Polysulfonylamine. XL Darstellung von Silber(I)-disulfonylamid-Acetonitril-Komplexen. Röntgenstrukturanalytische und thermochemische Charakterisierung von Tetraacetonitrilsilber(I)-bis(dimesylamido)argentat(I) und von (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilsilber(I)

Polysulfonyl Amines. XL. Preparation of Silver(I) Disulfonylamide Acetonitrile Complexes. Characterization of Tetraacetonitrilesilver(I) bis(dimesylamido)argentate(I) and (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilesilver(I) by X-Ray Diffractometry and Thermal Analysis The following silver(I) disulfonylamides were prepared for the first time or by improved procedures: AgN(SO₂CH₃)₂ ( 2a ); AgN(SO₂C₆H₄-4-X)₂ with X = F ( 2b ), Cl ( 2c ), Br ( 2d ), CH₃ ( 2e ); silver(I) 1,2-benzenedisulfonimide AgN(SO₂)₂C₆H₄ ( 2f ). With acetonitrile, the salts 2a to 2e form (1/2) complexes AgN(SO₂R)· 2 CH₃CN ( 4a to 4e ), whereas 2f gives the (1/1) complex AgN(SO₂)₂C₆H · CH₃CN ( 4f ). The crystallographic data (at - 95°C) for the title compounds 4a and 4f are: 4a , space group C2/c, a = 1 967.6(4), b = 562.2(1), c = 2 353.0(5) pm, β = 102.21(2)°, V = 2.5440 nm³, Z = 4, D_x = 1.891 Mg m^?3; 4f , space group P2₁/m, a = 741.5(3), b = 980.4(4), c = 756.6(3) pm, β = 99.28(2)°, V = 0.5428 nm³, Z = 2, D_x = 2.246 Mg m^?3. 4a forms an ionic crystal [Ag(NCCH₃)₄]^⊕[Ag{N(SO₂CH₃)₂}₂]^? with a tetrahedrally coordinated silver atom (lying on a twofold axis) in the cation (225.3/225.7 pm for the two independent Ag? N distances, N? Ag? N 106.2—114.5°) and a linear-dicoordinated silver atom in the centrosymmetric anion (Ag? N 213.9 pm, two intraionic secondary Ag…O contacts 303.4 pm). 4f consists of uncharged molecules [C₆H₄(SO₂)₂N¹AgN²CCH₃] with crystallographic mirror symmetry (Ag? N¹ 218.8, Ag? N² 216.1 pm, N¹? Ag? N² 174.3°), associated into strands by intermolecular secondary silver-oxygen contacts (Ag…O 273.8 pm, O…Ag…O 175.6, N? Ag…O 91.9/88.2°). The thermochemical behaviour of 4f was investigated using thermogravimetry, differential scanning calorimetry (DSC), time- and temperature-resolved X-ray diffractometry (TXRD), and solution calorimetry. The desolvation process occurs in the temperature range from 60 to 200°C and appears to be complex, although no crystalline intermediate could be detected. The desolvation enthalpy at 298 K was found to be + 26.8(4) kJ mol^?1. 4a is desolvated in two steps at - 15 to 60°C and 60 to 95°C (DSC), suggesting the formation of AgN(SO₂CH₃) · CH₃CN as an intermediate.     

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.     

Metallkomplexe mit biologisch wichtigen Liganden. CLVII [1] Halbsandwich‐Komplexe mit Isocyanoacetylaminosäureestern und Isocyanoacetyldi‐ und tripeptidestern („Isocyano‐Peptide”︁)

Metal Complexes of Biologically Important Ligands, CLVII [1] Halfsandwich Complexes of Isocyanoacetylamino acid esters and of Isocyanoacetyldi‐ and tripeptide esters (?Isocyanopeptides”?) N‐Isocyanoacetyl‐amino acid esters CNCH₂C(O) NHCH(R)CO₂CH₃ (R = CH₃, CH(CH₃)₂, CH₂CH(CH₃)₂, CH₂C₆H₅) and N‐isocyanoacetyl‐di‐ and tripeptide esters CNCH₂C(O)NHCH(R¹)C(O)NHCH(R²)CO₂C₂H₅ and CNCH₂C(O)NHCH(R¹)C(O)NHCH (R²)C(O)NHCH(R³)CO₂CH₃ (R¹ = R² = R³ = CH₂C₆H₅, R² = H, CH₂C₆H₅) are available by condensation of potassium isocyanoacetate with amino acid esters or peptide esters. These isocyanides form with chloro‐bridged complexes [(arene)M(Cl)(μ‐Cl)]₂ (arene = Cp*, p‐cymene, M = Ir, Rh, Ru) in the presence of Ag[BF₄] or Ag[CF₃SO₃] the cationic halfsandwich complexes [(arene)M(isocyanide)₃]⁺X^? (X = BF₄, CF₃SO₃).     

