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°.     

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.     

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 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.     

Silylierte Phosphanimin-Komplexe von Chrom(II), Palladium(II) und Kupfer(II). Die Kristallstrukturen von [CrCl2(Me3SiNPMe3)2], [PdCl2(Me3SiNPEt3)2] und [CuCl2(Me3SiNPMe3)]2

Silylated Phosphaneimine Complexes of Chromium(II), Palladium(II), and Copper(II). The Crystal Structures of [CrCl₂(Me₃SiNPMe₃)₂], [PdCl₂(Me₃SiNPEt₃)₂], and [CuCl₂(Me₃SiNPMe₃)]₂ The title compounds have been prepared by the reaction of the silylated phosphaneimines Me₃SiNPR₃ (R = CH₃, C₂H₅) with CrCl₂(THF)₂, PdCl₂ and CuCl₂, respectively, in dichloromethane suspensions. All donor-acceptor complexes were characterized by IR spectroscopy and by crystal structure determinations. [ CrCl₂(Me₃SiNPMe₃ )₂]: Space group Pccn, Z = 4, structure determination with 2104 observed unique reflections, R = 0.045. Lattice dimensions at ?70°C: a = 1326.3, b = 1562.5, c = 1171.5 pm. Within the monomeric molecular structure the chromium atom is planarly coordinated within the trans-configuration of the Cl atoms and the N atoms with distances of Cr? Cl = 235.94 pm and Cr? N = 211.7 pm. [ PdCl₂(Me₃SiNPEt₃)₂ ]: Space group P2₁/n, Z = 2, structure determination with 2412 observed unique reflections, R = 0.031. Lattice dimensions at 20°C: a = 917.3, b = 1390.2, c = 1161.7 pm, β = 95.80°. Within the monomeric molecular structure the palladium atom is planarly coordinated within the trans-configuration of the Cl atoms and the N atoms with distances of Pd? Cl = 222.9 pm and Pd? N = 209.5 pm. [ CuCl₂(Me₃SiNPMe₃)₂ ]: Space group Pbca, Z = 4, structure determination with 1861 observed unique reflections, R = 0.067. Lattice dimensions at ?70°C: a = 1440.2, b = 1205.1, c = 1536.5 pm. The compound forms centrosymmetric dimeric molecules, in which the Cu atoms are linked via almost symmetrical chloro-bridges with Cu? Cl distances of 231.4 pm. The distance Cu? N is 196.7 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°.     

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°.     

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 des Titans. Synthese und Kristallstrukturen von CpTiCl2(NPMe3), [TiCl3(NPMe3)]2, [Ti2Cl5(NPMe2Ph)3] und [Ti3Cl6(NPMe3)5][BPh4]

Phosphoraneiminato Complexes of Titanium. Synthesis and Crystal Structures of CpTiCl₂(NPMe₃), [TiCl₃(NPMe₃)]₂, [Ti₂Cl₅(NPMe₂Ph)₃], and [Ti₃Cl₆(NPMe₃)₅][BPh₄] The title compounds are formed from Cp₂TiCl₂ and titanium tetrachloride, respectively, and the corresponding phosphane imino compounds Me₃SiNPMe₃ and Me₃SiNPMe₂Ph. The tetraphenyl borate salt yielded from the reaction of [Ti₃Cl₆(NPMe₃)₅]Cl with NaBPh₄. All compounds form yellow crystals which are sensitive to moisture. They were characterized by IR-spectroscopy and crystal structure analyses. CpTiCl₂(NPMe₃) ( 1 ): Space group Pbca, Z = 8, solution of the structure with 1632 observed independent reflections, R = 0.037. Lattice dimensions at 19°C: a = 1202.6, b = 1224.2, c = 1766.7 pm. The molecules of the compound are monomeric with the (NPMe₃)^? ligand in almost linear array (bond angle Ti? N? P 170.7°). [TiCl₃(NPMe₃)]₂ ( 2 ): Space group Pbca, Z = 8, structure solution with 698 observed independent reflections, R = 0.030. Lattice dimensions at ?60°C: a = 1140.5, b = 1112.2, c = 1589.4 pm. In 2 the titanium atoms, which occur in trigonal bipyramidal coordination, are linked by the N atoms of the (NPMe₃)^? groups to form a centrosymmetric dimer with Ti? N bond lengths of 184.3 and 208.2 pm. [Ti₂Cl₅(NPMe₂Ph)₃] · CH₂Cl₂ ( 3 ): Space group Pca2₁, Z = 4, structure solution with 8477 observed independent reflections, R = 0.051. The lattice dimensions at 20°C are: a = 1221.0; b = 1407.5, c = 2139.3 pm. 3 can be understood as a reaction product of TiCl₂(NPMe₂Ph)₂ and TiCl₃(NPMe₂Ph). In the resulting, heavily distorted Ti₂N₂-four-membered ring the Ti? N bond lenghts are 1804., 194.4, 199.2, and 234.6 pm. The longest Ti? N bond is in trans-position to the N atom of the terminal (NPMe₂Ph)- ligand, in which the Ti? N distance is 175.6 pm. .[Ti₃CL₆(NPMe₃)₅][BPh₄] (4): Space group P2₁/n, structure solution with 2846 observed independent reflections, R = 0.062. The lattice dimensions at 20°C are: a = 1495.2, b = 2335.4, c = 155,8 pm, β = 93.28°. In the cation of 4 the three titanium atoms along with three (NPMe₃)- groups with μ2- N functions and two (NPMe₃)- groups with μ3- N functions form a nation number 6 with two terminal chlorine atoms.     

