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.     

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.     

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.     

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?.     

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.     

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.     

Synthese und Kristallstruktur des gemischt‐valenten Komplexes [Sn2I3(NPPh3)3]

Synthesis and Crystal Structure of the Mixed Valent Complex [Sn₂I₃(NPPh₃)₃] The mixed valent phosphoraneiminato complex [Sn₂I₃(NPPh₃)₃] ( 1 ) was prepared by the reaction of the tin(II) complex [SnI(NPPh₃)]₂ with sodium in tetrahydrofuran. 1 crystallizes with two formula units of THF to form yellow, moisture sensitive single crystals, which were characterized by a crystal structure determination. 1 · 2 THF: Space group P2₁/c, Z = 4, lattice dimensions at –80 °C: a = 1964.5(2), b = 1766.0(2), c = 2058.6(2) pm; β = 118.33(1)°, R = 0.052. 1 forms dimeric molecules in which the tin atoms are linked by two nitrogen atoms of two (NPPh₃^–) groups to form a planar Sn₂N₂ four‐membered ring. The Sn^IV atom is additionally coordinated by a terminal iodine atom and by a terminal (NPPh₃^–) group, whereas the Sn^II atom is additionally coordinated by two iodine atoms forming a ψ trigonal‐bipyramidal surrounding.     

[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.     

Die Reaktion von Ytterbium mit N‐Iod‐triphenylphosphanimin. Kristallstrukturen von [Yb2I(THF)2(NPPh3)4] · 2 THF, [YbI2(HNPPh3)(DME)2] und [{YbI2(DME)2}2(μ‐DME)]

The Reaction of Ytterbium with N‐iodo‐triphenylphosphaneimine. Crystal Structures of [Yb₂I(THF)₂(NPPh₃)₄] · 2 THF, [YbI₂(HNPPh₃)(DME)₂], and [{YbI₂(DME)₂}₂(μ‐DME)] When treated with ultrasound, the reaction of ytterbium powder with INPPh₃ in tetrahydrofuran leads to [YbI₂(THF)₄] and to the mixed‐valence phosphoraneiminato complex [Yb₂I(THF)₂(NPPh₃)₄] · 2 THF ( 1 ), which forms red single‐crystals. In the analogous reaction in 1,2‐dimethoxyethane (DME) only the ytterbium(II) iodide solvates [YbI₂(HNPPh₃)(DME)₂] ( 2 ) and [{YbI₂(DME)₂}₂ · (μ‐DME)] ( 3 ) can be isolated, which form yellow single crystals. All compounds were characterized by crystal structure analyses. 1 : Space group P1, Z = 2, lattice dimensions at –80 °C: a = 1337.6(5), b = 1389.6(5), c = 2244.2(17) pm; α = 86.11(7)°, β = 88.06(7)°, γ = 88.63(4)°; R = 0.0759. In 1 the two ytterbium atoms are connected via the N atoms of two phosphoraneiminato groups (NPPh₃^–) to form a planar Yb₂N₂ four‐membered ring. The structure can also be described as an ion pair consisting of [YbI(THF)₂]⁺ and [Yb(NPPh₃)₄]^–. 2 : Space group P2₁, Z = 2, lattice dimensions at –80 °C: a = 811.9(1), b = 1114.0(1), c = 1741.3(1) pm; β = 95.458(5)°; R = 0.0246. 2 forms molecules in which the ytterbium atom is coordinated in a pentagonal‐bipyramidal fashion with the iodine atoms in the axial positions. The O atoms of the two DME‐chelates and the N atom of the phosphaneimine ligand HNPPh₃ are in the equatorial positions. 3 : Space group P1, Z = 2, lattice dimensions at –70 °C: a = 817.5(1), b = 1047.7(1), c = 1115.5(2) pm; α = 90.179(10)°, β = 97.543(15)°, γ = 91.087(12)°; R = 0.0317. 3 has a dimeric molecular structure, in which the two fragments {YbI₂(DME)₂} are connected centrosymmetrically via a μ‐DME bridge. As in 2 , the ytterbium atoms are coordinated in a pentagonal‐bipyramidal fashion with the iodine atoms in the axial positions, as well as with the two DME chelates and with one O atom each of the μ‐DME ligand in the equatorial positions.     

Eine neue Synthese und die Kristallstruktur von Hexaphenyl‐cyclo‐triphosphazen, [NPPh2]3 · THF

A New Synthesis and the Crystal Structure of Hexaphenyl‐cyclo‐triphosphazene, [NPPh₂]₃ · THF [NPPh₂]₃ · THF ( 1 · THF) has been prepared from KNPPh₃ in THF solution in the presence of MoO₃ and 18‐crown‐6. According to the crystal structure determination all structural parameters are similar to known symmetric substituted cyclo‐triphosphazenes. The dihedral angles of the phenyl groups with the “best plane” P₃N₃ lie between 50 and 67°. 1 · THF: Space group P 1, Z = 2, lattice dimensions at –80 °C: a = 1146.5(1), b = 1360.5(1), c = 1382.9(1) pm, α = 108.06(1)°, β = 103.32(1)°, γ = 112.19(1)°, R₁ = 0.0441.     

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 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.     

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.     

Tris(triphenylphosphaniminato)boran,B(NPPh3)3

Tris(triphenylphosphoraneiminato)borane, B(NPPh₃)₃ B(NPPh₃)₃ has been prepared by the reaction of BF₃ · OEt₂ with LiNPPh₃ in toluene/tetrahydrofuran. Moisture sensitive single crystals of B(NPPh₃)₃ · 0.5 C₇H₈ were obtained and characterized by NMR and IR spectroscopy as well as by a crystal structure determination. Space group P2₁/n, Z = 4, lattice dimensions at –70 °C; a = 2147.8(3), b = 978.5(2), c = 2423.8(2) pm, β = 114.11(1)°, R₁ = 0.070. The compound forms monomeric molecules with a planar BN₃ skeleton and BN bond lengths of 144.7 pm on average.     

