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) 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.     

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 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 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°.     

Synthese und Kristallstrukturen der Phosphaniminato-Komplexe [SnI(NPPh3)]2 und [SnI3(NPPh3)]2

Synthesis and Crystal Structures of the Phosphoraneiminato Complexes [SnI(NPPh₃)]₂ and [SnI₃(NPPh₃)]₂ The phosphoraneiminato complex of the divalent tin, [SnI(NPPh₃)]₂ ( 1 ), originates from the reaction of metallic tin with N-iodine triphenylphosphaneimine, INPPh₃, in dichloromethane suspension. 1 forms yellow, moisture sensitive crystals, which can be converted into the red phosphoraneiminato complex of the tetravalent tin, [SnI₃(NPPh₃)]₂ ( 2 ), by oxidation with iodine. According to the crystal structure analyses 1 and 2 have centrosymmetric dimeric molecular structures in which the tin atoms are linked via the N atoms of the NPPh₃^– groups. The tin atoms in 1 have a ψ-tetrahedral coordination, those in 2 a trigonal-bipyramidal one. 1 : Space group P 1, Z = 1, lattice dimensions at –80 °C: a = 779.0(1), b = 1080.1(1), c = 1170.4(1) pm, α = 64.49(1)°, β = 88.42(1)°, γ = 79.13(1)°, R = 0.0293. 2 : Space group P2₁/n, Z = 2, lattice dimensions at –80 °C: a = 1252.4(1), b = 1421.3(3), c = 1260.1(1) pm, β = 108.50(1)°, R = 0.0518.     

[VCl3(NPPh3)(OPPh3)], ein Phosphaniminato-Komplex von Vanadium(IV)

[VCl₃(NPPh₃)(OPPh₃)], a Phosphorane Iminato Complex of Vanadium(IV) The title compound has been prepared from vanadium tetrachloride and Me₃SiNPPh₃ in the presence of OPPh₃ in CCl₄ solution, forming orange-red, moisture sensitive crystals, which were characterized by an X-ray structure determination. Space group Cc, Z = 4, 2 560 observed unique reflections, R = 0.049. Lattice dimensions at 0°C: a = 1 018(1), b = 1 826(2), c = 1 859(2) pm, β = 93.65(9)° [VCl₃(NPPh₃)(OPPh₃)] forms monomeric molecules, in which the vanadium atom is coordinated in a distorted square pyramidal fashion with the (NPPh₃)^? ligand in apical position. The three chlorine atoms and the oxygen atom of the OPPh₃ molecule occupy the basal positions. The phosphorane iminato group V?N?PPh₃ is nearly linear (bond angle VNP 161.4°), the bond lengths VN (169 pm) and PN (162 pm) correspond with double bonds.     

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.     

Phosphanimin- und Phosphaniminato-Komplexe von Bor. Synthese und Kristallstrukturen von [BF3(Me3SiNPEt3)], [BCl2(NPPh3)]2, [BCl2(NPEt3)]2, [B2Cl3(NPEt3)2]+BCl4− und [B2Cl2(NPiPr3)3]+BCl4−

