[(Me3PN)3SNS(NPMe3)2]Cl2, ein gemischtvalenter Phosphaniminato-Komplex des Schwefels

[(Me₃PN)₃SNS(NPMe₃)₂]Cl₂, a Mixed Valenced Phosphorane Iminato Complex of Sulfur The title compound has been prepared from trithiazyl chloride and the silylated phosphaneimine Me₃SiNPMe₃ in acetonitrile solution, forming red crystals, which were characterized by IR spectroscopy and by a crystal structure determination. Space group P2₁/c, Z = 4, structure solution with 4250 independent reflections, R = 0.054. Lattice dimensions at 20°C: a = 1077.8, b = 2036.6, c = 1480.5 pm, β = 102.39°. The compound consists of dications [(Me₃PN)₃SNS(NPMe₃)₂]²⁺ and chloride ions. In the cations the sulfur atoms of oxidation number +VI and +IV are connected by an asymmetric, bent nitrido bridge with SN bond lengths of 156.9 and 167.0 pm.     

Kristallstrukturen von [TiF3(NPPh3)(HNPPh3)]2 und von HNPPh3

Crystal Structures of [TiF₃(NPPh₃)(HNPPh₃)]₂ and of HNPPh₃ The phosphoraneiminato-phosphaneimine complex [TiF₃(NPPh₃)(HNPPh₃)]₂ was obtained by the reaction of TiF₄ with Me₃SiNPPh₃ in boiling dichloromethane. It crystallizes from 1,2-dichloroethane as yellow crystals which include four molecules C₂H₄Cl₂ per dimeric formula unit. Space group P2₁/n, Z = 2, structure solution with 7270 independent reflections, R = 0.060 for reflections with I > 2σ(I). Lattice dimensions at ?50°C: a = 1417.5, b = 1896.9, c = 1586.6 pm, β = 101.22°. The compound forms centrosymmetric dimeric molecules via μ₂-F bridges with TiF distances of 194.6 and 223.3 pm, the longer one being in trans-position to the N atom of the (NPPh₃)^? ligand. Its TiN bond length of 177.7 pm corresponds with a double bond. The TiN bond length of the HNPPh₃ donor molecule of 213.4 pm is typical for a donor acceptor bond. According to the crystal structure determination the phosphaneimine HNPPh₃ forms monomeric molecules without intermolecular hydrogen bridges with a PN bond length of 152.4 pm. Space group P2₁/c, Z = 4, structure solution with 3229 independent reflections, R = 0.062 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1460.4, b = 928.9, c = 1096.6 pm, β = 93.35°.     

Phosphaniminato-Komplexe des Schwefels. Synthese und Kristallstrukturen von [SO(Cl)(NPPh3)], [SO2(Cl)(NPPh3)] und [SCl(NPPh3)2]Cl

Phosphorane Iminato Complexes of Sulfur. Synthesis and Crystal Structures of [SO(Cl)(NPPh₃)], [SO₂(Cl)(NPPh₃)], and [SCl(NPPh₃)₂]Cl The title compounds have been prepared by the reaction of Me₃SiNPPh₃ with SOCl₂, SO₂Cl₂, and SCl₂, respectively. They form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations. [SO(Cl)(NPPh₃)]: Space group P2₁/n, Z = 4, structure determination with 2 434 observed unique reflections, R = 0.047. Lattice dimensions at 19°C: a = 1 304.8, b = 996.5, c = 1 339.5 pm, β = 93.75°. The compound forms monomeric molecules with a remarkably long S? Cl bond of 234.2 pm and distances SN and PN of 154.6 and 161.6 pm, respectively, which agree with double bonds. [SO₂(Cl)(NPPh₃)]: Space group P2₁/n, Z = 4, structure solution with 2 872 observed, unique reflections, R = 0.047. Lattice dimensions at 20°C: a = 956.9, b = 1 909, c = 1 002.0 pm, β = 106.06°. The compound forms monomeric molecules with distances S? Cl of 207.1 pm, SN of 154.5 pm, and PN of 161.6 pm. [SCl(NPPh₃)₂]Cl: Space group P2₁/c, Z = 4, structure solution with 5 224 observed, unique reflections, R = 0.042. Lattice dimensions at 20°C: a = 1 108.6, b = 1 603.8, c = 1 840.5 pm, β = 99.98°. The compound forms ions [SCl(NPPh₃)₂]⁺ and Cl^?. In the cation the sulfur atom is φ-tetrahedrally coordinated with a long S? Cl distance of 248.5 pm and SN bond lengths of 154.5 and 156.0 pm.     

