Cs[Yb(NPPh3)4] – ein homoleptischer Phosphaniminato‐Komplex des Ytterbiums

Cs[Yb(NPPh₃)₄] – a Homoleptic Phosphoraneiminato Complex of Ytterbium Cesium tetrakis(phosphoraneiminato)ytterbate, Cs[Yb(NPPh₃)₄] ( 1 ) has been prepared by the reaction of the dimeric complex [Yb(NPPh₃)₃]₂ with CsNPPh₃ in thf solution. 1 crystallizes from thf solution to give colourless moisture sensitive crystals which contain three molecules thf per asymmetric unit. According to the crystal structure determination 1 forms a dimeric ion ensemble [Cs{Yb(NPPh₃)₄}]₂ in which the Cs⁺ ions connect the [Yb(NPPh₃)₄]^– ions via Cs…N bridges. The ytterbium atoms are distorted tetrahedrally coordinated by the nitrogen atoms of the phosphoraneiminato ligands (NPPh₃^–) with short Yb–N‐bond lengths between 212.1 and 221.9(8) pm. The included thf molecules are without bonding contacts with the complex. [Cs{Yb(NPPh₃)₄}]₂ · 6 thf: Space group P 1, Z = 2, lattice dimensions at 193 K: a = 1837.2(2), b = 2041.5(2), c = 2095.8(2) pm, α = 79.953(13)°, β = 79.364(11)°, γ = 88.239(12)°, R = 0.0625.     

Die Reaktionen von Europium und Yttrium mit N‐Iod‐triphenylphosphanimin. Kristallstrukturen von [EuI2(DME)3], [Eu2I(NPPh3)5(DME)] und [Y2I(NPPh3)4(THF)4]+I3–

The Reactions of Europium and Yttrium with N‐Iodinetriphenylphosphoraneimine. Crystal Structures of [EuI₂(DME)₃], [Eu₂I(NPPh₃)₅(DME)] and [Y₂I(NPPh₃)₄(THF)₄]⁺I₃^– When treated with ultrasound, the reaction of europium metal with INPPh₃ in 1,2‐dimethoxyethane (DME) leads to the complexes [EuI₂(DME)₃] ( 1 ) and [Eu₂I(NPPh₃)₅(DME)] ( 2 ) which are separated from each other by fractional crystallization. On the other hand, the reaction of yttrium metal with INPPh₃ under similar conditions in THF gives the ionic phosphoraneiminato complex [Y₂I(NPPh₃)₄(THF)₄]⁺I₃^– ( 3 ). All complexes are characterized by crystal structure determinations. 1 : Space group P2₁, Z = 2, lattice dimensions at 188 K: a = 848.9(1); b = 1059.4(1); c = 1227.9(1) pm; β = 93.793(6)°; R = 0.0246. In the molecular structure of 1 the europium atom is eightfold coordinated with a bond angle I–Eu–I of 158.51°. 2 · 2 DME: Space group P1, Z = 2, lattice dimensions at 193 K: a = 1405.5(1); b = 1652.2(2); c = 2203.7(2) pm; α = 89.404(11)°; β = 72.958(11)°; γ = 78.657(11)°; R = 0.0391. In 2 the europium atoms are linked by the μ‐N‐atoms of two (NPPh₃^–) groups to form a planar Eu₂N₂ four‐membered ring. One of the Eu atoms is terminally coordinated by the N atoms of two (NPPh₃^–) groups, thus achieving a distorted tetrahedral surrounding. The second Eu atom is coordinated by the N atom of one (NPPh₃^–) group, by the terminally bounded iodine atom and by the oxygen atoms of the DME chelate, thus achieving a distorted octahedral surrounding. 3 · 6¹/₂ THF: Space group P1, Z = 2, lattice dimensions at 103 K: a = 1739.7(2); b = 1770.1(2); c = 2153.8(3) pm; α = 74.929(15)°; β = 84.223(14)°; γ = 64.612(12)°; R = 0.0638. In the cation [Y₂I(NPPh₃)₄(THF)₄]⁺ of 3 the yttrium atoms are linked by the μ‐N atoms of two (NPPh₃^–) groups as well as by the μ‐I atom. One (NPPh₃^–) ligand and two THF molecules complete the distorted octahedral coordination at each yttrium atom.     

