Synthese und Kristallstrukturen der Wolfram(VI)-Alkinkomplexe [WCl4(Ph - C≡C - I)(THF)] und [WCl4(Ph-C≡C-Te-C4H9)(THF)] / Synthesis and Crystal Structures of the Tungsten(VI) Alkyne Complexes [WCl4(Ph-C≡C-I)(THF)] and [WCl4(Ph-C≡C-Te-C4H9)(THF)]

1993 ◽  
Vol 48 (8) ◽  
pp. 1105-1111 ◽  
Author(s):  
Michael Plate ◽  
Peter Hofacker ◽  
Werner Massa ◽  
Birgit Schwarz ◽  
Bernhard Neumüller ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Ir Spectroscopy ◽  
Oxygen Atom ◽  
Crystal Structures ◽  
Molecular Structures ◽  
Trans Position ◽  
Space Group ◽  
Structure Determinations ◽  
In Trans ◽  
Alkyne Complexes

[WCl4(Ph-C≡C-I)(THF)] has been prepared by the reaction of trans-[WCl4(SEt2)2] with Ph - C≡C - I in THF solution, whereas [WCl4(Ph-C≡C-Te-nC4H9)(THF)] has been synthesized by the reaction of Ph-C≡C-Te-nC4H9 with tungsten hexacloride in the presence of C2Cl4 and THF. Both complexes were characterized by IR spectroscopy and by crystal structure determinations.[WCl4(Ph-C≡C-I)(THF)]: Space group P21/c, Z = 4, 2617 observed unique reflections, R = 0.064. Lattice dimensions at –70°C: a = 1518.2(3), b = 714.5(1), c = 1540.0(3) pm, β = 90.09(3)°.[WCl4(Ph-C≡C-Te–nC4H9)(THF)]. Space group P1̄, Z = 2, 3911 observed unique reflections, R = 0.067. Lattice dimensions at 20°C: a = 844.0(3), b = 974.6(4), c = 1002.4(3) pm, α = 76.00(4), β= 105.14(1), γ = 82.03(3)°.Both complexes have molecular structures, in which the tungsten atoms are seven-coordi-nate by four chlorine ligands, by the two alkyne carbon atoms, and in trans position to the latter by the oxygen atom of the THF molecule. The WC bond lengths are 198 and 200(1) in the telluro complex and 206 and 196(1) pm in the iodine derivative.

Die Kristallstrukturen von [MoCl2(NO)2(OPEt3)]2, [MoCl3(NO)(OPPh3)2•MoCl4(OPPh3)2], [MoCl2(NO)(PPh3)2(CH3CN)] und [MoCl4(NPPh3)(OPPh3)] / The Crystal Structures of [MoCl2(NO)2(OPEt3)]2, [MoCl3(NO)(OPPh3)2 • MoCl4(OPPh3)2], [MoCl2(NO)(PPh3)2(CH3CN)], and [MoCl4(NPPh3)(OPPh3)]

1995 ◽  
Vol 50 (1) ◽  
pp. 1-10 ◽  
Author(s):  
Gunnar Philipp ◽  
Sigrid Wocadlo ◽  
Werner Massa ◽  
Kurt Dehnicke ◽  
Dieter Fenske ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Ir Spectroscopy ◽  
Trans Position ◽  
Nitrosyl Complex ◽  
Centrosymmetric Dimer ◽  
Acetonitrile Molecule ◽  
Space Group ◽  
Structure Determinations ◽  
In Trans ◽  
Complex Forms