Phosphaniminato-Komplexe des Titans. Die Kristallstrukturen von [TiCl2(NPPh3)2] und [TiCl3(NPMe2Ph)(CH3CN)]2

Phosphorane Iminato Complexes of Titanium. The Crystal Structures of [TiCl₂(NPPh₃)₂] and [TiCl₃(NPMe₂Ph)(CH₃CN)]₂ [TiCl₂(NPPh₃)₂] has been prepared by the reaction of [TiCl₃(NPPh₃)] with excess Me₃SiNPPh₃ in a melt at 220°C, forming colourless crystals. [TiCl₃(NPMe₂Ph)(CH₃CN)]₂ is formed as yellow, moisture sensitive crystals from acetontrile solutions of [TiCl₃(NPMe₂Ph)]₂, which on its part has been obtained by the reaction of TiCl₄ with Me₃SiNPMe₂Ph. The complexes are characterized by IR spectroscopy and by crystal structure determinations. [TiCl₂(NPPh₃)₂] . Space group Fdd2, Z = 8, structure refinement with 2875 observed unique reflections, R = 0.039. Lattice dimensions at 19°C: a = 2080.9, b = 3308.5, c = 973.6 pm. The compound forms monomeric molecules with bond lengths TiN of 179.0 pm and PN of 156.8 pm, which correspond with double bonds. The bond angle TiNP is 166.6°. [TiCl₃(NPMe₂Ph)(CH₃CN)]₂ . Space group P1 , Z = 1, structure refinement with 2577 unique reflections, R = 0.039 for reflections with I > 2σ(I). Lattice dimensions at 20°C: a = 856.6, b = 923.1, c = 1008.3 pm, α = 81.23°, β = 71.63°, γ = 81.41°. The compound forms centrosymmetric, dimeric molecules, in which the titanium atoms are linked via chloro bridges TiCl₂Ti with TiCl bond lengths of 243.9 and 270.3 pm. In trans-position to the longer TiCl bonds the nitrogen atoms of the phosphorane iminato groups are coordinated with bond lengths TiN of 173.9 pm and PN of 161.4 pm which again correspond with double bonds. The bond angle TiNP is 156.4°.     

Synthese und Kristallstruktur des Selenyl-Phosphaniminato-Komplexes SeO(NPPh3)2

Synthesis and Crystal Structure of the Selenyl-Phosphoraneiminato Complex SeO(NPPh₃)₂ SeO(NPPh₃)₂ has been prepared from SeO₂ and Me₃SiNPPh₃ in a SeO₂ suspension in acetonitrile, forming colourless crystals. The compound is characterized by IR spectroscopy and by a crystal structure determination. Space group P1 , Z = 2, structure solution with 5 344 observed unique reflections, R = 0.064. Lattice dimensions at ?40°C: a = 931.6, b = 947.6, c = 1 762 pm, α = 77.50°, β = 81.78°, γ = 79.23°. The compound forms monomeric molecules in which the selenium atom is φ-tetrahedrally surrounded with bond lengths SeO = 161.7 pm and SeN = 179.9 and 181.6 pm.     