Oxo-Phosphaniminato-Komplexe von Molybdän und Wolfram. Die Kristallstrukturen von [Mo(O)2(NPPh3)2] und [WO(NPPh3)3]2[W6O19]

Oxo-phosphoraneiminato Complexes of Molybdenum and Tungsten. Crystal Structures of [Mo(O)₂(NPPh₃)₂] and [WO(NPPh₃)₃]₂[W₆O₁₉] The dioxo-phosphoraneiminato complexes [Mo(O)₂(NPPh₃)₂] ( 1 ) and [W(O)₂(NPPh₃)₂] ( 2 ) originate from hydrolysis of the nitrido complexes [MN(NPPh₃)₃] (M = Mo, W). They form colourless crystals, which are characterized by IR and NMR spectroscopy as well as by mass spectrometry. According to the crystal structure analysis of 1 (space group Fdd2, Z = 8; lattice dimensions at –83 °C: a = 1953.3(1), b = 3275.8(3), c = 953.4(1) pm) there are monomeric molecules with tetrahedrally coordinated molybdenum atoms. The distances MoO of 171.2 pm and MoN of 185.9 pm correspond to double bonds. In dichloromethane solution 2 undergoes further hydrolysis with colourless crystals of [WO(NPPh₃)₃]₂[W₆O₁₉] ( 3 ) originating, which are characterized crystallographically (space group Pbcn, Z = 4; lattice dimensions at –50 °C: a = 3225.1(6), b = 1803.6(3), c = 1811.9(3) pm). 3 consists of cations [WO(NPPh₃)₃]⁺ with tetrahedrally coordinated tungsten atoms and of the known [W₆O₁₉]^2– anions. The tungsten atoms of the cations show distances WO of 171.8 pm and WN of 182 pm which correspond to double bonds as in 1 .     

[Sb(NPPh3)4]+SbF6−: Synthese,Kristallstruktur und 121Sb-Mößbauer-Spektrum

[Sb(NPPh₃)₄]⁺SbF₆^?: Synthesis, Crystal Structure, and ¹²¹Sb Mössbauer Spectrum The title compound as well as the hexachloro antimonate [Sb(NPPh₃)₄]⁺SbCl₆^? have been prepared by the reaction of Me₃SiNPPh₃ with SbF₅ and SbCl₅, respectively, in acetonitrile solutions. The compounds form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy, by ¹²¹Sb Mössbauer spectroscopy, and by crystal structure analyses. A complete crystal structure analysis, however, could be carried out with [Sb(NPPh₃)₄]⁺SbF₆^? only. The compound crystallizes orthorhombically in the space group Pccn with four formula units per unit cell. The structure determination was done with 3 972 observed unique reflections, R = 0.053. Lattice dimensions at 19°C: a = 1 658,6; b = 1 698.9, c = 2 361.9 pm. In the cation [Sb(NPPh₃)₄]⁺ the antimony atom is tetrahedrally coordinated by the four nitrogen atoms of the phosphoraneiminato ligands with extremely short Sb? N bond lengths of 193 pm.     

Neue Phosphaniminato‐Komplexe von Molybdän und Wolfram. Die Kristallstrukturen von [(μ‐S2N2){MoCl4(NPPh3)}2], [Mo(NPPh3)4][BF4]2, [W(S)2(NPPh3)2] und [Ph3PNH2]+[SCN]–