Polysulfonylamine. XXXVII. Darstellung von Quecksilberdimesylamiden. Kristall- und Molekülstrukturen von Hg[N(SO2CH3)2]2, Hg[{N(SO2CH3)2}2(DMSO)2] und Hg[{N(SO2CH3)2}2(HMPA)]

Polysulfonyl Amines. XXXVII. Preparation of Mercury Dimesylamides. Crystal and Molecular Structures of Hg[N(SO₂CH₃)₂]₂, Hg[{N(SO₂CH₃)₂}₂(DMSO)₂], and Hg[{N(SO₂CH₃)₂}₂(HMPA)] Hg[N(SO₂CH₃)₂]₂ ( 1 ) and Hg₂[N(SO₂CH₃)₂]₂ ( 2 a ) are formed as colourless, sparingly soluble precipitates when solutions of Hg(NO₃)₂ or Hg₂(NO₃)₂ in dilute nitric acid are added to an aqueous HN(SO₂CH₃)₂ solution. By a similar reaction, Hg₂[N(SO₂C₆H₄ ? Cl? 4)₂]₂ is obtained. 1 forms isolable complexes of composition Hg[N(SO₂CH₃)₂]₂ · 2 L with L = dimethyl sulfoxide (complex 3 a ), acetonitrile, dimethyl formamide, pyridine or 1,10-phenanthroline and a (1/1) complex Hg[N(SO₂CH₃)₂]₂ · HMPA ( 4 ) with hexamethyl phosphoramide. Attempted complexation of 2 a with some of these ligands induced formation of Hg⁰ and the corresponding Hg^II complexes. Crystallographic data (at -95°C) are for 1: space group 14₁/a, a = 990.7(2), c = 2897.7(8) pm, V = 2.844 nm³, Z = 8, D_x = 2.545Mgm^?3; for 4a: space group P1 , a = 767.8(2), b = 859.2(2), c = 925.2(2)pm α = 68.44(2), β = 86.68(2), γ = 76.24(2)°, V = 0.551nm³, Z = 1, D_x = 2.113 Mgm^?3; for 4: space group P2₁/c, a = 1041.3(3), b = 1545.4(3), c = 1542.5(3) pm, β = 100.30(2)°, V = 2.474nm³, Z = 4, D_x = 1.944Mgm³. The three compounds form molecular crystals. The molecular structures contain a linear or approximately linear, covalent NHgN moiety; the Hg? N distances and N? Hg? N angles are 206.7(4) pm and 176.3(2)° for 1, 207.2(2) pm and 180.0° for 3a, 205.7(4)/206.7(4) pm and 170.5(1)° for 4. In the complexes 3a and 4, the 0-ligands are bonded to the Hg atoms perpendicularly to the N? Hg? N axes, leading in 3a to a square-planar trans-(N₂O₂) coordination with Hg? 0 261.2(2) pm and N? Hg? O 92.3(1)/87.7(1)°, in 4 to a slightly distorted T-shaped (N₂O) geometry with Hg? 0 246.2(4)pm and N? Hg? 0 96.7(1)/92.0(1)°. In all three structures, the primary coordination is extended to a severely distorted (N₂O₄) hexacoordination by the appropriate number of secondary, inter- and/or intramolecular Hg…?0 inter-actions (0 atoms from sulfonyl groups, Hg…?O distances in the range 280—300pm). The intramolecular Hg…?O interactions give rise to nearly planar four-membered [HgNSO] rings. The molecule of 1 has a two-fold axis through the bisector of the N? Hg? N angle, the molecule of 3a an inversion center at the Hg atom. The molecule of 4 has no symmetry.     

Triorganoantimon- und Triorganobismutderivate von Carbonsäuren fünfgliedriger Heterocyclen Kristall- und Molekülstruktur von (C6H5)3Sb(O2C-2-C4H3S)2