Phosphaniminato-Komplexe des Iods. Synthese und Kristallstrukturen von Ph3PNIO2 und Ph3PNSiMe3 · I2

Phosphoraneiminato Complexes of Iodine. Syntheses and Crystal Structures of Ph₃PNIO₂ and Ph₃PNSiMe₃ · I₂ Ph₃PNIO₂ has been prepared as yellow crystals by the reaction of Ph₃PNSiMe₃ with I₂O₅ in boiling acetonitrile, whereas the molecular complex Ph₃PNSiMe₃ · I₂ is formed as brown crystals by the reaction of Ph₃PNSiMe₃ with iodine in acetonitrile solution. Both complexes were characterized by crystal structure determinations. Ph₃PNIO₂: Space group P2₁/n, Z = 4, 2 858 observed unique reflections, R = 0.039. Lattice dimensions at 19°C: a = 972.8(2), b = 1 743.4(3), c = 1 073.7(2) pm, β = 115.46(3)°. The compound forms monomeric molecules with pyramidal geometry at the iodine atom. The bond angle PNI (126.9°) is unusually small; the PN bond length of 159.2 pm corresponds with a double bond. Ph₃PNSiMe₃ · I₂: Space group P1 , Z = 2, 3 560 observed unique reflections, R = 0.033. Lattice dimensions at 19°C: a = 941.2(2), b = 1 041.7(2), c = 1 287.4(3) pm, α = 78.34(1)°, β = 72.00(2)°, γ = 86.08(2)°. The compound forms monomeric molecules, in which the I₂ molecule and the nitrogen atom of the phosphoraneimine molecule realize a linear N? I? I axis with a bond length N? I of 243.2 pm.     

Phosphanimin- und Phosphaniminato-Komplexe von Eisen. Die Kristallstrukturen von [FeCl3(Me3SiNPEt3)], [FeCl2(Me3SiNPEt3)]2, [FeCl2(NPEt3)]2 und [Fe(O2C?CH3)2(NPEt3)]2