New Phosphoraneiminato Complexes of Molybdenum and Tungsten. Crystal Structures of [(μ‐S₂N₂){MoCl₄(NPPh₃)}₂], [Mo(NPPh₃)₄][BF₄]₂, [W(S)₂(NPPh₃)₂], and [Ph₃PNH₂]⁺[SCN]^– The binuclear molybdenum(V)phosphoraneiminato complex [(μ‐S₂N₂){Mo^VCl₄(NPPh₃)}₂] ( 1 ) has been prepared by the reaction of the chlorothionitreno complex [Mo^VICl₄(NSCl)]₂ with Me₃SiNPPh₃ in dichloromethane forming green crystals. The temperature dependent magnetic susceptibility in the range of 2–30 K shows ideal behaviour according to the Curie law with a magnetic moment of 1.60 B.M. According to the crystal structure determination 1 forms centrosymmetric molecules in which the molybdenum atoms are connected by the nitrogen atoms of the S₂N₂ molecule. In trans‐position to it the nitrogen atoms of the phosphoraneiminato groups (NPPh₃^–) are coordinated with Mo–N bond lengths of 171(1) pm. The tetrakis(phosphoraneiminato) complex [Mo(NPPh₃)₄]‐ [BF₄]₂ ( 2 ) has been obtained as colourless crystal needles by the reaction of MoN(NPPh₃)₃ with boron trifluoride etherate in toluene solution. In the dication the molybdenum atom is tetrahedrally coordinated by the nitrogen atoms of the (NPPh₃^–) groups with Mo–N bond lengths of 179,8–181,0(3) pm. The dithio‐bis(phosphoraneiminato) tungsten complex [W(S)₂(NPPh₃)₂] ( 3 ) is formed as yellow crystals as well as [Ph₃PNH₂]⁺[SCN]^– ( 4 ) from the reaction of WN(NPPh₃)₃ with carbon disulfide in tetrahydrofurane in the presence of traces of water. 3 has a monomeric molecular structure with tetrahedrally coordinated tungsten atom with bond lengths W–S of 214.5(5) pm and W–N of 179(1) pm. In the structure of 4 the thiocyanate ions are associated by hydrogen bonds of the NH₂ group of the [Ph₃PNH₂]⁺ ion to give a zigzag chain. 1 : Space group Pbca, Z = 4, lattice constants at –80 °C: a = 1647.9(3), b = 1460.8(2), c = 1810.4(4) pm; R₁ = 0.0981. 2 : Space group P1, Z = 2, lattice constants at –80 °C: a = 1162.5(1), b = 1238.0(1), c = 2346.2(2) pm; α = 103.14(1)°, β = 90.13(1)°, γ = 97.66(1)°; R₁ = 0.0423. 3 : Space group Fdd2, Z = 8, lattice constants at –80 °C: a = 3310.1(4), b = 2059.7(2), c = 966,7(1) pm; R₁ = 0.0696. 4 : Space group P2₁2₁2₁, Z = 4, lattice constants at –80 °C: a = 1118.4(1), b = 1206.7(1), c = 1279.9(1) pm; R₁ = 0.0311.     

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.     

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.     

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.     

Synthese und Kristallstrukturen der homoleptischen Phosphaniminato‐Kationen [E(NPPh3)3]+ (E = S,Se, Te) mit Iodid und Triiodid als Gegenionen

Synthesis and Crystal Structures of the homoleptic Phosphoraneiminato Cations [E(NPPh₃)₃]⁺ (E = S, Se, Te) with Iodide and Triiodide Counter Ions N‐Iod‐triphenylphosphaneimine, INPPh₃, reacts with the chalcogenes sulfur, selenium and tellurium in boiling tetrahydrofuran to give the phosphoraneiminato complexes [E(NPPh₃)₃]⁺[¹/₂ I₃^–, ¹/₂ I^–] · THF (E = S ( 1 ), E = Se ( 2 )) and [Te(NPPh₃)₃]⁺I₃^– ( 3 ), respectively. The componds form red crystals which are characterized by IR spectroscopy and by crystal structure determinations. The homoleptic cations [E(NPPh₃)₃]⁺ have pyramidal structures with short EN and PN bond lengths, corresponding to double bonds. 1 : Space group Pa 3, Z = 8, lattice dimensions at –80 °C: a = b = c = 2192.9(1) pm, R₁ = 0.0299. 2 : Space group Pa 3, Z = 8, lattice dimensions at –80 °C: a = b = c = 2202.5(1) pm, R₁ = 0.0357. 3 : Space group Pca2₁, Z = 4, lattice dimensions at –90 °C; a = 1075.8(2); b = 1988.8(4); c = 2437.2(3) pm, R₁ = 0.0443.     

Phosphaniminato‐Komplexe des Hafniums. Die Kristallstrukturen von [Hf(NPPh3)4] · 3 THF und [Hf(NPPh3)2Cl2(HNPPh3)2]