The title compounds have been prepared by reactions of MoCl2(NO)2 with PPh3, OPPh3, or Me3SiNPR3 (R = Et, Ph) in dichloromethane and acetonitrile suspension, respectively. All complexes were characterized by IR spectroscopy and by crystal structure determinations. [MoCl2(NO)2(OPEt3)]2: Space group C2/c, Z = 4, 2950 observed unique reflections, R = 0.029. Lattice dimensions at —70 °C: a = 2390.5(11), b = 875.5(5), c = 1399.1(6) pm, β = 113.18(2)°. The complex forms a centrosymmetric dimer with MoCl2Mo bridges, the nitrosyl groups being in a cis-arrangement. The OPEt3 ligand is coordinated in trans position to one of the nitrosyl ligands.[MoCl3(NO)(OPPh3)2 • MoCl4(OPPh3)2]: Space group P21/c, Z = 4, 10243 observed unique reflections, R = 0.060. Lattice dimensions at —60 °C: a = 1900.4(3), b = 1689.1(5), c = 2209.3(7) pm, β = 95.92(2)°. The structure consists of the two independent complexes [MoCl3(NO)(OPPh3)2] and [MoCl4(OPPh3)2]. In both complexes the OPPh3 groups are in a cis-arrangement at the octahedrally coordinated Mo atoms; in the nitrosyl complex one of the OPPh3 molecules is in trans-position to the nitrosyl ligand.[MoCl2(NO)(PPh3)2(CH3CN)]: Space group P21/n, Z = 4, 5107 observed unique reflections, R = 0.028. Lattice dimensions at 20 °C: a = 1006.5(2), b = 1527.2(2), c = 2342.3(2) pm, β = 90.97(1)°. The PPh3 molecules are in trans-positions to one another at the octahedrally coordinated Mo atom, whereas the acetonitrile molecule is in trans-position to the nitrosyl ligand.[MoCl4(NPPh3)(OPPhi)]: Space group P21, Z = 2, 3323 observed unique reflections, R = 0.057. Lattice dimensions at —70 °C: a = 985.7(8), b = 1471.2(9), c = 1215.9(11) pm, β = 100.50(3)°. The OPPh3 molecule coordinates in trans-position to the phosphorane iminato ligand at the octahedrally coordinated Mo atom.

μ2-Halogenokomplexe von N-Bromsuccinimid und N-Bromphthalimid. Die Kristallstrukturen von PPh4[X(N-Bromsuccinimid)2] und von PPh4[X(N-Bromphthalimid)2] mit X = CI und Br / μ2-Halogeno Complexes of N-Bromosuccinimide and N-Bromophthalimide. The Crystal Structures of PPh4 [X(N-Bromosuccinimide)2] and PPh4 [X(N-Brom ophthalimide)2] with X = Cl and Br

1994 ◽  
Vol 49 (5) ◽  
pp. 593-601 ◽  
Author(s):  
Mitra Ghassemzadeh ◽  
Klaus Harms ◽  
Kurt Dehnicke ◽  
Dieter Fenske
Keyword(s):  
Crystal Structure ◽  
Ir Spectroscopy ◽  
Crystal Structures ◽  
Yellow Crystal ◽  
Halide Ions ◽  
Space Group ◽  
Bond Angles ◽  
Structure Solution ◽  
Structure Determinations ◽  
Acetonitrile Solutions

The μ2-halogeno complexes PPh4[X(N-bromosuccinimide)2] and PPh4[X(N-bromophthali- mide)2] with X = Cl and Br have been prepared by reactions of N-bromosuccinimide and N-bromophthalimide, respectively, with the corresponding tetraphenylphosphonium halides PPh4X in acetonitrile solutions. The compounds form pale yellow crystal needles, which were characterized by IR spectroscopy and by crystal structure determinations. PPh4[Cl(N-Bromosuccinimide)2] (1): Space group P21/n, Z = 4, structure solution with 2516 observed unique reflections, R = 0.040. Lattice dimensions at -25 °C: a = 1775.9(1), b = 764.3(1), c = 2341.7(2) pm, β = 101.84(1)°. PPh4[Br(N-Bromosuccinimide)2] (2): Space group P21/n, Z = 4, structure solution with 5620 observed unique reflections, R = 0.061. Lattice dimensions at 20 °C: a = 1776.9(9), b = 762.2(3), c = 2331(1) pm, β = 103.02(3)°. PPh4[Cl(N-Bromophthalimide)2] (3): Space group P1̅, Z = 4, structure solution with 3812 observed unique reflections, R = 0.039. Lattice dimensions at -50 °C: a = 918.5(2), b = 1115.0(3), c = 2584.4(5) pm, α = 88.22(3)°, β = 83.20(3)°, γ = 85.10(3)°. PPh4[Br(N-Bromophthalimide)2] (4): Space group P1̅, Z = 2, structure solution with 3413 observed unique reflections, R = 0.044. Lattice dimensions at -50 °C: a = 1120.2(2), b = 1308.6(3), c = 1343.2(3) pm, α = 105.10(3)°, β = 104.16(3)°, γ = 92.99(3)°. The structures of 1-4 consist of PPh4+ ions, anions [X(N-bromosuccinimide)2]- and [X(N-bromophthalimide)2]-, respectively, in which the halide ions X- are coordinated by the bromine atoms of N-bromosuccinimide and N-bromophthalimide molecules, respectively. The bond angles Br···X···Br are 86.48(5)° for 1, 85.1(1)° for 2, 102.31(6)° and 93.61(6)° for 3, and 91.86(4)° for 4. The bond angles N-Br···X are nearly linear.