Phosphaniminato-Komplexe von Titan(IV) und Titan(III). Die Kristallstrukturen von [TiCl2(OMe)(NPPh3)]2, [TiBr2(NPPh3)]2 · 3 C7H8 sowie von [Ph3PNH2]Br · CH2Cl2

Phosphorane Iminato Complexes of Titanium(IV) and Titanium(III). The Crystal Structures of [TiCl₂(OMe)(NPPh₃)]₂, [TiBr₂(NPPh₃)]₂ · 3C₇H₈, and [Ph₃PNH₂]Br · CH₂Cl₂ TiCl₃(NPPh₃) reacts with a solution of methyllithium in diethyl ether in the presence of lithiummethylate forming yellow [TiCl₂(OMe)(NPPh₃)]₂. On reaction with benzyl magnesium bromide TiCl₃(NPPh₃) in diethyl ether is converted into green [TiBr₂(NPPh₃)]₂ under reduction and ligand exchange. [TiBr₂(NPPh₃)]₂ crystallizes from toluene with three molecules C₇H₈. [Ph₃PNH₂]Br · CH₂Cl₂ originates as a side product of this reaction. The products are characterized by their i.r. spectra and by crystal structure analyses. [TiCl₂(OMe)(NPPh₃)]₂ . Space group P1 , Z = 2, structure solution with 2909 independent reflections, R = 0.063. Lattice dimensions at 20°C: a = 1005.1, b = 1044.5, c = 1068.6 pm, α = 66.98°, β = 89.35°, γ = 80.24°. The compound forms centrosymmetric dimeric molecules with μ₂-OMe bridges and five-fold coordinated titanium atoms. The (NPPh₃^?) ligand is terminally connected with a Ti = N distance of 174.8 pm and with a TiNP bond angle of 165.3°. [TiBr₂(NPPh₃)]₂ · 3 C₇H₈ . Space group P1 , Z = 2, structure solution with 5548 independent reflections, R = 0.053. Lattice dimensions at ?70°C: a = 983.3, b = 1162.7, c = 1376.5 pm, α = 100.53°, β = 110.30°, γ = 105.24°. The compound forms centrosymmetric dimeric molecules with μ₂-NPPh₃ bridges and tetrahedral coordination at the titanium atoms. With 195.9 pm the Ti–N bonds correspond with single bonds. The Ti …? Ti distance of 260.0 pm is exceptionally short. [Ph₃PNH₂]Br · CH₂Cl₂ . Space group P1 , Z = 1, structure solution with 3091 independent reflections, R = 0.049. Lattice dimensions at 20°C: a = 909.4, b = 1004.4, c = 1158.5 pm, α = 108.09°, β = 94.67°, γ = 91.92°. The bromide ions are bonded to a one-dimensional infinite network via hydrogen bridge bonds of the cation and of the dichloromethane.     

[Cu4(NPMe3)3(O2C?CH3)5] – ein tetramerer Phosphaniminato-Komplex von Kupfer(II). Synthese,Kristallstruktur, magnetisches Verhalten und EPR-Spektrum

[Cu₄(NPMe₃)₃(O₂C? CH₃)₅] – a Tetrameric Phosphorane Iminato Complex of Copper(II). Synthesis, Crystal Structure, Magnetic Behaviour, and EPR Spectrum The title compound and the corresponding benzoate complex [Cu₄(NPMe₃)₃(O₂C? C₆H₅)₅] have been prepared by reactions of copper(II)acetate and copper(II)benzoate, respectively, with Me₃SiNPMe₃ in dichloromethane. Both complexes are characterized by IR spectroscopy. The acetate complex is additionally characterized by the measurement of the magnetic susceptibility, by its EPR spectrum, and by a crystal structure determination. [Cu₄(NPMe₃)₃(O₂C? CH₃)₅] · CH₂Cl₂: Space group I4₁/a, Z = 16, structure solution with 7 960 independent reflections, R = 0.044. Lattice dimensions at ?70°C: a = b = 3 670.6; c = 1 091.9 pm. The structure consists of four Cu atoms which are arranged at the corners of a distorted tetrahedron with Cu…?Cu distances between 290 and 318 pm. Three of the faces of the tetrahedron are linked by μ₃-N atoms of the phosphorane iminato groups. Three of the acetate ligands form chelates, the other two are monofunctionally coordinated. Three of the copper atoms have a planar surrounding, the forth Cu atom has a (4 + 1) coordination.     