Phosphoraneiminato Complexes of Hafnium. Crystal Structures of [Hf(NPPh₃)₄] · 3 THF and [Hf(NPPh₃)₂Cl₂(HNPPh₃)₂] The phosphoraneiminato complexes [Hf(NPPh₃)₄] · 3 THF ( 1 · 3 THF) and [Hf(NPPh₃)₂Cl₂(HNPPh₃)₂] ( 2 ) have been prepared as colourless, moisture sensitive single crystals by reactions of hafnium tetrachloride with [CsNPPh₃]₄ · 2 toluene in tetrahydrofurane solutions by application of different ratios of the educts. Both complexes are characterized by IR spectroscopy and X‐ray crystal structure determinations. 1 · 3 THF: space group P 1, Z = 4, lattice dimensions at 193 K: a = 2007.6(1); b = 2064.2(1); c = 2115.9(1) pm; α = 109.193(4)°; β = 111.285(4)°; γ = 96.879(4)°; R₁ = 0.0506. 1 forms monomeric molecules with tetrahedral coordination of the nitrogen‐atoms of the (NPPh₃^–)‐groups towards the Hafnium atom. The HfN distances of 200.9 pm in average correspond with double bonds. 2 : space group P 1, Z = 4, lattice dimensions at 193 K: a = 1444.0(1); b = 1928.1(1); c = 2455.8(2) pm; α = 67.273(8)°; β = 87.445(8)°; γ = 87.082(8)°; R₁ = 0.0312. 2 has a monomeric molecular structure with octahedral coordination of the hafnium atom. The chlorine atoms are in trans position to one another, whereas the nitrogen atoms of the phosphoraneiminato groups (NPPh₃^–) are in trans position towards the nitrogen atoms ot the phosphorane imine molecules (HNPPh₃). The HfN bond lengths of the (NPPh₃^–) groups of 199.7 pm in average correspond with double bonds, whereas the HfN distances of the HNPPh₃ molecules with bond lengths of 230.2 pm in average are of donor‐acceptor type.     

[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.     

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.     

Oxidative Addition von N‐Chlortriphenylphosphanimin an Phosphortrichlorid und Antimontrichlorid. Kristallstrukturen von (Cl3PNPPh3)2[PCl6][ClHCl],[SbCl4(HNPPh3)2][SbCl6] und [Sb(NPPh3)4][SbCl6]

Oxidative Addition of N‐chlorotriphenylphosphoraneimine onto Phosphorus(III) Chloride and Antimony(III) Chloride. Crystal Structures of (Cl₃PNPPh₃)₂[PCl₆][ClHCl], [SbCl₄(HNPPh₃)₂][SbCl₆], and [Sb(NPPh₃)₄][SbCl₆] Phosphorus(III) chloride reacts with N‐chlorotriphenylphosphoraneimine, ClNPPh₃, in CH₂Cl₂ solution strongly exothermically via oxidative addition to give (Cl₃PNPPh₃)₂[PCl₆][ClHCl] ( 1 ). As a by‐product, Ph₃PNP(O)Cl₂ can be obtained, which is formed from PCl₃ and ClNPPh₃ in the presence of POCl₃. In contrast to these results, antimony(III) chloride reacts with ClNPPh₃ in CH₂Cl₂ solution to give a mixture of the phosphoraneimine complex [SbCl₄(HNPPh₃)₂][SbCl₆] ( 2 ) and the phosphoraneiminato complex [Sb(NPPh₃)₄][SbCl₆] ( 3 ). The complexes 1 ‐ 3 were characterized by IR spectroscopy and by single crystal X‐ray determinations. 1 : Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 3282.0(2), b = 798.7(1), c = 1926.1(2) pm, β = 107.96(1)°, R₁ = 0.0302. 1 contains [Cl₃PNPPh₃]⁺ cations with PN bond lengths of 152.5(2) and 160.9(2) pm, and a PNP bond angle of 140.5(1)°. 2 ·CH₂Cl₂: Space group , Z = 2, lattice dimensions at 193 K: a = 1031.2(1), b = 1448.3(2), c = 1811,4(2) pm, α = 70.96(1)°, β = 87.67(1)°, γ = 75.37(1)°, R₁ = 0.0713. 2 ·CH₂Cl₂ contains cations [SbCl₄(HNPPh₃)₂]⁺ with octahedrally coordinated Sb atom and the HNPPh₃ ligand molecules being in trans‐position. Sb–N bond lengths are 207.6(6) and 209.3(6) pm, PN bond lengths 162.3(7) and 160.8(7), which approximately corresponds with double bonds. 3 ·0.5CH₂Cl₂: Space group P4/n, Z = 2, lattice dimensions at 193 K: a = b = 1678.8(1), c = 1244.3(1) pm, R₁ = 0.0618. 3 ·0.5CH₂Cl₂ contains [Sb(NPPh₃)₄]⁺ cations with tetrahedrally coordinated Sb atom and short Sb–N bond lengths of 193.7(6) pm. The PN distances of the phosphoraneiminato ligands, (NPPh₃)^? with 156.5(6) pm, correspond with double bonds, the SbNP bond angles are 130.6(3)°.     