μ2-Halogenokomplexe von N-Iodsuccinimid. Die Kristallstrukturen von PPh4[X(N-Iodsuccinimid)2] · CH3CN mit X = Cl, Br, / μ2-Halogeno Complexes of N-Iodosuccinimide. The Crystal Structures of PPh4[X(N-Iodosuccinimide)2] · CH3CN with X = Cl, Br, I

1994 ◽  
Vol 49 (5) ◽  
pp. 602-608 ◽  
Author(s):  
Mitra Ghassemzadeh ◽  
Kurt Dehnicke ◽  
Helmut Goesmann ◽  
Dieter Fenske
Keyword(s):  
Crystal Structure ◽  
Ir Spectroscopy ◽  
Crystal Structures ◽  
Yellow Crystal ◽  
Halide Ions ◽  
Space Group ◽  
Bond Angles ◽  
Pale Yellow ◽  
Structure Determinations ◽  
Acetonitrile Solutions

The μ2-halogeno complexes PPh4[X(N-Iodosuccinimide)2] · CH3CN with X = CL Br, I have been prepared by reactions of N-Iodosuccinimide with the corresponding tetraphenylphos- phonium halides PPh4X in acetonitrile solutions. The compounds form pale yellow crystal needles, which were characterized by IR spectroscopy and by crystal structure determinations. PPh4[Cl(N-Iodosuccinimide)2] · CH3CN (1): Space group Pna21, Z = 4, 4461 observed unique reflections. R = 0.027. Lattice dimensions at -60 °C: a = 1840.5(9), b = 2589(1), c = 728.2(4) pm. PPh4[Br(N-Iodosuccinimide)2] · CH3CN (2): Space group Pna21 Z = 4, 4284 observed unique reflections, R = 0.034. Lattice dimensions at -70 °C: a = 724.8(4), b = 1838.6(9), c = 2601(1) pm. PPh4[I(N-Iodosuccinimide)2] · CH3CN (3): Space group Pna21, Z = 4, 5775 observed unique reflections. R = 0.031. Lattice dimensions at -60 °C: a = 1849.2(9). b = 2644(1), c = 730.3(4) pm. 1-3 are isotypical. There structures consist of PPh4+ ions, including acetonitrile molecules without bonding interactions, and anions [X(iodosuccinimide)2]-, in which the halide ions X- are coordinated bv the iodine atoms of the N-iodosuccinimide molecules. The bond angles I··· X···I range from 90.13(4)° (X = Cl) and 88.84(3)° (X = Br) to 87.83(3)° (X = I). The bond angles N- I ··· X are nearly linear.