Phosphanimine and Phosphoraneiminato Complexes of Iron. The Crystal Structures of [FeCl₃(Me₃SiNPEt₃)], [FeCl₂(Me₃SiNPEt₃)]₂, [FeCl₂(NPEt₃)]₂, and [Fe(O₂C? CH₃)₂(NPEt₃)]₂ The phosphanimine complexes [FeCl₃(Me₃SiNPEt₃)] (red-orange) and [FeCl₂(Me₃SiNPEt₃)]₂ (colourless) have been prepared by reactions of Me₃SiNPEt₃ with FeCl₃ and FeCl₂, respectively, in CH₂Cl₂ suspensions. Thermal decomposition of these donor-acceptor complexes in boiling toluene leads to the phosphoraneiminato complex [FeCl₂(NPEt₃)]₂ (black), whereas [Fe(O₂C? CH₃)₂(NPEt₃)]₂ (brown) is formed from iron(II) acetate and Me₃SiNPEt₃ in boiling acetonitrile. The complexes are characterized by IR spectroscopy and by crystal structure determinations. [FeCl₃(Me₃SiNPEt₃)] (1) : Space group P2₁/c, Z = 8, structure determination with 4 673 unique reflections, R = 0.033. Lattice dimensions at ?15°C: a = 1 607.8, b = 1 602.0, c = 1 417.2 pm, β = 106.56°. 1 forms monomeric molecules with tetrahedrally coordinated iron atoms. Bond lengths in average: Fe? N = 196.9 pm, Fe? Cl = 219.7 pm. [FeCl₂(Me₃SiNPEt₃)]₂ (2) : Space group P2₁/c, Z = 4, structure determination with 4 992 unique reflections, R = 0.048. Lattice dimensions at 20°C: a = 1 457.9, b = 1 685.4, c = 1 507.3 pm, β = 116.74°. 2 forms dimeric molecules, which are associated by chloro bridges. The iron atoms are tetrahedrally coordinated with trans positions of the phosphanimine ligands. Both lengths in average: Fe? N = 202.2 pm, Fe? Cl_terminal = 224.7 pm, Fe? Cl bridge = 241.0 pm. [FeCl₂(NPEt₃)]2 (3): Space group P2₁/n, Z = 2, structure determination with 2763 unique reflections, R = 0.039. Lattice dimensions at ?70°C: a = 799.1, b = 1009.0, c = 1441.9 pm, β = 93.45°. 3 forms centrosymmetric dimeric molecules, in which the tetrahedrally coordinated iron atoms are associated by the nitrogen atoms of the phosphoraneiminato ligands. Bond lengths in average: Fe? N = 191.4 pm, Fe? Cl = 222.7 pm. [Fe(O₂C? CH₃)₂(NPEt₃]2 (4): Space group P2₁/n, Z = 2, structure determination with 3005 observed unique reflections, R = 0.034. Lattice dimensions at -65°C: a = 886.4, b = 1444.6 pm, β = 90.60°. 4 forms centrosymmetric dimeric molecules, in which the octahedrally coordinated iron atoms are associated by the nitrogen atoms of the phosphoraneiminato ligands with bond lengths Fe? N of 191.9 and 195.0 pm. The acetate groups are coordinated in a chelating fashion.     

Synthese und Kristallstrukturen der silylierten Tris-Phosphanimine R?C(CH2PPh2NSiMe3)3 mit R  H und CH3

Synthesis and Crystal Structures of the Silylated λ⁵-Phosphazenes R? C(CH₂PPh₂NSiMe₃)₃ with R = H and CH₃ The title compounds are obtained by Staudinger reaction from the corresponding tripodal phosphanes R? C(CH₂PPh₂)₃ and trimethylsilylazide. Both complexes are characterized by their IR and NMR spectra and by crystal structure analyses. H? C(CH₂PPh₂NSiMe₃)₃ ( 1 ): Space group P2₁/c, Z = 4, structure determination with 7833 independent reflections, R = 0.055. Lattice dimensions at ?50°C: a = 1399.5, b = 2311.4, c = 1678.9 pm, β = 112.92°. CH₃? C(CH₂PPh₂NSiMe₃)₃ ( 2 ): Space group P1 , Z = 2, structure determination with 9251 independent reflections, R = 0.057. Lattice dimensions at ?50°C: a = 1276.5, b = 1386.9, c = 1790.2 pm; α = 85.55°, β = 69.39°, γ = 62.99°. 1 and 2 form monomeric molecules which are distinguished by their conformation.     