Phosphaniminato-Komplexe von Niob und Tantal. Die Kristallstrukturen von [NbCl4(NPiPr3)(CH3CN)], [NbCl3(NPiPr3)2], [TaCl4(NPiPr3)]2 und [TaCl3(NPiPr3)2]

Phosphorane Iminato Complexes of Niobium and Tantalum. Crystal Structures of [NbCl₄(NPⁱPr₃)(CH₃CN)], [NbCl₃(NPⁱPr₃)₂], [TaCl₄(NPⁱPr₃)]₂, and [TaCl₃(NPⁱPr₃)₂] The title compounds have been prepared from the pentachlorides of niobium and tantalum with the silylated phosphorane imine Me₃SiNPⁱPr₃. They are characterized by IR spectroscopy and crystal structure determinations. NbCl₄(NPⁱPr₃)(CH₃CN)] . Space group Pna2₁, Z = 4, 2102 observed unique reflections, R = 0.022. Lattice dimensions at ?50°C: a = 1627.2, b = 876.3, c = 1335.3 pm. The compound forms monomeric molecules with the acetonitrile molecule in trans position to the phosphorane iminato group. This group shows a short NbN distance of 178.2 pm with a NbNP bond angle of 165.2°. [NbCl₃(NPⁱPr₃)₂] . Space group Cc, Z = 4, 2534 observed unique reflections, R = 0.046. Lattice dimensions at 20°C: a = 1302.65, b = 1321.69, c = 1672.04 pm, β = 111.713°. The compound forms monomeric molecules with a distorted bipyramidal surrounding of the niobium atom and equatorially arranged phosphorane iminato groups. [TaCl₄(NPⁱPr₃)]₂ . Space group Pbca, Z = 4, 1537 observed unique reflections, R = 0.037. Lattice dimensions at ?40°C: a = 1420.6, b = 1483.9, c = 1622.0 pm. The compound forms centrosymmetric dimeric molecules with dissimilarly long Ta₂Cl₂ bridges and equatorially arranged phosphorane iminato groups. [TaCl₃(NPⁱPr₃)₂] . Space group Cc, Z = 4, 5737 observed unique reflections, R = 0.039. Lattice dimensions at ?50°C: a = 1303.9, b = 1327.2, c = 1682.1 pm, β = 111,92°. The compound is isotypical with the corresponding niobium compound.     

[Mo(NPPh3)4]2+ [MoNCl3(NPPh3)]2− · C7H8, ein Phosphaniminato-Komplex mit einem Dikation von Molybdän(VI)

[Mo(NPPh₃)₄]²⁺ [MoNCl₃(NPPh₃)]₂^? · C₇H₈, a Phosphoraneiminato Complex with a Dication of Molybdenum(VI). The title compound was prepared by the reaction of MoNCl₃ with Me₃SiNPPh₃ in acetonitrile solution. Red single crystals separated upon addition of toluene. They were characterized by IR spectroscopy and by an X-ray structure determination. (Space group P1 , Z = 2, 6918 observed unique reflections, R = 0.059. Lattice dimensions at 20°C: a = 1 181.4, b = 2 021.4, c =2 409.7pm; α = 65.87°, β = 101.09°, γ= 78.97°). In the dication [Mo(NPPh₃)₄]²⁺ the molybdenum atom is surrounded in a tetrahedral fashion by the four nitrogen atoms of the phosphorane iminato ligands. The MoN and PN bond lengths correspond well with double bonds. In the two anions [MoNCl₃(NPPh₃)]^?, which occur in different conformations, the molybdenum atoms are fivefold coordinated by the terminal nitride ligand Mo?N: in axial positions and by the three chlorine atoms and the nitrogen atom of the (NPPh₃)^? ligand in the equatorial positions.     