Ionische Phosphaniminato-Komplexe von Schwefel(IV) und Selen(IV ). Die Kristallstrukturen von [S(NPMe3)3]Cl · CH2Cl2, [S(N PPh3)3]S4N5 und [Se(NPMe3)3]Cl · C7H8 / Ionic Phosphorane Iminato Complexes of Sulfur(IV) and Selenium(IV). Crystal Structures of [S(NPMe3)3]Cl ·CH2Cl2, [S(NPPh3)3]S4N5 and [Se(NPMe3)3]Cl · C7H8

1995 ◽  
Vol 50 (10) ◽  
pp. 1455-1463 ◽  
Author(s):  
Frank Kunkel ◽  
Hella Folkerts ◽  
Sigrid Wocadlo ◽  
Hak-Chul Kang ◽  
Werner Massa ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Ir Spectroscopy ◽  
Crystal Structures ◽  
Acetonitrile Solution ◽  
Formula Unit ◽  
Selenium Compound ◽  
Space Group ◽  
Sulfur Dichloride ◽  
Structure Determinations ◽  
Moisture Sensitive

[S(NPMe3)3]Cl · CH2C12 and [S(NPPh3)3]S4N5 were prepared by the reaction of Me3SiNPMe3 or Me3SiNPPh3 with sulfur dichloride and S3N2Cl2, respectively, in CH2Cl2 solutions as colourless, moisture sensitive crystals. The corresponding selenium compound was prepared from SeCl4 and Me3SiNPMe3 in acetonitrile solution; it crystallizes from toluene solutions with one mole of toluene per formula unit. All complexes have been characterized by IR spectroscopy and by crystal structure determinations.[S(NPMe3)3]Cl-CH2Cl2: Space group Pna21, Z = 8 , 3930 observed unique reflections, R = 0.033. Lattice dimensions at -120 °C: a = 1200.9(1), b = 1020.2(1), c = 1790.5(1) pm.[S(NPPh3)3]S4N5: Space group P63, Z = 2, 2586 observed unique reflections, R = 0.054. Lattice dimensions at -100 °C: a = b = 1334.7(2), c = 1652.6(2) pm.[Se(NPMe3)3]Cl · C7H8: Space group C2/c, Z = 8 , 1475 observed unique reflections, R = 0.059. Lattice dimensions at -40 °C: a = 1853.6(8), b = 1159.2(4), c = 2053.2(4) pm. β = 101.92(3)°.All compounds contain cations [E(NPR3)3]+ (E = S, Se) with pyramidal structures. Bond lengths and bond angles are in average: S-N 162.5 pm, S-N-P 120.5° (R = Me), S-N 161.8 pm, S-N-P 119.2° (R = Ph), Se-N 177.8 pm, Se-N-P 120.3°.

N,N′-Dim ethylharnstoff als chelatisierende Lewis-Säure: Synthese und Kristallstrukturen von PPh4[Cl(H2Me2N2CO)] und (PPh4)2[Cl(H2Me2N2CO)]Cl / N.N′-Dimethylurea as a Chelating Lewis Acid: Synthesis and Crystal Structures of PPh4[Cl(H2Me2N2CO)] and (PPh4)2[Cl(H2Me2N2CO)]Cl

1996 ◽  
Vol 51 (10) ◽  
pp. 1423-1427
Author(s):  
Mitra Ghassemzadeh ◽  
Klaus Harms ◽  
Kurt Dehnicke
Keyword(s):  
Crystal Structure ◽  
Ir Spectroscopy ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Lewis Acid ◽  
Acid Synthesis ◽  
Space Group ◽  
Molar Ratios ◽  
Tetraphenylphosphonium Chloride ◽  
Structure Determinations

The title compounds have been prepared from tetraphenylphosphonium chloride and N,N′- dimethylurea in acetonitrile using different molar ratios of the educts. Both compounds were characterized by IR spectroscopy and by crystal structure determinations. PPh4[Cl(H2,Me2,N2,CO)]: Space group P1̅, Z = 4 ,a = 1021.8(2), b = 1192.7(2), c = 2143.9(4) pm, α = 87.21(3)°, β = 85.95(3)°, γ = 74.16(3)° (-50°C). (PPh4)2[Cl(H2Me2N2CO)]Cl: Space group P21/n, Z = 4, a = 1138.4(2), b = 2855.4(3), c = 1394.0(1) pm, β = 91.19(10)° (-60°C). In both compounds the N.N′-dimethylurea molecule acts as a chelating Lewis acid via two Cl···H hydrogen bonds forming nearly planar ClH2N2C-six-membered heterocycles.