Sterisch abgeschirmte Nitridokomplexe von Molybdän und Wolfram Die Kristallstrukturen von [MoN(NPh2)3] und [W4N4(NPh2)6(OnC4H9)2]

Stericly Shielded Nitrido Complexes of Molybdenum and Tungsten. The Crystal Structures of [MoN(NPh₂)₃] and [W₄N₄(NPh₂)₆(OⁿC₄H₉)₂] The reactions of MoNCl₃ and WNCl₃, respectively, with lithium diphenylamide in tetrahydrofurane produce the monomeric nitrido complexes MN(NPh₂)₃ with CN = 4 at the metal atoms. In the presence of lithium-n-butyl LiNPh₂ and WNCl₃ also form the tetrameric nitrido complex [W₄N₄(NPh₂)₆(OⁿC₄H₉)₂] which contains W^V and W^VI. The compounds are characterized by their i.r. spectra, by X-ray structural analysis, and, partially, by ¹H and ¹³C n.m.r. spectroscopy. MoN(NPh₂)₃: Space group P1 , Z = 2, 4060 observed independent reflexions, R = 0.031. Lattice dimensions at 20°C: a = 956.2(4) pm, b = 1 015.9(2) pm, c = 1 598.1(3) pm; α = 79.06(2)°, β = 85.67(3)°, γ = 82.57(3)°. The compound forms monomeric molecules with Mo?N bond lengths of 163.4 pm and mean Mo? NPh₂ distances of 199.2 pm. [W₄N₄(NPh₂)₆(OⁿC₄H₉)₂]: Space group P2₁/n, Z = 2, 1903 observed independent reflexions, R=0.039. Lattice parameters at 19°C: a = 1582.2(3) pm, b = 1182.4(2) pm, c = 2053.3(4) pm; β = 103.77(2)°. The compound forms centrosymmetric molecules, in which the central W–W dumb-bell (bond length 253.5 pm) is linked by the nitrido ligands of two WN₂(NPh₂)₂=units in a T shaped order of the N-atoms.     

Synthese und Kristallstrukturen der Phosphanimin-Komplexe MCl2(Me3SiNPMe3)2 mit M = Zn und Co,und CoCl2(HNPMe3)2

Syntheses and Crystal Structures of the Phosphaneimine Complexes MCl₂(Me₃SiNPMe₃)₂ with M = Zn and Co, and CoCl₂(HNPMe₃)₂ The molecular complexes MCl₂(Me₃SiNPMe₃)₂ (M = Zn, Co) have been prepared by the reaction of the dichlorides of zinc and cobalt with Me₃SiNPMe₃ in CH₃CN and CH₂Cl₂, respectively, whereas the complex CoCl₂(HNPMe₃)₂ has been prepared by the reaction of CoCl₂ with NaF in boiling acetonitrile in the presence of Me₃SiNPMe₃. All complexes were characterized by IR spectroscopy and by crystal structure determinations. The complexes MCl₂(Me₃SiNPMe₃)₂ crystallize isotypically. ZnCl₂(Me₃SiNPMe₃)₂: Space group P2₁2₁2₁, Z = 4, 2677 observed unique reflections, R = 0.024. Lattice dimensions at ?70°C: a = 1243.6; b = 1319.0; c = 1464.7 pm. CoCl₂(Me₃SiNPMe₃)₂: Space group P2₁2₁2₁, Z = 4, 3963 observed unique reflections, R = 0,071. Lattice dimensions at ?80°C: a = 1236.3; b = 1317.4; c = 1457.6 pm. CoCl₂(HNPMe₃)₂ · CH₂Cl₂: Space group Pbca, Z = 8, 1354 observed unique reflections, R = 0.055. Lattice dimensions at ?80°C: a = 1247.3; b = 998.4; c = 2882.4 pm. All complexes have monomeric molecular structures, in which the metal atoms are coordinated in a distorted tetrahedral fashion by the two chlorine atoms and by the nitrogen atoms of the phosphaneimine molecules.     

[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.     

Reaktionen silylierter Phosphanimine mit Iodmonochlorid und Iodtrichlorid. Die Kristallstrukturen von [Me3SiNPMe3 · ICl], [Ph3PNCl · ICl] und [Me3PN(H)PMe3] [ICl2]2