Phosphaneimine and Phosphoraneiminato Complexes of Boron. Synthesis and Crystal Structures of [BF₃(Me₃SiNPEt₃)], [BCl₂(NPPh₃)]₂, [BCl₂(NPEt₃)]₂, [B₂Cl₃(NPEt₃)₂]⁺BCl₄^?, and [B₂Cl₂(NPⁱPr₃)₃]⁺BCl₄^? The title compounds have been prepared from the corresponding silylated phosphaneimines and boron trifluoride etherate and boron trichloride, respectively. The compounds form white moisture sensitive crystals, which were characterized by ¹¹B-nmr-spectroscopy, IR-spectroscopy and by crystal structure determinations. [BF₃(Me₃SiNPEt₃)] : Space group P2₁/c, Z = 4, R = 0.032 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1361.0, b = 819.56, c = 1422.5 pm, β = 109.86°. The donor acceptor complex forms monomeric molecules with a B? N bond length of 157.8 pm. [BCl₂(NPPh₃)]₂ · 2 CH₂Cl₂ : Space group P2₁/c, Z = 2, R = 0.049 for reflections with I > 2σ(I). Lattice dimensions at ?50°C: a = 1184.6, b = 2086.4, c = 843.0 pm, β = 96.86°. The compound forms centrosymmetric dimeric molecules in which the boron atoms are linked to B₂N₂ four-membered rings with B? N distances of 152.7 pm via μ₂-N bridges of the NPPh₃ groups. [BCl₂(NPEt₃)]₂ : Space group Pbca, Z = 4, R = 0.029 for reflections with I > 2σ(I). Lattice dimensions at ?90°C: a = 1269.5, b = 1138.7, c = 1470.3 pm. The compound has a molecular structure corresponding to the phenyl compound with B? N ring distances of 151.0 pm. [B₂Cl₃(NPEt₃)₂]⁺BCl₄^? : Space group Pbca, Z = 8, R = 0.034 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1309.3, b = 1619.8, c = 2410.7 pm. Within the cations the boron atoms are linked to planar, asymmetrical B₂N₂ four-membered rings with B? N distances of 155.1 and 143.1 pm via the μ₂-N atoms of the NPEt₃ groups. [B₂Cl₂(NPⁱPr₃)₃]⁺BCl₄^? · CH₂Cl₂: Space group Pna2, Z = 4, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1976.5, b = 860.2, c = 2612.7 pm. Within the cations the boron atoms are linked to planar, asymmetrical B₂N₂ four-membered rings with B? N distances of 153.7 and 150.5 pm via the μ₂-N atoms of two of the NPⁱPr₃ groups. The third NPⁱPr₃ group is terminally connected to the sp²-hybridized boron atom with a B? N distance of 133.5 pm and with a B? N? P bond angle of 165.3°.     

Synthese und Kristallstruktur von [ReNCl(NPPh2C6H4)]2 · [Ph3PNH2]Cl · CH3CN,einem rheniumorganischen Nitrido-Phosphaniminato-Komplex

Synthesis and Crystal Structure of [ReNCl(NPPh₂C₆H₄)]₂ · [Ph₃PNH₂]Cl · CH₃CN, a Rhenium Organic Nitrido Phosphoraneiminato Complex The title compound is synthesized by the reaction of ReNCl₄ with Me₃SiNPPh₃ in boiling acetonitrile, forming colourless crystals, which are characterized by an X-ray structure determination. Space group P1 , Z = 2, 4 037 observed unique reflections, R = 0.043. Lattice dimensions at 19°C: a = 1 005.5; b = 1 695.2; c = 1 744.7 pm, α = 105.86°; β = 101.49°; γ = 104.45°. The structure consists of dimeric molecules [ReNCl(NPPh₂C₆H₄)]₂, triphenylphosphorane ammoniumchloride and included acetonitrile molecules. In the nitrido phosphoraneiminato complex the rhenium atoms are μ₂-bridged via the N-Atoms of the phosphoraneiminato ligands. Because of this bridging and a Re? Re bond, one terminal nitrido ligand, one terminal chloro ligand, and a Re? C bond of an -C-atom of one phenylene group of Re-atoms attain co-ordination number six.     

[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-Komplexe von Seltenerdelementen. Die Kristallstrukturen von [Yb2Cp3(NPPh3)3], [YCp(NPPh3)(μ-OSiMe2NPPh3)]2 und [M(NPPh3)2(μ-OSiMe2NPPh3)]2 mit M = Y und Sm