Phosphanimin-Komplexe von Mangan(II)halogeniden. Die Kristallstrukturen von [MnCl2(Me3SiNPEt3)]2, [Mnl2(Me3SiNPEt3)2] und [MnI2(Me2Si(NPEt3)2)] / Phosphaneimine Complexes of Manganese(II)halides. The Crystal Structures of [MnCl2(Me3SiNPEt3)]2, [Mnl2(Me3SiNPEt3)2] and [MnI2(Me2Si(NPEt3)2)]

1995 ◽  
Vol 50 (8) ◽  
pp. 1215-1221 ◽  
Author(s):  
Hans-Joachim Mai ◽  
Sigrid Wocadlo ◽  
Werner Massa ◽  
Frank Weller ◽  
Kurt Dehnicke ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Thermal Decomposition ◽  
Ir Spectroscopy ◽  
Crystal Structures ◽  
Structure Refinement ◽  
Chelate Complex ◽  
Space Group ◽  
Bond Lengths ◽  
Structure Solution ◽  
Structure Determinations

The phosphaneimine complexes [MnCl2(Me3SiNPEt3)]2 (1) and [MnI2(Me3SiNPEt3)2] (2) have been prepared by the reaction of Me3SiNPEt3 with MnCl2 and Mnl2, respectively. Thermal decomposition of 2 leads to the chelate complex [MnI2(Me2Si(NPEt3)2)] (3) by cleaving SiMe4. The complexes are characterized by IR spectroscopy and by crystal structure determinations. 1: Space group P21/c, Z = 4, structure solution with 5062 observed unique reflections, R = 0.047. Lattice dimensions at -55 °C: a = 1175.8(5), b = 1634.5(2), c = 1740.2(8), β = 99.58(2)°. 1 forms dimeric molecules via chloro bridges and a cis-arrangement of the Me3SiNPEt3 donor molecules with Mn-N bond lengths of 210.4(5) and 208.2(4) pm. 2: Space group P 41212, Z = 4, structure refinement with 1633 independent reflections, 1072 observed unique reflections, R = 0.053. Lattice dimensions at -60 °C: a = b = 949.5(1), c = 3345.2(7) pm. 2 forms monomeric molecules with tetrahedrally coordinated Mn atoms and Mn-N bond lengths of 220.7(13) pm. 3: Space group P21/c, Z = 4, structure refinement with 8419 independent reflections, 4584 observed unique reflections, R = 0.047. Lattice dimensions at 20 °C: a = 1343.3(1), b = 2508.2(2), c = 1535.1(1) pm, β = 91.742(5)°. 3 forms monomeric molecules with the [Me2Si(NPEt3)2] ligand bound in a chelating fashion with Mn-N bond lengths of 212.9 pm in average.

Die isoelektronischen Molekülkomplexe TiCl3(NPPh3) und TiCl3(OSiPh3) / The Isoelectronic Molecular Complexes TiCl3(NPPh3) and TiCl3(OSiPh3)

1994 ◽  
Vol 49 (1) ◽  
pp. 15-20 ◽  
Author(s):  
Thilo Rübenstahl ◽  
Dorothea Wolff von Gudenberg ◽  
Frank Weller ◽  
Kurt Dehnicke ◽  
Helmut Goesmann
Keyword(s):  
Crystal Structure ◽  
Nitrogen Atom ◽  
Ir Spectroscopy ◽  
Oxygen Atom ◽  
Structure Analysis ◽  
Titanium Tetrachloride ◽  
Titanium Atom ◽  
Molecular Complexes ◽  
Space Group ◽  
Structure Determinations