Inhaltsübersicht. Triorganoantimon- und Triorganobismutdicarboxylate R₃M[O₂C(CH₂)ⁿ-2-C₄H₃X]₂ (M = Sb, R = CH₃, C₆H₁₁, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄; n = 0, X = O, S, NH, NCH₃. M = Sb, R = CH₃, C₆H₅; M = Bi, R = C₆H₅; n = 1, X = O, S. M = Sb, R = C₆H₁₁, n = 1, X = S; R = 4-FC₆H₄, n = 0, X = O, S, NCH₃; R = 2,4,6-(CH₃)₃C₆H₂, n = 0, X = O, S, NH) wurden durch Reaktionen von R₃Sb(OH)₂ (R = CH₃, C₆H₁₁, 2,4,6-(CH₃)₃C₆H₂), R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄, 4-FC₆H₄) bzw. R₃BiCO₃ mit den entsprechenden fünfgliedrigen heterocyclischen Carbonsäuren 2-C₄H₃X(CH₂)_nCOOH dargestellt. Auf der Basis schwingungsspektroskopischer Daten wird für alle Verbindungen eine trigonal bipyramidale Umgebung vom M (zwei O-Atome von einzähnigen Carboxylatliganden in den apikalen, drei C-Atome von R in den äquatorialen Positionen) vorgeschlagen, ferner eine schwache Wechselwirkung zwischen O(=C) jeder Carboxylatgruppe und M. Die Kristallstrukturbestimmung von (C₆H₅)₃Sb(O₂C–2-C₄H₃S)₃ stützt diesen Vorschlag. Die Verbindung kristallisiert triklin [Raumgruppe P$1; a = 891,8(14), b = 1058,2(12), c = 1435,6(9) pm, α = 68,53(8), β = 85,47(9), γ = 85,99(11)°; Z = 2; d(ber.) = 1,607 Mg m^–3; V(Zelle) = 1255,6 ų; Strukturbestimmung anhand von 3947 unabhängigen Reflexen (F_o > 3σ(F²_o)), R(ungewichtet) = 0,037]. Sb bindet drei C₆H₅-Gruppen in der äquatorialen Ebene [mittlerer Abstand Sb–C: 211,1(5)pm] und zwei einzähnige Carboxylatliganden in den apikalen Positionen einer verzerrten trigonalen Bipyramide [mittlerer Abstand Sb–O: 212,0(4) pm]. Aus den relativ kurzen Sb – O(=C)-Abständen [274,4(4) und 294,9(4) pm] und aus der Aufweitung des dem O(=C)-Atom nächsten äquatorialen C–Sb–C-Winkels auf 145,9(2)° [andere C-Sb-C-Winkel: 104,4(2), 109,5(2)°] wird auf schwache Sb–O(=C)-Koordination geschlossen. Schließlich wird eine Korrelation zwischen dem (+, –)I-Effekt des Organoliganden R an M (M = Sb, Bi) und der Stärke der M–O(=C)-Koordination in den Dicarboxylaten R₃M[O₂C(CH₂)_n–2-C₄H₃X]₂ vorgeschlagen. Triorganoanümony and Triorganobismuth Derivatives of Carbonic Acids of Five-membered Heterocycles. Crystal and Molecular Structure of (C₆H₅)₃Sb(O₂C–2-C₄H₃S)₂ Triorganoantimony- and triorganobismuth dicarboxylates R₃M[O₂C(CH₂)_n–2-C₄H₃X]₂ (M = Sb, R = CH₃, C₆H₁₁, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄; n = 0, X = O, S, NH, NCH₃. M = Sb, R = CH₃, C₆H₅; M = Bi, R = C₆H₅; n = 1, X = O, S. M = Sb, R = C₆H₁₁, n = 1, X = S; R = 4-FC₆H₄, n = 0, X = O, S, NCH₃; R = 2,4,6-(CH₃)₃C₆H₂, n = 0, X = O, S, NH) have been prepared by reaction of R₃Sb(OH)₂ (R = CH₃, C₆H₁₁; 2,4,6-(CH₃)₃C₆H₂), R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄, 4-FC₆H₄) or R₃BiCO₃ with the appropriate five-membered heterocyclic carboxylic acid. From vibrational data for all compounds a trigonal bipyramidal environment around M (two O atoms of unidendate carboxylate ligands in apical, three C atoms (of R) in equatorial positions) is proposed and also an additional weak interaction of O(=C) of each carboxylate group and M. The crystal structure determination of Ph₃Sb(O₂C–2-C₄H₃S)₂ gives additional prove to this proposal. It crystallizes triclinic [space group P$1; a = 891.8(14), b = 1058.2(12), c = 1435.6(9) pm, α = 68.53(8), β = 85.47(9), γ = 85.99(11)°; Z = 2; d(calc.) = 1.607 Mg m^–3; V_cell = 1255.6 ų; structure determination from 3 947 independent reflexions (F_o > 3σ(F²_o)), R(unweighted) = 0.037]. Sb is bonding to three C₆H₅ groups in the equatorial plane [mean distance Sb–C: 211.1(5) pm] and two unidentate carboxylate ligands in the apical positions of a distorted trigonal bipyramid [mean distance Sb–O: 212.0(4) pm]. From the relatively short Sb–O(=C) distances [274.4(4) and 294.9(4) pm] and from the enlarged value of the equatorial C–Sb–C angle next to the O(=C) atom [145.9(2)°; other C–Sb–C angles: 104.4(2), 109.5(2)°] additional weak Sb–O(=C) coordination is inferred. Finally a correlation between the (+, –) I-effect of the organic ligands It at M and the strength of the M–O = C interaction is suggested.     

d,h-μ-Benzylalkoxophosphonato-e-μ-alkoxo-f-μ-oxo-bis[trichloroantimon(V)]-Verbindungen

d, h-μ-Benzylalkoxophosphonato-e-μ-alkoxo-f-μ-oxo-bis[trichloroantimony(V)] Compounds The binuclear antimony(V) complexes Cl₃Sb(O)[R³(R¹O)PO₂](OR²)SbCl₃ 1 – 6 with R¹ = R² = CH₃, C₂H₅ and R³ = C₆H₅CH₂, (CH₃)₃C₆H₂CH₂ in solution slowly exchanges the R² groups between the oxygen atoms of the Sb₂O₂ ring. The SbOPOSb ringsystem makes rapid pseudorotation. The isomeres are detected by nmr spectroscopy. 1 (R¹ = R² = CH₃) crystallizes in the orthorhombic space group Pnma with a = 1247.0, b = 1324.1, c = 1207.9 pm and Z = 4. 2 (R¹ = CH₃, R² = C₂H₅) and 5 (R¹ = R² = CH₃, R³ = (CH₃)₃ · C₆H₂CH₂) crystallizes triclinic in the space group P-1 with a = 984.1, b = 1026.7, c = 1079.9 pm, α = 87.93, β = 75.70, γ = 87.62° and Z = 2 and a = 1164.6, b = 1296.9, c = 1712.9 pm, α = 109.9, β = 96.3, γ = 100.2° and Z = 4 resp., with two crystallographically independent molecules in the asymmetric unit.     

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.     