Syntheses and Spectroscopic Study of Some New N‐4‐Fluorobenzoyl Phosphoric Triamides; Crystal Structures of 4‐F‐C6H4C(O)N(H)P(O)R2, R = NH‐C(CH3)3, NH‐CH2C6H5, N(CH3)(CH2C6H5)

Some new N‐4‐Fluorobenzoyl phosphoric triamides with formula 4‐F‐C₆H₄C(O)N(H)P(O)X₂, X = NH‐C(CH₃)₃ ( 1 ), NH‐CH₂‐CH=CH₂ ( 2 ), NH‐CH₂C₆H₅ ( 3 ), N(CH₃)(C₆H₅) ( 4 ), NH‐CH(CH₃)(C₆H₅) ( 5 ) were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR and Mass spectroscopy and elemental analysis. The structures of compounds 1 , 3 and 4 were investigated by X‐ray crystallography. The P=O and C=O bonds in these compounds are anti. Compounds 1 and 3 form one dimensional polymeric chain produced by intra‐ and intermolecular ‐P=O···H‐N‐ hydrogen bonds. Compound 4 forms only a centrosymmetric dimer in the crystalline lattice via two equal ‐P=O···H‐N‐ hydrogen bonds. ¹H and ¹³C NMR spectra show two series of signals for the two amine groups in compound 1 . This is also observed for the two α‐methylbenzylamine groups in 5 due to the presence of chiral carbon atom in molecule. ¹³C NMR spectrum of compound 4 shows that ²J(P,C_aliphatic) coupling constant for CH₂ group is greater than for CH₃ in agreement with our previous study. Mass spectra of compounds 1 ‐ 3 (containing 4‐F‐C₆H₄C(O)N(H)P(O) moiety) indicate the fragments of amidophosphoric acid and 4‐F‐C₆H₄CN⁺ that formed in a pseudo McLafferty rearrangement pathway. Also, the fragments of aliphatic amines have high intensity in mass spectra.     

Phosphaniminate von Alkalimetallen: Die Kristallstrukturen von [KNPCy3]4, [KNPCy3]4·2OPCy3, [CsNPCy3]4·4OPCy3 und [Li4(NPPh3)(OSiMe2NPPh3)3(DME)]

The alkalimetal phosphoraneiminates [KNPCy₃]₄, ( 1 ) [KNPCy₃]₄·2OPCy₃ ( 2 ) and [CsNPCy₃]₄·4OPCy₃ ( 3 ) (Cy = cyclohexyl) which are obtainable by the reaction of pottassium amide or cesium amide with Cy₃PI₂ or Cy₃PBr₂ in liquid ammonia, as well as the lithium derivative [Li₄(NPPh₃)(OSiMe₂NPPh₃)₃(DME)] ( 4 ) have been characterized by crystal structure determinations. 4 has been formed by the insertion reaction of silicon greaze (‐OSiMe₂)n into the LiN bonds of [LiNPPh₃]₆ in DME solution (DME = 1, 2‐dimethoxyethane). 1 : Space group P&1macr;, Z = 2, lattice dimensions at 193 K: a = 1389.8(1); b = 1408.1(1); c = 2205.2(2) pm; α = 78.952(10)?; β = 81.215(10)?; γ = 66.232(8)?; R1 = 0.0418. 2 : Space group Pbcn, Z = 4, lattice constants at 193 K: a = 2943.6(2); b = 2048.2(1); c = 1893.8(1) pm; R1 = 0.0428. 3 : Space group Cmc2₁, Z = 4, lattice dimensions at 193 K: a = 2881.6(2); b = 2990.2(2); c = 1883.7(2) pm; R1 = 0.0586. 4 ·1/2DME: Space group R&3macr;c, Z = 12, lattice dimensions at 193 K: a = b = 1583.5(1); c = 11755.3(5) pm; R1 = 0.0495. All complexes have heterocubane structures. In 1‐3 they are formed by four alkali metal atoms and by the nitrogen atoms of the (μ₃‐NPCy₃^‐) groups, whereas 4 forms a "heteroleptic" Li₄NO₃ heterocubane.     

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.     

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.     

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)°.     

Syntheses,Crystal Structures,and Photocatalytic Activities of Three Copper Coordination Polymers Based on Bis(1H‐imidazol‐4‐yl)benzene/3‐(2‐Pyridyl)pyrazole

Three copper(II) coordination polymers (CuCPs), namely, [Cu_0.5(1,4‐bib)(SO₄)_0.5]_n ( 1 ), {[Cu(1,3‐bib)₂(H₂O)] · SO₄ · H₂O}_n ( 2 ), and [Cu(bpz)(SO₄)_0.5]_n ( 3 ), were assembled from the reaction of three N‐donors [1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and Hbpz = 3‐(2‐pyridyl)pyrazole] with copper sulfate under hydrothermal conditions. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric analyses (TGA). Structure analyses reveal that complex 1 is a 3D 6‐connected {4¹² · 6³}‐ pcu net, complex 2 is a fourfold 3D 4‐connected 6⁶‐ dia net, whereas complex 3 is a 1D snake‐like chain, which further expanded into 3D supramolecular architectures with the help of C–H ··· O hydrogen bonds. Moreover, the photocatalytic tests demonstrate that the obtained CuCPs are photocatalysts in the degradation of MB with the efficiency is 86.4 % for 1 , 75.3 % for 2 , and 91.3 % for 3 after 2 h, respectively.