Phosphoraneiminato Complexes of Rare-Earth Elements. Crystal Structures of [Yb₂Cp₃(NPPh₃)₃], [YCp(NPPh₃)(μ-OSiMe₂NPPh₃)]₂, and [M(NPPh₃)₂(μ-OSiMe₂NPPh₃)]₂ with M = Y and Sm The ytterbium complex [Yb₂Cp₃(NPPh₃)₃] with sesqui distribution of cyclopentadienide and phosphoraneiminato ligands is made from YbCp₂Cl and LiNPPh₃ in boiling toluene and isolated as yellow, moisture sensitive crystals, which enclose three molecules of toluene per unit cell. [Yb₂Cp₃(NPPh₃)₃] · 3 C₇H₈ ( 1 ): Space group Pbca, Z = 8, lattice dimensions at –80 °C: a = 2727.6(2), b = 1977.5(1), c = 2848.9(2) pm; R = 0.0541. Two of the (NPPh₃)^–-groups link the ytterbium atoms to a nonplanar Yb₂N₂ four-membered ring with a folding angle of 17.1° along the Yb…Yb connecting line. The third (NPPh₃)^– group is terminally bonded with a short Yb–N distance of 214.2 pm. [YCp(NPPh₃)(μ-OSiMe₂NPPh₃)]₂ · 4 C₇H₈ ( 2 ) originates from YCpCl₂ and LiNPPh₃ in boiling toluene with Baysilon-paste participating forming colourless, moisture sensitive crystals. Space group P2₁/c, Z = 2, lattice dimensions at –80 °C: a = 1469.0(1), b = 1234.1(1), c = 2761.5(2) pm, β = 93.196(10)°; R = 0.0518. In 2 the yttrium atoms are linked via the oxygen atoms of the (OSiMe₂NPPh₃)^– groups to form a centrosymmetric Y₂O₂ four-membered ring with Y–O bonds of different lengths. Together with the terminally bonded (NPPh₃)^–-ligand, the η⁵-C₅H₅^– group, and the N atom of the siloxyphosphaneimine group, which functions as a donor atom, the Y atoms achieve coordination number five. [Y(NPPh₃)₂(μ-OSiMe₂NPPh₃)]₂ · 2 C₇H₈ ( 3 ) and [Sm(NPPh₃)₂(μ-OSiMe₂NPPh₃)]₂ ( 4 ) originate from the metal trichlorides with KNPPh₃ in THF with Baysilon paste participating and subsequent crystallization from toluene as colourless, moisture sensitive crystal needles. 3 : Space group P2₁/n, Z = 2, lattice dimensions at –80 °C: a = 1804.1(2), b = 1401.8(1), c = 2221.6(2) pm, β = 98.716(9)°; R = 0.0537. 4 : Space group P 1, Z = 1, lattice dimensions at –80 °C: a = 1363.4(1), b = 1364.9(1), c = 1650.6(1) pm; α = 112.457(8)°, β = 91.948(9)°, γ = 114.974(8)°; R = 0.0308. 3 and 4 form centrosymmetric dimeric molecules in which the metal atoms are linked via the oxygen atoms of the (OSiMe₂NPPh₃)^– groups to form M₂O₂ four-membered rings with M–O bonds of varying length. Together with the terminally bonded (NPPh₃)^– ligands and the N atom of the siloxyphosphaneimine ligand, which functions as a donor atom, the metal atoms achieve coordination number five.     

Phosphaniminato‐Komplexe des Zirconiums: Die Kristallstrukturen von [ZrCl3(NPPh3)(HNPPh3)2] und [ZrCl2(NPPh3)2(HNPPh3)2]