Polysulfonylamine. LVII. Zwei Silber(I)-di(organosulfonyl)-amide mit einer Silber-η2-Aryl- beziehungsweise einer Silber-Silber-Wechselwirkung: Kristallstrukturen von Silberdi(benzolsulfonyl)-amid-Wasser (1/0,5) und von wasserfreiem Silberdi(4-toluolsulfonyl)-amid

Polysulfonyl Amines. LVII. Two Silver(I) Di(organosulfonyl)-amides with Silver-η²-Aryl or Silver-Silver Interactions: Crystal Structures of Silver Di(benzenesulfonyl)amide-Water (1/0.5) and of Anhydrous Silver Di(4-toluenesulfonyl)-amide Crystals of [(PhSO₂)₂NAg(μ-H₂O)AgN(SO₂Ph)₂]_n ( 5 ) and [(4-Me? C₆H₄SO₂)₂NAgAgN(SO₂C₆H₄-4-Me)₂]_n ( 6 ) were obtained from aqueous solutions. The crystallographic data are for 5 (at ?95°C): monoclinic, space group C2/c, a = 2 743.8(5), b = 600.49(12), c = 1 664.5(3) pm, β = 101.143(15)°, V = 2.6908 nm³, Z = 8, D_x = 2.040 Mg m^?3; for 6 (at ?130°C): monoclinic, space group P2₁/n, a = 1 099.8(5), b = 563.7(3), c = 2 487.7(13) pm, β = 99.68(4)°, V = 1.5203 nm³, Z = 4, D_x = 1.888 Mg m^?3. In both crystals, the silver atom has a fivefold coordination. The structure of 5 displays [(RSO₂)₂N? Ag(μ-H₂O)Ag′? N(SO₂R)₂] units with Ag? N 226.9 pm, Ag? O 236.7 pm and Ag? O? Ag′ 95.3°; the water oxygen lies on a crystallographic twofold axis. These units are extended to two fused six-membered rings by intramolecular dative bonds (S)O → Ag′ and S(O)′ → Ag (249.3 pm). One phenyl group from each (PhSO₂)₂N moiety is η²-coordinated with its p-C and one m-C atom to a silver atom of a neighbouring bicyclic unit related by a glide plane to form infinite parallel strands (p-C? Ag 252.2, m-C? Ag 263.9 pm). The strands are interconnected into parallel layers through hydrogen bonds between H₂O and sulfonyl oxygens [O …? O(S) 276.1 pm]. These layers consist of a hydrophilic inner region containing metal ions, N(SO₂)₂ fragments and water molecules, and hydrophobic surfaces formed by phenyl groups. The structure of 6 features centrosymmetric [(RSO₂)₂N? Ag? Ag′? N(SO₂R)₂] units with two intramolecular dative bonds (S)O → Ag′ and (S)O′ → Ag (Ag? Ag′ 295.4, Ag? N 226.0, Ag? O 229.4 pm). These bi-pentacyclic units are associated by translation parallel to y into infinite strands by two dative (S)O → Ag bonds per silver atom (Ag? O 243.2 and 253.3 pm).     

Polysulfonylamine. XLII. Ein Aquasilber(I)-Komplex mit einem Ag(m̈-H2O)2Ag-Strukturmotiv: Röntgenstrukturanalytische und thermoanalytische Charakterisierung von Aqua(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido)silber(I)

Polysulfonyl Amines. XLII. An Aquasilver(I) Complex with an Ag(m?-H₂O)₂Ag Structural Unit: Characterization of Aqua(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido)silver(I) by X-Ray Diffractometry and Thermal Analysis The title compound C₆H₄(SO₂)₂NAg · H₂O, where C₆H₄(SO₂)₂N^º is the anion of 1,2-benzenedisulfonimide, crystallizes in the monoclinic space group C2/m with (at ?95°C) a = 1 129,7(3), b = 1 196.1(3), c = 810.7(2) pm, β = 124.25(2)°, V = 0.9055 nm³, Z = 4, D_x = 2.524 Mg m^?3. The crystal packing consists of [Ag(m?-H₂O)₂Ag{m?-C₆H₄(SO₂)₂N}₂]_n bands with crystallographic mirror symmetry, associated into layers by H-bonds with O(W)—O(S) 289.7 pm. The Ag(m?-H₂O)₂Ag moiety forms a planar four-membered ring with Ag? O(W)? Ag 97.3°, O(W)? Ag? O(W) 82.7° and Ag°Ag 372.1 pm. In the Ag{C₆H₄(SO₂)₂N}₂Ag′ unit, the anions act as tridentate (N, 1-O, 3-O)-ligands: One is N-bonded to Ag and O,O-chelated to Ag′, the other N-bonded to Ag′ and O,O-chelated to Ag. The silver atoms are (O₄N)-pentacoordinate, with nitrogen in the apical position of a distorted square pyramid [Ag? N 223.6, Ag? O(W) 247.8, Ag? O(S) 259.4 pm]. The thermochemical behaviour of the hydrate was investigated by thermal analysis and calorimetry. Water is only released at temperatures above 220°C. The dehydration enthalpy at 298 K is + 13.9 kJ mol^?1.     

(CH3)2SBr2 – einige Reaktionen und Strukturen

(CH₃)₂SBr₂ – Reactions and Structures (CH₃)₂SBr₂ ( 1 ) is a donor acceptor complex (8-S-3 + 10-Br-2) which reacts with (CH₃)₂S(?O)NSi(CH₃)₃ to yield [(CH₃)₂S(O)?N? S(CH₃)₂]⁺Br^? ( 2 ). With SbBr₃ (CH₃)₂SBr⁺SbBr₄^? ( 3 ) can be isolated. 1 crystallizes monoclinic in the space group P2₁/c with a = 733.8, b = 734.2, c = 1132.7 pm, β = 92.8° and Z = 4. 2 crystallizes in the orthorhombic space group Pnma with a = 967.2, b = 793.3, c = 1168.3 pm and Z = 4. The SBr and BrBr force constants of 1 are compared with those of S₂Br₂, 3 and Br₂ resp. The nmr and mass spectra of 1 and 2 are communicated.     