AbstractTiCl3(NPPh3) and TiCl3(OSiPh3) have been prepared from titanium tetrachloride and Me3SiNPPh3 and HOSiPh3, respectively. Both complexes were characterized by IR spectroscopy and by crystal structure determinations. TiCl3(NPPh3): Space group R3̄̅, Z = 6, structure analysis with 959 observed unique reflections, R = 0.039. Lattice dimensions at -68°C: a = b = 1370.5(7), c = 1845.9(9) pm. TiCl3(OSiPh3): Space group P21/c, Z = 8, structure analysis with 4549 observed unique reflections, R = 0.049. Lattice dimensions at 19°C: a = 2127.7(2), b = 947.2(1), c = 2136.8(1) pm, β = 105.081(5)°. Both complexes form monomeric molecules in which the titanium atom is tetrahedrally coordinated by three chlorine atoms, the nitrogen atom of the phosphorone iminato ligand and the oxygen atom of the silyloxy group, respectively. The bond lengths TiN of 171.9(4) pm and TiO of 171.0(3) (in average) correspond to double bonds.

Acetylenkomplexe von Rhenium(+ VI). Die Kristallstrukturen von [ReCl4(n-C3H7 – C= C – n-C3H7)(POCl3)] und ReCl4(THF)2 / Alkyne Complexes of Rhenium(+VI). The Crystal Structures of [ReCl4(n-C3H7 – C= C – n-C3H7)(POCl3)] and ReCl4(THF)2

1990 ◽  
Vol 45 (9) ◽  
pp. 1227-1234 ◽  
Author(s):  
Hans-Walter Swidersky ◽  
Jürgen Pebler ◽  
Kurt Dehnicke ◽  
Dieter Fenske
Keyword(s):  
Crystal Structure ◽  
Ir Spectroscopy ◽  
Structure Determination ◽  
Crystal Structure Determination ◽  
Space Group ◽  
Bond Lengths ◽  
In Trans ◽  
Alkyne Complexes ◽  
In Cis ◽  
Ray Methods

The results of the magnetic susceptibility measurements of the previously reported rhenium alkyne complexes [ReCl4(PhC≡CPh)]2.2 CH2Cl2 and [ReCl4(PhC=CPh)(CH3CN)] in the temperature range of 4.2-293 K suggest d1-configurations, corresponding with oxidation state +VI for the rhenium atoms. The new alkyne complex [ReCl4(n-C3H7–C=C–n-C3H7)(POCl3)] has been prepared by the reaction of ReCl5·OPCl3 with n-C3H7-C≡C–n-C3H7 in CCl4 solution, forming dark red single crystals, which were characterized by IR spectroscopy as well as by a crystal structure determination with X-ray methods (space group P2,/c, Z = 4, 3235 observed unique reflexions, R = 0.026; lattice dimensions at –70 °C: a = 805.6(2), b = 1000.6(4), c = 2188.8(6) pm, β = 79.59(2)°). [ReCl4(n-C3H7-C=C–n-C3H7)(POCl3)] has a molecular structure with the alkyne ligand bonded side-on (bond lengths Re-C 198.4 and 198.2(5) pm). The oxygen atom of the solvating POCl3 molecule is coordinated in trans position to the ReC2 unit of the alkyne ligand (bond length Re—O = 223.7(3) pm).In THF solutions the alkyne complexes of this type undergo a slow reaction forming ReCl4(THF)2, which was also characterized by IR spectroscopy and a crystal structure determination (space group P212121, Z = 4, 2243 observed unique reflexions, R = 0.053; lattice dimensions at –70 °C: a = 773.0(14), b = 1267.1(6), c = 1398.6(7) pm). In ReCl4(THF)2 the THF molecules coordinate in cis-position (bond lengths Re–O 208 and 212(1) pm).

