→ 1 ), by metathesis of AgN(SO₂Me)₂ with Ph₂BiCl (→ 1 ) or PhBiBr₂ (→ 2, 3 ), by condensation of BiCl₃ with Me₃SiN(SO₂Me)₂ (→ 4 ; in presence of 12-crown-4: → 5 ), or by oxidative addition of ClN(SO₂Me)₂ to Ph₃Bi (→ 6 ). Independently of the molar ratio employed, triphenylarsane oxide and dimesylamine form the crystalline 2/1 complex [H(OAsPh₃)₂]^⊕(MeSO₂)₂N^? ( 7 ). The crystal packing of 7 (monoclinic, space group C2/c) consists of discrete cations displaying crystallographic C_i symmetry and a strong O …? H …? O hydrogen bond (H atom located on a centre of symmetry, O …? O′ 241.2 pm, As? O …? O′ 120°, As? O 168.3 pm), and chiral anions with crystallographic C₂ symmetry (N? S 157.3 pm, S? N? S 122,9°). In the solid state, the bismuth(III) compound 1 (triclinic, space group P1 ) is a cyclodimer with crystallographic C_i symmetry, in which two Ph₂Bi^⊕ cations are connected through two (α-O, ω-O)-donating dimesylamide ligands to form a roughly twelve-membered [BiOSNSO]₂ ring (Bi? O 239.7 and 246.6, O? S 148.0 and 145.4, S? N 157.7 and 159.2 pm, Bi? O? S 126.6 and 127.5°). The bismuth atom adopts a pseudo-trigonal-bipyramidal geometry (O? Bi? O 165.4, C? Bi? C 93.0, O? Bi? C 83.8 to 86.5°). The essentially similar conformations of the discrete anion in 7 and of the bidentate bridging ligand in 1 are discussed in detail.     

Polysulfonylamine. XLVI Molekülkomplexe von Di(organosulfonyl)aminen mit Dimethylsulfoxid und Triphenylphosphinoxid. Röntgenstrukturanalyse von Di(4-fluorbenzolsulfonyl)amin-Dimethylsulfoxid(2/1)

Polysulfonyl Amines. XLVI. Molecular Adducts of Di(organosulfonyl)amines with Dimethyl Sulfoxide and Triphenylphosphine Oxide. X-Ray Structure Determination of Di(4-fluorobenzenesulfonyl)amine-Dimethyl Sulfoxide(2/1) From equimolar solutions of the respective components in CH₂Cl₂/petroleum ether, the following crystalline addition compounds were obtained: (X? C₆H₄SO₂)₂NH …? OS(CH₃)₂, where X = H, 4? CH₃, 4? Cl, 4? Br, 4? I, 4? NO₂ or 3? NO₂; [(4? F? C₆H₄SO₂)₂NH]₂ · (OS(CH)₃)₂ ( 8 ); (4? I? C₆H₄SO₂)₂NH · OP(C₆H₅)₃. A (2/1) complex of (4? F? C₆H₄SO₂)₂NH with OP(C₆H₅)₃ could not be isolated. The solid-state structure of the (2/1) compound 8 is compared with the known structure of the (1/1) complex (CH₃SO₂)₂NH · OS(CH₃)₂. The crystallographic data for 8 at ?95°C are: monoclinic, space group C2/c, a = 2 369.9(13), b = 1 006.8(4), c = 2 772.6(13) pm, β = 110.71(4)°, U = 6.187 nm³, Z = 8. Two N? H …? O hydrogen bonds with N …? O 275 and 280 pm connect the disulfonylamine molecules with the dimethyl sulfoxide molecule. The O atom of the latter has a trigonal-planar environment consisting of the S atom and the two hydrogen bond H atoms.