Reaktivität von Monophosphan-Platin(0)-Verbindungen gegenüber Schwefeldioxid

Reactivity of Monophosphine Platinum(0) Complexes with SO₂ . The addition reaction of (PPh₃)Pt(ViSi) (ViSi = {η²-H₂C?CHSiMe₂}₂O) ( 1 ) with SO₂ gives within 30 min the red SO₂ complex (PPh₃)Pt(η²-H₂C?CHSiMe₂- OSiMe₂CH?CH₂)(SO₂) ( 2 ). A reaction time of 24 h with SO₂ leads to the elimination of the ViSi ligand, and the unstable monomeric intermediate (PPh₃)Pt(SO₂) cyclo- trimerizes to the stable cluster [Pt(PPh₃)(SO₂)]₃ ( 3 ). 3 is also obtained within 30 min by the reaction of (PPh₃)Pt(C₂H₄)₂ ( 4 ) with SO₂. The crystal structure of 3 has been determined; space group P2₁/n, Z = 4, a = 1 606.1(3), b = 1 019.3(1), c = 3 624.6(5) pm, β = 93.67°, R/R_w = 0.102/0.121.     

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.     

Triorganoantimon- und Triorganobismutderivate von 2-Pyridincarbonsäure und 2-Pyridylessigsäure Kristall- und Molekülstrukturen von (C6H5)3Sb(O2C-2-C5H4N)2 und (CH3)3Sb(O2CCH2-2-C5H4N)2

Triorganoantimony and Triorganobismuth Derivatives of 2-Pyridinecarboxylic Acid and 2-Pyridylacetic Acid. Crystal and Molecular Structures of (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ Triorganoantimony and triorganobismuth dicarboxylates R₃M(O₂C-2-C₅H₄N)₂ (M = Sb, R = CH₃, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄) and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ have been prepared from (CH₃)₃Sb(OH)₂, R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄), or R₃BiCO₃ (R = C₆H₅, 4-CH₃C₆H₄) and the appropriate heterocyclic carboxylic acid. Vibrational spectroscopic data indicate a trigonal bipyramidal environment of M the O(? C)-atoms of the carboxylate ligands being in the apical and three C atoms (of R) in the equatorial positions; in addition coordinative interaction occurs in the 2-pyridinecarboxylates between M and O(?C) of one and N of the other carboxylate ligand and in (CH₃)₃)Sb(O₂CCH₂-2-C₅H₄N)₂ between Sb and O(?C) of both carboxylate ligands. (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂/(CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ crystallize monoclinic [space group P2₁/c/P2₁/n; a = 892.6(9)/1043.4(6), b = 1326.9(6)/3166.2(18), c = 2233.1(9)/1147.5(7) pm, β = 99.74(8)°/97.67(5)° Z = 4/8; d(calc.) = 1.522/1.553 × Mg m^?3; V_cell = 2606.7 × 10⁶/3757.0 × 10⁶pm³, structure determination from 3798/4965 independent reflexions (F ≥ 4.0 σ(F))/(I ≥ 1.96 σ(I), R(unweighted) = 0.024/0.036]. Sb is bonding to three C₆H₅/CH₃ groups in the equatorial plane [mean distances Sb? C: 212.2(3)/208.7(6) pm] and two carboxylate ligands via O in the apical positions [Sb? O distances: 218.5(2), 209.9(2)/212.1(3), 213.2(3) pm]. In (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ there is a short Sb? O(?C) and a short Sb? N contact [Sb? O: 272.1(2), Sb? N: 260.2(2) pm] and distoritions of the equatorial angles [C? Sb? C: 99.2(1)°, 158.2(1)°, 102.0(1).] and of the axial angle [O? Sb? O: 169.9(1)°], and in (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂, which contains two different molecules in the asym-metric unit, there are two Sb? O(?C) contacts [Sb? O, mean: 302.2(4), and 310.7(4)pm, respectively] and distortions of the equatorial angles [C? Sb? C: 114.5(2)°, 132.4(3)° 113.1(2)°, and 123.9(3)° 115.5(2)°, 120.6(3)°, respectively] and of the axial angles [O? Sb? O: 174,9(1)°, 177.9(1)°, respectively].     

Synthese von Kupfer- und Silberkomplexen mit fünfzähnigen N,S- und sechszähnigen N,O-Chelatliganden – Charakterisierung und Kristallstrukturen von {Cu2[C6H4(SO2)NC(O)]2(C5H5N)4}, {Cu2[C5H3N(CHNC6H4SCH3)2]2}(PF6)2 und {Ag[C5H3N(CHNC6H4SCH3)2]}PO2F2