Synthesen und Kristallstrukturen der Lithiumphosphide {Li(DME)[P(t-Bu)2]}2 und [Li(DME)PPh2]∞ / Syntheses and Crystal Structures of the Lithium Phosphides {Li(DME)[P(t-Bu)2]}2 and [Li(DME)PPh2]∞

1993 ◽  
Vol 48 (2) ◽  
pp. 156-160 ◽  
Author(s):  
Gudrun Stieglitz ◽  
Bernhard Neumüller ◽  
Kurt Dehnicke
Keyword(s):  
Crystal Structure ◽  
Crystal Structures ◽  
Membered Ring ◽  
Space Group ◽  
Bond Lengths ◽  
Polymeric Chains ◽  
Structure Determinations ◽  
Centrosymmetric Dimers

AbstractThe title compounds have been prepared by the reaction of n-butyllithium with the corresponding diorganophosphanes HPR2 (R = t-Bu, Ph) in DME solutions. Both compounds were characterized by crystal structure determinations.{Li(DME)[P(t-Bu)2]}2: Space group P 1̄, Z = 1, 2027 observed unique reflections, R = 0.055. Lattice dimensions at -80 °C: a = 879.9(3), b = 986.3(1), c = 1064.0(2) pm, α = 70.69(1)°, β = 70.63(2)°, γ - 69.89(2)°. The compound forms centrosymmetric dimers of symmetry Ci with Li-P bond lengths of 260.0 and 257.3 pm for the Li2P2 four-membered ring.[Li(DME)PPh2]∞: Space group P21/n, Z = 4. 3437 observed unique reflections, R = 0.055. Lattice dimensions at - 80 °C: a = 1034.8(2), b = 812.48(9), c = 1978.4(3) pm, β = 103.30(2)°. The compound forms polymeric chains via LiP bridges with Li-P bond lengths o f 256.3 and 254.1 pm.

Substitutionsreaktionen an der N-Chlornitrenogruppe des [WCl4(NCl)]2. Die Kristallstrukturen von [CH3CN—WCl4(NSMe)] und [WNCl3 · NC—CH3]4 / Substitution Reactions at the N-Chloronitreno Group of [WCl4(NCl)]2. The Crystal Structures of [CH3CN—WCl4(NSMe)] and [WNCl3 · NC—CH3]4

1989 ◽  
Vol 44 (8) ◽  
pp. 903-910 ◽  
Author(s):  
Astrid Görge ◽  
Ute Patt-Siebel ◽  
Ulrich Müller ◽  
Kurt Dehnicke
Keyword(s):  
Crystal Structure ◽  
Ir Spectra ◽  
Structure Determination ◽  
Monoclinic Space Group ◽  
Trans Position ◽  
Crystal Data ◽  
Substitution Reactions ◽  
Space Group ◽  
X Ray ◽  
Structure Determinations

[WCl4(NCl)]2 reacts in acetonitrile with the trimethylsilyl compounds Me3SiSR (R = Me, Ph), and Me3SiESiMe3 (E = S, Se), with substitution of the chlorine atom of the N-chloronitreno group W=N–Cl and formation of CH3CN–WCl4(NSR) and CH3CN–WCl4(NEN)WCl4–NCCH3, respectively. Excess Me3SiBr reacts with CH3CN–WCl4(NSMe) to afford CH3CN–WBr4(NSMe). [CH3CN–WNCl3]4 was obtained from CH3CN–WCl4(NCl) and N(SiMe3)3. The products were characterized by their IR spectra. Two X-ray crystal structure determinations were also carried out. CH3CN—WCl4(NSMe) forms twinned crystals, and only non-overlapping reflexions of one of the twin individuals were used for the structure determination (846 unique values, R = 0.055). Crystal data: a = 592.4(2), b = 758.8(2), c = 1203.7(8) pm, β = 95.06(4)°, monoclinic, space group P21/m, Z = 2. The compound is a monomer in which the acetonitrile ligand is situated in the trans position to the W≡N–S̱̅–Me group. The bond lengths (W≡N 174(2), N–S 161(2) pm) and bond angles (WNS 176(1), NSC 102.1(9)°) are in agreement with the proposed formula. Crystal data for [CH3CN–WNCl3]4: a = 1009.5(2), b = 1274.5(2), c = 1287.9(2) pm, β = 108.17(1)°, monoclinic, space group P21/c, Z = 2 (2113 unique reflexions, R = 0.057). The compound forms tetrameric units, in which the W atoms form a square and are linked with one another via N atoms at alternating distances (W=N 171(2), W–N 207(2), W–NCMe 238(2) pm).

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