[W(NPPh3)4]Cl2 — Ein Phosphaniminato-Komplex mit einem Wolfram-Dikation

[W(NPPh₃)₄]Cl₂ — a Phosphoraneiminato Complex with a Dication of Tungsten The title compound has been prepared by the reaction of Me₃SiNPPh₃ with WNCl₃ and WO₂Cl₂, respectively, in acetonitrile, forming colourless crystals, which were characterized by IR spectroscopy and by an X-ray structure determination. Space group P2₁/n, Z = 4, 4 424 observed unique reflections, R = 0.045. Lattice dimensions at 20°C: a = 1 206.5(2), b = 2 225.3(2), c = 2 421.0(3) pm, β = 101.09(1)°. In the dication [W(NPPh₃)₄]²⁺ the tungsten atom is surrounded in a tetrahedral fashion by the four nitrogen atoms of the phosphoraneiminato ligands. The bond lengths WN and PN correspond with double bonds.     

Phosphaniminato-Trichloroselenate(II): Synthese und Kristallstrukturen von [SeCl(NPPh3)2]+SeCl3− und [Me3SiN(H)PMe3]2+[Se2Cl6]2−

Phosphorane Iminato-Trichloroselenates(II): Syntheses and Crystal Structures of [SeCl(NPPh₃)₂]⁺SeCl₃^? and [Me₃SiN(H)PMe₃]₂⁺[Se₂Cl₆]^2? [SeCl(NPPh₃)₂]⁺SeCl₃^? has been synthesized by the reaction of Se₂Cl₂ with Me₃SiNPPh₃ in acetonitrile solution, forming orangered crystals, whereas red crystals of [Me₃SiN(H)PMe₃]₂⁺[Se₂Cl₆]^2? were obtained by the reaction of Me₃SiNPMe₃ with SeOCl₂ in acetonitrile solution. Both complexes were characterized by X-ray structure determinations. [SeCl(NPPh₃)₂]⁺SeCl₃^?: Space group P2₁/n, Z = 4, structure solution with 7 489 observed unique reflections, R = 0.057. Lattice dimensions at ?60°C: a = 1 117.0; b = 2 241, c = 1 407.5 pm, β = 95.61°. In the cation [SeCl(NPPh₃)₂]⁺ the selenium atom is φ-tetrahedrally coordinated by the chlorine atom and by the nitrogen atoms of the phosphorane iminato ligands, whereas the anion SeCl₃^? has a T-shaped structure with φ-trigonal-bipyramidale surrounding of the selenium atom. [Me₃SiN(H)PMe₃]₂⁺[Se₂Cl₆]^2?: Space group P2₁/c, Z = 4, structure solution with 2 093 observed unique reflections, R = 0.080. Lattice dimensions at ?70°C: a = 956, b = 828, c = 1 973 pm, β = 93.80°. The structure consists of [Me₃SiN(H)PMe₃]⁺ ions and planar [Se₂Cl₆]^2? anions, in which the selenium atoms are bridged nearly symmetrically by two chlorine atoms.     

Phosphaniminato-Komplexe des Schwefels. Synthese und Kristallstrukturen von [O3SS(NPPh3)2] · CH3CN, [SO(NPPh3)2] und [SCl(NPMe3)2]Cl