Synthesis of Copper and Silver Complexes with Pentadentate N,S and Hexadentate N,O Chelate Ligands – Characterization and Crystal Structures of {Cu₂[C₆H₄(SO₂)NC(O)]₂(C₅H₅N)₄}, {Cu₂[C₅H₃N(CHNC₆H₄SCH₃)₂]₂}(PF₆)₂, and {Ag[C₅H₃N(CHNC₆H₄SCH₃)₂]}PO₂F₂ In the course of the reaction of copper(II)-acetate monohydrate with 2,2′-bisbenzo[d][1,3]thiazolidyl in methanol the organic component is transformed to N,N′-bis-(2-thiophenyl)ethanediimine and subsequently oxidized to the N,N′-bis-(2-benzenesulfonyl)ethanediaciddiamide H₄BBSED, which coordinates in its deprotonated form two Cu²⁺ ions. Crystallisation from pyridine/n-hexane yields [Cu₂(BBSED)(py)₄] · MeOH. It forms triclinic crystals with the space group P1 and a = 995.5(2) pm, b = 1076.1(3) pm, c = 1120.7(2) pm, α = 104.17(1)°, β = 105.28(1)°, γ = 113.10(1)° and Z = 1. In the centrosymmetrical dinuclear complex the copper ions are coordinated in a square-pyramidal arrangement by three nitrogen and two oxygen atoms. The Jahn-Teller effect causes an elongation of the axial bond by approximately 30 pm. The reactions of the pentadentate ligand 2,6-Bis-[(2- methylthiophenyl)-2-azaethenyl]pyridine BMTEP with salts of copper(I), copper(II) and silver(I) yield the complexes [CU₂(BMTEP)₂](PF₆)₂, [Cu(BMTEP)]X₂ (X = BF, C1O) and [Ag(BMTEP)]X (X = PO₂F, ClO). [Cu₂(BMTEP)₂](PF₆)₂ crystallizes from acetone/diisopropyl- ether in form of monoclinic crystals with the space group C2/c, and a = 1833.2(3) pm, b = 2267.30(14) pm, c = 1323.5(2) pm, β= 118.286(5)°, and 2 = 4. In the dinuclear complex cation with the symmetry C₂ the copper ions are tetrahedrally coordinated by two bridging BMTEP ligands. The Cu? Cu distance of 278.3pm can be interpreted with weak Cu? Cu interactions which also manifest itself in a temperature independent paramagnetism of 0.45 B.M. The monomeric silver complex [Ag(BMTEP)]PO₂F₂ crystallizes from acetone/thf in the triclinic space group P1 with a = 768.7(3) pm, b = 1074.0(5) pm, c = 1356.8(5) pm, α = 99.52(2)°, β = 96.83(2)°, γ = 99.83(2)° and Z = 2. The central silver ion is coordinated by one sulfur and three nitrogen atoms of the ligand in a planar, semicircular arrangement. The bond lengths Ag? N = 240.4–261.7 and Ag? S = 257.2 pm are significantly elongated in comparison with single bonds.     

Polysulfonylamine. XLI. Ein Silber(I)-Hydrat ungewöhnlicher Zusammensetzung: Röntgenstrukturanalytische und thermochemische Charakterisierung von Tetrakis(dimesylamido)aquatetrasilber(I) [Ag4(N(SO2CH3)2}4(H2O)]

Polysulfonyl Amines. XLI. A Silver(I) Hydrate with an Unusual Composition: Characterization of Tetrakis(dimesylamido)aquatetrasilver(I) [Ag₄(N)SO₂CH₃)₂}₄(H₂O)] by X-Ray Diffraction and Thermal Analysis The title compound is obtained by crystallizing AgN(SO₂CH₃)₂ from water at room temperature. Crystallographic data (at ?95°C): Triclinic space group P1 , a = 864.6(4), b = 1 211.2(5), c = 1 399.1(5) pm, α = 90.97(3), β = 90.90(3), γ = 98.25(4)°, V = 1.4496 nm³, Z = 2, D_x = 2.608 Mg m^?3. The four independent silver atoms and the water molecule form zigzag chains Ag(1)-Ag(2)-(μ-H₂O)-Ag(3) …? Ag(4) …? Ag(1′) with distances Ag(1)-Ag(2) 309.7, Ag(2)-O(w) 241.8, O(w)-Ag(3) 241.4, Ag(3) …? Ag(4) 342.9, Ag(4) …? Ag(1′) 361.4 pm. The catenated silver atoms are further connected by the dimesylamide anions acting as tridentate bridging (α-O, N, ω-O)-ligands. The resulting strands are interconnected into layers through one O(S)-Ag′ contact (247 pm) and one hydrogen bond O(w)-H(l) …? O′(S) per repeating unit. Between the layers, a weak O(S) …? Ag″ interaction (271 ptn) and a hydrogen bond O(w)-H(2) …? O(S) per repeating unit are observed. The silver atoms Ag(l) to Ag(4) display the coordination numbers 5 [NO,Ag(2), distorted trigonal bipyramid], 5[NO₂,O(w)Ag(I), distorted trigonal bipyramid], 5[O₄,O(w), trigonal bipyramid], and 2 + 1 (N₂, li-near; plus a secondary Ag …? 0 contact). The dehydration of the title compound and a solid-solid phase transformation in anhydrous AgN(SO₂CH₃)₂, were quantitatively investigated by thermoconductometry and time- and temperature-resolved X-ray diffractometry (TXRD).     