Phosphoraneiminato Complexes of Zirconium: Crystal Structures of [ZrCl₃(NPPh₃)(HNPPh₃)₂] and [ZrCl₂(NPPh₃)₂(HNPPh₃)₂] The phosphoraneiminato complexes [ZrCl₃(NPPh₃)(HNPPh₃)₂] ( 1 ) and [ZrCl₂(NPPh₃)₂(HNPPh₃)₂] ( 2 ) have been obtained by reaction of [ZrCl₄(THF)₂] with [CsNPPh₃]₄ in THF solution to give colourless moisture sensitive crystals which are characterized by X‐ray structure determinations. [ZrCl₃(NPPh₃)(HNPPh₃)₂] ( 1 ): Space group P 1, Z = 2, lattice dimensions at 193 K: a = 1209.4(2); b = 1480.8(2); c = 1814.2(2) pm; α = 71.203(13)°, β = 71.216(13)°, γ = 74.401(13)°; R = 0.0476. The zirconium atom of 1 is oktahedrally coordinated by the three chlorine atoms in meridional arrangement and by the three nitrogen atoms of the (NPPh₃^–) ligand and of the two phosphane imine molecules HNPPh₃. The ZrN bond distance of the (NPPh₃^–) group (193.5 pm) corresponds with a double bond. [ZrCl₂(NPPh₃)₂(HNPPh₃)₂] ( 2 ): Space group P 1, Z = 4, lattice dimensions at 193 K: a = 1447.6(2); b = 1925.7(2), c = 2457.0(2) pm; α = 67.317(12)°, β = 87.376(12)°, γ = 87.103(13)°; R = 0.0408. The zirconium atom in 2 is octahedrally coordinated by the two chlorine atoms in trans position, and by the nitrogen atoms of the two (NPPh₃^–) groups as well as by the two HNPPh₃ molecules. The ZrN distance of the (NPPh₃^–) ligands (198.9 and 202.0 pm) suggest some π‐interaction between the zirconium and the nitrogen atoms.     

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)°.     

Neue Koordinations-Motive bei Cyclothiazeno-Komplexen von Molybdän und Wolfram. Die Kristallstrukturen von [{Mo(N3S2)(Cl)(OtBu)2}{Mo(O)(N3S2)(OtBu)}]2 und [W(N3S2)2(LiCl){N≡W(NPPh3)3}2]

New Coordination Motives at Cyclothiazeno Complexes of Molybdenum and Tungsten. Crystal Structures of [{Mo(N₃S₂)(Cl)(O^tBu)₂}{Mo(O)(N₃S₂)(O^tBu)}]₂ and [W(N₃S₂)₂(LiCl){N≡W(NPPh₃)₃}₂] The metalla cyclothiazeno complexes (Cyclo-1λ⁶-metalla-3,5-dithia-2,4,6-triazino complexes) [{Mo(N₃S₂)(Cl) · (O^tBu)₂}{Mo(O)(N₃S₂)(O^tBu)}]₂ ( 1 ) and [W(N₃S₂)₂(LiCl) · {N≡W(NPPh₃)₃}₂] ( 2 ) are formed from [MoCl₃(N₃S₂)]₂ and LiO^tBu in toluene, and from [WCl₃(N₃S₂)]₂ and LiNPPh₃ in THF, respectively. The complexes form moisture sensitive, black ( 1 ) or brown ( 2 ) crystals, which we characterized by crystal structure analyses. 1 · Toluene: Space group P 1, Z = 1, lattice dimensions at –83 °C: a = 934.2(1), b = 964.4(1), c = 1700.3(1) pm; α = 83.54(1)°, β = 78.35(1)°, γ = 71.56(1)°, R₁ = 0.0339. 2 · 1.625 Toluene · 0.75 THF: Space group P 1, Z = 4, lattice dimensions at –80 °C: a = 1313.8(1), b = 2896.8(2), c = 3384.9(3) pm; α = 82.42(1)°, β = 88.71(1)°, γ = 77.28(1)°, R₁ = 0.0603.     