Phosphorane Iminato Complexes of Sulfur. Syntheses and Crystal Structures of [O₃SS(NPPh₃)₂] · CH₃CN, [SO(NPPh₃)₂], and [SCl(NPMe₃)₂]Cl The title compounds have been prepared by the reaction of Me₃SiNPPh₃ with SO₂ and SOCl₂, respectively, and by the reaction of Me₃SiNPMe₃ with S₂Cl₂. They form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations. [O₃SS((NPPh₃)₂)] · CH₃CN : Space group Pca2₁, Z = 4, structure solution with 4016 observed unique reflections, R = 0.050. Lattice dimensions at ?60°C: a = 1865.1, b = 1168.4, c = 1569.0 pm. The compound has a zwitterionic structure with a S? S bond length of 218.2 pm and bond lengths S? N of 161.2 and P? N of 160.1 pm. [SO(NPPh₃)₂] : Space group P2₁/c, Z = 4, structure solution with 2854 observed unique reflections, R = 0.113. Lattice dimensions at ?50°C: a = 1173.1, b = 1585.6, c = 1619.2 pm, b? = 98.13°. The compound forms monomeric molecules, in which the positions of S and N atoms are disordered in two positions. The bond lengths are S? N 166 pm and P? N 163 pm in average. [SCl(NPMe₃)₂]Cl : Space group P1 , Z = 2, structure solution with 2416 observed unique reflections, R = 0.038. Lattice dimensions at 20°C: a = 613.2, b = 1030.3, c = 1111.4 pm, α = 88.48°, b? = 88.01°, γ = 83.10°. The compound forms ions [SCl(NPMe₃)₂]⁺ and Cl^?. In the cation the sulfur atom is ?-tetrahedrally coordinated with a long S? Cl distance of 246.9 pm and bond lengths S? N of 155.3 pm and P? N of 164.3 pm in average.     

Phosphaniminato-Komplexe von Titan(IV). Die Kristallstrukturen von [TiCl3(NPEt3)]2, [TiCl3(NPEt3)(THF)2] und [TiCl4{Me2Si(NPEt3)2}]

Phosphoraneiminato Complexes of Titanium(IV). Crystal Structures of [TiCl₃(NPEt₃)]₂, [TiCl₃(NPEt₃)(THF)₂], and [TiCl₄{Me₂Si(NPEt₃)₂}] [TiCl₃(NPEt₃)]₂ ( 1 ) is formed from titanium(IV) chloride and the silylated phosphaneimine Me₃SiNPEt₃ in dichloromethane as reddish-brown, moisture-sensitive crystals. According to the crystal structure analysis these crystals show centrosymmetric Ti₂N₂ four-membered rings with Ti–N distances of 184.7 and 210.3 pm. With tetrahydrofurane 1 forms yellow, moisture sensitive crystals of the solvate [TiCl₃(NPEt₃)(THF)₂] ( 2 ), in which the titanium atom is octahedrally coordinated. The THF molecule which is in trans position to the phosporaneiminato ligand realizes but a very weak Ti–O bond of 238.0 pm, the cis THF molecule shows a Ti–O distance of 213.7 pm. With 173.4 pm along with a TiNP bond angle of 160.0° the TiN distance is very short. The bis(phosphaneimine) complex [TiCl₄{Me₂Si(NPEt₃)₂}] ( 3 ) is formed as colourless crystals in low yield in the reaction of titanium(IV) chloride with Me₃SiNPEt₃ and trimethylcyclopentadienylsilane. In 3 the titanium atom is surrounded by four chlorine atoms in a distorted octahedral fashion and by the two N atoms of the Me₂Si(NPEt₃)₂ molecule with TiN distances of 205.6 pm.     

Azidokomplexe von Vanadium(IV) und Vanadium(V): (Ph4P)2[VOCl2(μ‐N3)]2 und (Ph4P)2[VOCl(μ‐N3)(N3)2]2