Zur Bildung und Struktur der Phosphinophosphiniden-phosphorane tBu2P?PP(Me)tBu2 1, tBu(Me3Si)P?PP(Me)tBu2 2 und tBu2P?PP(Br)tBu2 3

Synthesis and Structure of Phosphinophosphinidene-phosphoranes tBu₂P? P?P(Me)tBu₂ 1, tBu(Me₃Si)P? P?P(Me)tBu₂ 2, and tBu₂P? P?P(Br)tBu₂ 3 A new method for the synthesis of 1 and 2 (Formulae see ?Inhaltsübersicht”?) is reported based on the reaction of 5 with substitution reagents (Me₂SO₄ or CH₃Cl). The results of the X-ray structure determination of 1 and 2 are given and compared with those of 3 . While in 3 one P? P distance corresponds to a double bond and the other P? P distance to a single bond (difference 12.5 pm) the differences of the P? P distances in 1 and 2 are much smaller: 5.28 pm in 1 , 4.68 pm in 2 . Both 1 and 2 crystallize monoclinic in the space group P2₁/n (Z = 4). 2 additionally contains two disordered molecules of the solvent pentane in the unit cell. Parameters of 1 : a = 884.32(8) pm, b = 1 924.67(25) pm, c = 1 277.07(13) pm, β = 100.816(8)°, and of 2 : a = 1 101.93(12) pm, b = 1 712.46(18) pm, c = 1 395.81(12) pm, β = 111.159(7)°, all data collected at 143 K. The skeleton of the three P atoms is bent (PPP angle 100.95° for 1 , 100.29° for 2 and 105.77° for 3 ). Ab initio SCF calculations are used to discuss the bonding situation in the molecular skeleton of the three P atoms of 1 and 3 . The results show a significant contribution of the ionic structure R₂P? P(^?)? P(⁺)(X)R₂. The structure with (partially) charged P atoms is stabilized by bulky polarizable groups R (as tBu) as compared to the fully covalent structure R₂P? P(X)? PR₂.     

The synthesis,NMR (1H, 13C, 119Sn) and IR spectral studies of some di‐ and tri‐organotin(IV) sulfonates: X‐ray crystal structure of [(n‐C4H9)2Sn(OSO2C6H4CH3‐4)2·2H2O]

A number of alkyltin(IV) paratoluenesulfonates, R_nSn(OSO₂C₆H₄CH₃‐4)_4?n (n = 2, 3; R = C₂H₅, n‐C₃H₇, n‐C₄H₉), have been prepared and IR spectra and solution NMR (¹H, ¹³C, ¹¹⁹Sn) are reported for these compounds, including (n‐C₄H₉)₂Sn(OSO₂X)₂ (X = CH₃ and CF₃), the NMR spectra of which have not been reported previously. From the chemical shift δ(¹¹⁹Sn) and the coupling constants ¹J(¹³C, ¹¹⁹Sn) and ²J(¹H, ¹¹⁹Sn), the coordination of the tin atom and the geometry of its coordination sphere in solutions of these compounds is suggested. IR spectra of the compounds are very similar to that observed for the paratoluenesulfonate anion in its sodium salt. The studies indicate that diorganotin(IV) paratoluenesulfonates, and the previously reported compounds (n‐C₄H₉)₂Sn(OSO₂X)₂ (X = CH₃ and CF₃), contain bridging SO₃X groups that yield polymeric structures with hexacoordination around tin and contain non‐linear C? Sn? C bonds. In triorganotin(IV) sulfonates, pentacoordination for tin with a planar SnC₃ skeleton and bidentate bridging paratoluenesulfonate anionic groups are suggested by IR and NMR spectral studies. The X‐ray structure shows [(n‐C₄H₉)₂Sn(OSO₂C₆H₄CH₃‐4)₂·2H₂O] to be monomeric containing six‐coordinate tin and crystallizes from methanol–chloroform in monoclinic space group C2/c. The Sn? O (paratoluenesulfonate) bond distance (2.26(2) Å) is indicative of a relatively high degree of ionic character in the metal–anion bonds. Copyright © 2003 John Wiley & Sons, Ltd.     

Phosphanimin‐ und Phosphaniminato‐Komplexe von Beryllium. Kristallstrukturen von [BeCl2(HNPPh3)2], [BeCl(HNPPh3)2(Py)]Cl und [Be3Cl2(NPPh3)4]