Reaktionen von MoNCl3 und WNCl3 mit elementarem Fluor. Kristallstrukturen von [MoO2F2(THF)2] und [WF4(NCl)(CH3CN)]

Reactions of MoNCl₃ and WNCl₃ with Elemental Fluorine. Crystal Structures of [MoO₂F₂(THF)₂] and [WF₄(NCl)(CH₃CN)] The nitrido chlorides MoNCl₃ and WNCl₃ as well as WCl₄(NCl) react with elemental fluorine forming the N-chloro imido complexes MoF₄(NCl) and WF₄(NCl), which were characterized by IR spectroscopy. With tetrahydrofurane MoF₄(NCl) reacts to give [MoF₄(NCl)(THF)], which in THF solution slowly converts into [MoO₂F₂(THF)₂]. From WF₄(NCl) with acetonitrile the complex [WF₄(NCl)(CH₃CN)] is obtained. Both donor acceptor complexes were characterized by crystal structure determinations. [MoO₂F₂(THF)₂] : Space group P2₁/n, Z = 4, structure solution with 1823 unique reflections, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?40°C: a = 636.2, b = 1119.5, c = 1625.2 pm; β = 93.92(1)º. The compound has a monomeric molecular structure with the fluorine atoms in trans-position to one another and with the oxygen atoms of the THF molecules in trans to the oxo ligands. [WF₄(NCl)(CH₃CN)] : Space group P2₁/m, Z = 2, structure solution with 1119 unique reflections, R = 0.038 for reflections with I > 2σ(I). Lattice dimensions at 20°C: a = 511.7, b = 714.9, c = 1002.5 pm; β = 102.59(10)º. The compound has a monomeric molecular structure in which the nitrogen atom of the acetonitrile molecule coordinates in trans-position to the N-chloro imido group W?N? Cl. The structural parameters of this group are WN = 172.2 pm, NCl = 161.1 pm, WNCl = 178.6º.     

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 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.     

[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.     

Synthese und Kristallstrukturen der Samarium-Komplexe [SmI2(DME)3] und [Sm2I(NPPh3)5(DME)]

Synthesis and Crystal Structures of the Samarium Complexes [SmI₂(DME)₃] and [Sm₂I(NPPh₃)₅(DME)] When treated with ultrasound, the reaction of samarium metal with N-iodine-triphenylphosphaneimine in 1,2-dimethoxyethane (DME) leads to the two samarium complexes [SmI₂(DME)₃] ( 1 ) and [Sm₂I(NPPh₃)₅(DME)] ( 2 ), which are separated from each other by fractional crystallization. 1 could be isolated in two different crystallographic forms, namely as brownish black crystals ( 1 a ) and as violet-black crystals ( 1 b ), both of them are characterized by crystal structure analyses. 1 a : Space group P2₁/c, Z = 4, lattice dimensions at –80 °C: a = 1459.4(1), b = 1314.4(1), c = 2293.6(2) pm, β = 99.245(8)°, R = 0.0344. The structure of 1 a holds two crystallographically independent molecules [SmI₂(DME)₃], in which the samarium atoms have coordination number eight. The two individuals differ from each other particularly in their I–Sm–I bond angles, which are 157.94 and 178.45°. 1 b : Space group P2₁, Z = 2, lattice dimensions at –80 °C: a = 849.4(3), b = 1060.1(3), c = 1235.1(6) pm, b = 93.86(5)°, R = 0.0251. 1 b has a molecular structure similar to that of 1a with a bond angle I–Sm–I of 158.40°. The phosphoraneiminato complex [Sm₂I(NPPh₃)₅(DME)] ( 2 ) forms colourless, moisture sensitive crystals which contain two molecules DME per formula unit. 2 · 2 DME: Space group P1, Z = 2, lattice dimensions at –80 °C: a = 1405.0(4), b = 1656.5(3), c = 2208.3(7) pm, α = 89.60(3)°, β = 72.96(4)°, γ = 78.70(3)°, R = 0.0408. In 2 the two samarium atoms are linked via the μ-N atoms of two phosphoraneiminato ligands to form a planar Sm₂N₂ four-membered ring. One of the Sm atoms is terminally coordinated by the N atoms of two (NPPh₃)^– groups, thus achieving a distorted tetrahedral surrounding. The second Sm atom is coordinated by the N atom of one (NPPh₃)^– group, by the terminally bonded iodine atom, and by the O atoms of the DME chelate, thus achieving a distorted octahedral surrounding.