Azido Complexes of Vanadium(IV) and Vanadium(V): (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ and (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ ( 1 ) was prepared by reaction of (Ph₄P)[VO₂Cl₂] with trimethylsilylazide in the molar ratio 1:2 in dichloromethane solution to give dark green, moisture sensitive, non‐explosive single crystals. The reaction is accompanied by the formation of the dark blue side‐product (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ ( 2a ), which can be obtained as the main product by application of a large excess of Me₃SiN₃. Dark blue needles of 2a crystallize spontaneously from the CH₂Cl₂ solution within one hour at 4 °C. After standing at 4 °C under its mother liquid within 24 hours a first‐order phase transition of 2a occurs forming dark blue prismatic single crystals of 2b . According to single crystal X‐ray structure determinations, 2a and 2b crystallize in the same type of space group , however, with different lattice dimensions. The vanadium(IV) complex 1 is characterized by X‐ray structure determination and by vibrational spectroscopy (IR, Raman) as well as by EPR spectroscopy, whereas 2b is characterized by IR spectroscopy. 1 : Space group P2₁/n, Z = 2, a = 1009.5(1), b = 1226.6(2), c = 1943.0(2) pm, β = 98.42(1)°, R₁ = 0.0672. The complex anion forms centrosymmetric units with V₂N₂‐four‐membered rings with a V···V distance of 335.6(1) pm and coordination number five on the vanadium(IV) atoms. 2a : Space group , Z = 1, a = 1089.0(2), b = 1097.1(2), c = 1310.1(2) pm, α = 92.99(1)°, β = 106.12(2)°, γ = 117.05(2)°, V = 1309.8(4) ų, d_calc. = 1.440 g·cm^?3, R₁ = 0.0384. The complex anion forms centrosymmetric units of symmetry C_i with V₂N₂ four‐membered rings and VN bond lengths of 200.4(3) and 234.4(2) pm, respectively. The non‐bonding V···V distance amounts to 356.2(1) pm. 2b : Space group , Z = 1, a = 1037.3(2), b = 1157.6(2), c = 1177.2(2) pm, α = 98.48(2)°, ° = 103.82(2)°, γ = 106.33(2)°, V = 1281.8(4) ų, d_calc. = 1.471 g·cm^?3, R₁ = 0.0724. The structure of the complex anion is similar to the anion of 2a with VN bond lengths of the four‐membered V₂N₂ ring of 203.3(4) and 235.2(4) pm, respectively, and a non‐bonding V···V distance of 357.5(1) pm.     

Struktur von Bis[salicylaldehyd-2-hydroxyanilato(2—)]vanadium(IV)

Molecular Structure of Bis[salicylaldehyde-2-hydroxyanilato(2—)]vanadium(IV) By the reaction of tris(acetylacetonato)vanadium(III) with salicylaldehyde-2-hydroxyanil the non-oxo vanadium(IV) complex of this ligand was prepared. Bis[salicylaldehyde-2-hydroxyanilato(2—)]vanadium(IV) has a distorted octahedral structure. Crystallographic data see “Inhaltsübersicht”.     

Tetrakis(triphenylphosphaniminato)titan, [Ti(NPPh3)4]

Tetrakis(triphenylphosphoraneiminato)titanium, [Ti(NPPh₃)₄] The title compound has been prepared by the reaction of [TiCl₂(NPPh₃)₂] with methyllithium and cyclopentadienyllithium, respectively, in hexane solution. [Ti(NPPh₃)₄] · 3 C₇H₈ crystallizes from toluene solution to form colourless, only slightly moisture sensitive crystals which were characterized by a crystal structure determination. Space group I4₁/a, Z = 8, lattice dimensions at ?80°C: a = b = 2160.7(2), c = 3334.2(3) pm, merohedral (110) twin, R = 0.077. The compound forms monomeric molecules with tetrahedrally coordinate titanium atoms and bonding parameters of TiN = 187.3 pm, PN = 155.1 pm, TiNP 150.4° in average.     