Phosphanimine and Phosphoraneiminato Complexes of Beryllium. Crystal Structures of [BeCl₂(HNPPh₃)₂], [BeCl(HNPPh₃)₂(Py)]Cl, and [Be₃Cl₂(NPPh₃)₄] Tetraphenylphosphonium hexachlorodiberyllate, (Ph₄P)₂[Be₂Cl₆], reacts with lithium phosphoraneiminate, [LiNPPh₃]₆, in dichloromethane to give the three‐nuclear beryllium phosphoraneiminate [Be₃Cl₂(NPPh₃)₄] ( 3 ). As a by‐product the phosphaneimine complex [BeCl₂(HNPPh₃)₂] ( 1 ) can be isolated, which reacts with pyridine to give the ionic complex [BeCl(HNPPh₃)₂(Py)]Cl ( 2 ). On the other hand, the silylated phosphanimine Me₃SiNP(p‐tolyl)₃ ( 5 ) does not react with BeCl₂ or (Ph₄P)₂[Be₂Cl₆] forming the expected phosphoraneiminates. From CH₂Cl₂ solutions only the amino‐phosphonium salt [(C₇H₇)₃PNH₂]Cl ( 4 ) can be obtained. The compounds 1 ‐ 5 are characterized by single X‐ray analyses and by IR spectroscopy. 1 ·C₇H₈: Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 1408.9(2), b = 1750.9(2), c = 1633.2(2) pm, β = 106.50(1)°; R₁ = 0.0385. 1 forms a molecular structure with short Be—N distances of 169.8(3) pm. 2 ·Py: Space group P1¯, Z = 4, lattice dimensions at 193 K: a = 969.5(1), b = 2077.1(2), c = 2266.4(2) pm, α = 72.24(1)°, β = 87.16(1)°, γ = 77.42(2)°, R₁ = 0.0776. 2 forms ion pairs in which the NH atoms of the phosphaneimine ligands act as hydrogen bridges with the chloride ion. The HNPPh₃ ligand realizes short Be—N bonds of 169.0(6) pm, the Be—N distance of the pyridine molecule is 182.5(6) pm. 3 ·3CH₂Cl₂: Space group P1¯, Z = 2, lattice dimensions at 193 K: a = 1333.2(2), b = 1370.2(2), c = 2151.8(3) pm, α = 107.14(1)°, β = 91.39(1)°, γ = 105.15(1)°, R₁ = 0.0917. The structure of the three‐nuclear molecule 3 corresponds with a Be²⁺ ion which is tetrahedrally coordinated by the nitrogen atoms of two {ClBe(NPPh₃)₂}^— chelates. 4 ·CH₂Cl₂: Space group P2₁/c, Z = 4, lattice dimensions at 193 K: a = 1206.6(2), b = 1798.0(2), c = 1096.2(1) pm, β = 97.65(1)°, R₁ = 0.0535. 4 forms dimeric units in which the NH₂ groups of the [(C₇H₇)₃PNH₂]⁺ cations act as hydrogen bridges with the chloride ions to give centrosymmetric eight‐membered rings. 5 : Space group P2₁/n, Z = 4, lattice dimensions at 193 K: a = 1074.3(2), b = 2132.2(3), c = 1075.5(2) pm, β = 110.68(1)°, R₁ = 0.0664. 5 forms molecules with distances PN of 154.6(3), SiN of 168.8(3) pm, and bond angle SiNP of 134.4(2)°.     

Synthese und Struktur von [(Ph3C6H2)Te]2, [(Ph3C6H2)Te(AuPPh3)2]PF6 und [(Ph3C6H2)TeAuI2]2

Synthesis and Structure of [(Ph₃C₆H₂)Te]₂, [(Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ and [(Ph₃C₆H₂)TeAuI₂]₂ [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with Ph₃PAu⁺ to yield [2,4,6-Ph₃C₆H₂TeAuPPh₃₂]PF₆ which can be oxidized by I₂ to form the gold(III) complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂. [(2,4,6-Ph₃C₆H₂)Te]₂ crystallizes in the monoclinic space group P2₁/c with a = 810.6(2); b = 2026.5(5); c = 2260.6(7) pm; β = 99.23(3)° and Z = 4. In the crystal structure the ditelluride exhibits a dihedral angle C11? Te1? Te2? C21 of 66.1(2)°. The distance Te1? Te2 is 269.45(6) pm. In the cation of the triclinic complex [(2,4,6-Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ (space group P1 ; a = 1197.4(3); b = 1457.2(4); c = 1680.0(6) pm; α = 84.69(3)°; β = 85.11(3)°; γ = 75.54(3)°; Z = 2) a pyramidal skeleton RTeAu₂ with distances Te? Au = 259.2(1) and 257.8(2) pm and Au? Au = 295.3(1) pm is present. [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ crystallizes in the triclinic space group P1 with a = 1086.3(3); b = 1462.9(6); c = 1654.2(2) pm; α = 85.25(2)°; β = 87.44(1)°; γ = 80.90(3)°; Z = 2. In the centrosymmetrical dinuclear complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ the Au atoms exhibit a square-planar coordination by two iodine atoms and two tellurolate ligands. The tellurolate ligands form symmetrical bridges with distances Te? Au = 260.0 pm. The distances Au? I are in the range of 260.3(1) and 263.7(1) pm.     

Die ersten Hydrogencarbonate mit einer trimeren [H2(CO3)3]4−-Baugruppe: Zur Darstellung und Kristallstruktur von Rb4H2(CO3)3 · H2O und K4H2(CO3)3 · 1,5 H2O

The First Hydrogencarbonates with a Trimeric [H₂(CO₃)₃]^4? Group: Preparation and Crystal Structure of Rb₄H₂(CO₃)₃ · H₂O and K₄H₂(CO₃)₃ · 1.5 H₂O Rb₄H₂(CO₃)₃ · H₂O and K₄H₂(CO₃)₃ · 1,5 H₂O were prepared by means of the reaction of (CH₃)₂CO₃ with RbOH resp. KOH in aqueous methanole. Trimer [H₂(CO₃)₃]^4?-anions were found in the crystal structure of Rb₄H₂(CO₃)₃ · H₂O (orthorhombic, Pnma (no. 62), a = 1 218.0(1) pm, b = 1 572.3(6) pm, c = 615.9(1) pm, V_EZ = 1 179.5(5) · 10⁶ pm³, Z = 4, R1(I ≥ 2σ(I)) = 0.027, wR2(I ≥ 2σ(I)) = 0.055). K₄H₂(CO₃)₃ · 1,5 H₂O crystallizes in an OD-structure. The determined superposition structure (orthorhombic, Pbam (no. 55), a = 1 161.8(1) pm, b = 597.0(1) pm, c = 383.85(3) pm, V_EZ = 266.3(1) · 10⁶ pm³, Z = 1, R1(I ≥ 2σ(I)) = 0.035, wR2(I ≥ 2σ(I)) = 0.074) can be derived from the structure of the rubidium compound. The thermal decomposition of the substances is discussed.