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 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.     

Molekül‐ und Kristallstruktur von Bis[chloro(μ‐phenylimido)(η5‐pentamethylcyclopentadienyl)tantal(IV)](Ta–Ta), [{TaCl(μ‐NPh)Cp*}2]

Molecular and Crystal Structure of Bis[chloro(μ‐phenylimido)(η⁵‐pentamethylcyclopentadienyl)tantalum(IV)](Ta–Ta), [{TaCl(μ‐NPh)Cp*}₂] Despite the steric hindrance of the central atom in [TaCl₂(NPh)Cp*] (Ph = C₆H₅, Cp* = η⁵‐C₅(CH₃)₅), caused by the Cp* ligand, the imido‐ligand takes a change in bond structure when this educt is reduced to the binuclear complex [{TaCl(μ‐NPh)Cp*}₂] in which tantalum is stabilized in the unusual oxidation state +4.     

Phosphaniminato‐Komplexe von Bismut(III). Die Kristallstrukturen von [BiF2(NPEt3)(HNPEt3)]2 und [Bi2I(NPPh3)4]I3

Phosphoraneiminato Complexes of Bismuth(III). Crystal Structures of [BiF₂(NPEt₃)(HNPEt₃)]₂ and [Bi₂I(NPPh₃)₄]I₃ [BiF₂(NPEt₃)(HNPEt₃)]₂ ( 1 ) has been obtained by the reaction of BiF₃ with Me₃SiNPEt₃ at 100 °C and subsequent extraction with 1,2‐dimethoxyethane in the presence of traces of water forming pale‐yellow, moisture sensitive crystals, which were characterized by a crystal structure determination. Space group P2₁/n, Z = 4, lattice dimensions at –83 °C: a = 2105.0, b = 1195.8, c = 728.2 pm, β = 92.55°. 1  forms centrosymmetric dimeric molecules, in which the Bi atoms are linked via Bi–N bonds of varying length (213.9 and 240.1 pm) of the NPEt₃^– groups to form a Bi₂N₂ four‐membered ring. The longer one of the two Bi–N bonds is trans to one terminal F atom. [Bi₂I(NPPh₃)₄]I₃ ( 2 ) has been obtained by the reaction of bismuth with N‐iodine triphenylphosphaneimine in dichloromethane forming red crystals. Crystal structure determination of 2 · 2.5 CH₂Cl₂: Space group P2₁/n, Z = 4, lattice dimensions at –50 °C: a = 1542.6, b = 2409.1, c = 2173.5 pm, β = 105.82°. In 2 the Bi atoms are linked via two N atoms of two NPPh₃^– groups to form a non‐planar Bi₂N₂ four‐membered ring with a fold angle of 27° along the N…N connection line. The two remaining NPPh₃^– groups are terminally connected and bent in the same direction. The iodide ion caps the two Bi atoms so that a [Bi₂I(NPPh₃)₄]⁺ cation is formed.     

Kristallstruktur und Schwingungsspektrum von (H2NPPh3)2[SnCl6]·2CH3CN

Crystal Structure and Vibrational Spectrum of (H₂NPPh₃)₂[SnCl₆]·2CH₃CN Single crystals of (H₂NPPh₃)₂[SnCl₆]·2CH₃CN ( 1 ) were obtained by oxidative addition of tin(II) chloride with N‐chloro‐triphenylphosphanimine in acetonitrile in the presence of water. 1 is characterized by IR and Raman spectroscopy as well as by a single crystal structure determination: Space group , Z = 2, lattice dimensions at 193 K: a = 1029.6(1), b = 1441.0(2), c = 1446.1(2) pm, α = 90.91(1)°, β = 92.21(1)°, γ = 92.98(1)°, R₁ = 0.0332. 1 forms an ionic structure with two different site positions of the [SnCl₆]^2? ions. One of them is surrounded by four N‐hydrogen atoms of four (H₂NPPh₃)⁺ ions, four CH₃CN molecules form N–H···N≡C–CH₃ contacts with the other four N‐hydrogen atoms of the cations. Thus, 1 can be written as [(H₂NPPh₃)₄(CH₃CN)₄(SnCl₆)]²⁺[SnCl₆]^2?.     

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)°.     

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.