Synthese und Kristallstrukturen der Phosphaniminato-Komplexe [MCl2(NPPh3)]2 mit M = Al und Ga, [SbCl2(NPMe3)(DMF)]2 sowie des Phosphanimin-Komplexes [Ph3PNH · BF3] · THF

Syntheses and Crystal Structures of the Phosphorane Iminato Complexes [MCl₂(NPPh₃)]₂ with M = Al and Ga, [SbCl₂(NPMe₃)(DMF)]₂, and of the Phosphorane Imine Complex [Ph₃PNH · BF₃] · THF The phosphorane iminato complexes [MCl₂(NPPh₃)]₂ with M = Al and Ga and [SbCl₂(NPMe₃)(DMF)]₂ are formed as colourless crystals by reactions of the anhydrous trichlorides MCl₃ (M = Al, Ga, Sb) with the corresponding silylated phosphorane imines Me₃SiNPR₃ in acetonitrile and in dimethyl formamide, respectively. The phosphorane imine derivative [Ph₃PNH · BF₃] · THF is formed from Me₃SiNPPh₃ and boron trifluoride etherate in boiling tetrahydrofuran. The compounds are characterized by their i. r. spectra and by crystal structure analyses. [AlCl₂(NPPh₃)]₂ : Space group P1 , Z = 1, structure solution with 1 585 observed unique reflections, R = 0.061. Lattice dimensions at ?70°C: a = 917.6, b = 1 053.5, c = 1 145.2 pm, α = 111.72°, β = 100.80°, γ = 109.95°. [GaCl₂(NPPh₃)]₂ : Space group P1 , Z = 1, structure solution with 2 586 observed unique reflections, R = 0.066. Lattice dimensions at ?70°C: a = 917.5, b = 1 058.3, c = 1 153.7 pm, α = 105.52°, β = 107.75°, γ = 109.88°. In both compounds the metal atoms are linked to planar M₂N₂ four-membered rings via the N-atoms of the phosphorane iminato groups. [SbCl₂(NPMe₃)(DMF)]₂ : Space group P2₁/n, Z = 4, structure solution with 3 805 observed unique reflections, R = 0.038. Lattice dimensions at ?70°C: a = 1 913.0, b = 726.8, c = 2 040.7 pm, β = 113.62°. The unit cell contains two symmetry independent dimeric molecules, in which the antimony atoms are centrosymmetricly μ₂ linked via the N-atoms of the phosphorane iminato groups. Along with the oxygen atom of the dimethyl formamide molecule the Sb atoms achieve a ψ-octahedral environment. [Ph₃PNH · BF₃] · THF : Space group C2/c, Z = 8, structure solution with 2 048 observed unique reflections, R = 0.058. Lattice dimensions at ?70°C: a = 2 460.4, b = 869.2, c = 1 978.0 pm, β = 116.35°.     

[MoN(NPPh3)3] – ein monomerer Nitrido-Komplex des Molybdäns

[MoN(NPPh₃)₃] – a Monomeric Nitrido Complex of Molybdenum [MoN(NPPh₃)₃] ( 1 ) has been prepared from [MoCl₃(N₃S₂)]₂ and LiNPPh₃ in toluene suspension in good yields. From n-hexane/dichloromethane solutions 1 · 2 CH₂Cl₂ crystallizes as colourless single crystals, which were suitable for a crystal structure determination. 1 forms monomeric molecules with a Mo≡N distance of 166.6 pm for the nitrido ligand, which corresponds to a triple bond, and MoN-bonds of 193.6 pm on average of the NPPh₃^–-ligands, corresponding to shortened single bonds.     

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.     

Trans-methyl-azido-bis(triisopropylphosphin)platin(II), [PtN3(CH3)(PiPr3)2]

Trans-methyl-azido-bis(triisopropylphosphine)platinum(II), [PtN₃(CH₃)(PⁱPr₃)₂] [PtN₃(CH₃)(PⁱPr₃)₂] has been prepared by reductive elimination of ethane from [Pt(CH₃)₃N₃]₄ in the presence of triisopropylphosphine at 80 °C. The complex is characterized by IR and NMR spectroscopy and by crystal structure determination, as well as by ab initio calculations. [PtN₃(CH₃)(PⁱPr₃)₂], which is in trans-configuration here, crystallizes in the monoclinic space group P2₁, Z = 2, and with the lattice dimensions a = 806.9(1), b = 1384.3(1), c = 1093.8(1) pm, β = 94.107(10)°.