Reactions of Silylated Phosphorane Imines with Iodine Monochloride and Iodine Trichloride. The Crystal Structures of [Me₃SiNPMe₃ · ICl], [Ph₃PNCl · ICl], and [Me₃PN(H)PMe₃][ICl₂]₂ The donor-acceptor complex [Me₃SiNPMe₃ · ICl] has been prepared from Me₃SiNPMe₃ and ICl in acetonitrile solution forming yellow-orange crystals. [Ph₃PNCl · ICl] can be prepared by the reaction of Me₃SiNPPh₃ with ICl₃ in dichloromethane solution forming pale yellow crystals. [Me₃PN(H)PMe₃][ICl₂]₂ is formed in a small amount by a slow reaction of Me₃SiNPMe₃ with ICl₃ in CCl₄ suspension in the presence of traces of moisture. All samples are characterized by IR spectroscopy and by X-ray structure analyses. [Me₃SiNPMe₃ · ICl] (1) : Space group Iba2, Z = 8, structure solution with 1 727 observed unique reflections, R = 0.051. Lattice dimensions at ?60°C: a = 1 510.7, b = 1 862.8, c = 988.9 pm. 1 has a molecular structure in which the N atom of the phosphorane imine is connected with the iodine atom of the ICl molecule in a linear arrangement N? I? Cl. Bond lengths N? I = 222.7 pm, I? Cl = 265.1 pm. [Ph₃PNCl · ICl] (2) : Space group Pna2₁, Z = 4, structure solution with 1 530 observed unique reflections, R = 0.030. Lattice dimensions at 20°C: a = 1 522.8, b = 1 408.3, c = 865.8 pm. 2 has a molecular structure in which the N atom of the N chlorophosphorane imine is connected with the iodine atom of the ICl molecule in a linear arrangement. Bond lengths N? Cl = 174.4 pm, N? I = 229.5 pm, I? Cl = 251.2 pm. [Me₃PN(H)PMe₃][ICl₂]₂ (3) : Space group P2₁/c, Z = 4, structure solution with 1 989 observed unique reflections, R = 0.029. Lattice dimensions at ?50°C: a = 1 223.1, b = 1 090.2, c = 1 482.8 pm, β = 112.21°. 3 consists of [Me₃PN(H)PMe₃]²⁺ ions and ICl₂^? anions. The PNP bond angle of the dication amounts to 134.4° with PN distances of 165.6 and 166.1 pm, approximately according to double bonds.     

Chelatkomplexe von Rheniumtetrachlorid. Die Kristallstrukturen von ReCl4(DME) und ReCl4(DPPE) · Tolan

Chelate Complexes of Rhenium Tetrachloride. The Crystal Structures of ReCl₄(DME) and ReCl₄(DPPE) · Tolan Bright green crystals of ReCl₄(DME) have been prepared by the reaction of rhenium pentachloride with dimethoxyethane (DME) in dichloromethane. ReCl₄(DPPE) · tolan was obtained in form of red crystals by the reaction of the alkyne complex [ReCl₄(Ph? C?C? Ph)(POCl₃)] with bis(diphenylphosphino)ethane (DPPE) in dichloromethane. The complexes were characterized by X-ray structure determinations. ReCl₄(DME): Space group I4 2d, Z = 8, 829 observed unique reflexions, R = 0.022. Lattice dimensions at 19.5°C: a = b = 960.60(6), c = 2337.2(6) pm. The complex forms monomeric molecules with DME as chelating ligand; the Re? O bond lengths are 213.1 pm. The chlorine atoms, arranged in trans position to the chelating ligand, have slightly shorter Re? Cl bonds than the chlorine atoms in cis position (232,1 pm). ReCl₄(DPPE) · tolan: Space group P2₁/n, Z = 4,4313 observed unique reflexions, R = 0.040. Lattice dimensions at ?80°C: a = 1095.7(1), b = 1764.2(2), c = 1898.0(2) pm, β = 99.229(8)°. The compound consists in form of monomeric molecules [ReCl₄(DPPE)] and diphenylacetylene molecules, which are incorporated in the lattice. The two phenyl rings of the tolan molecules are twisted towards each other along the C? C axis with a dihedral angle of 21°. The DPPE molecules are bonded to the rhenium atom in a chelating fashion with medium Re? P lengths of 250.4 pm. The chlorine atoms, arranged in trans position to this ligand, with Re? Cl bond lengths of 234.5 pm are slightly longer than the Re? Cl bonds in cis position with 232.3 pm.     

Die Kristallstrukturen von SeCl3 +SbCl6−, SeBr3+GaBr4−, PCl4+SeCl5− und (PPh4+)2SeCl42− · 2 CH3CN

Crystal Structures of SeCl₃⁺SbCl₆^?, SeBr₃⁺GaBr₄^?, PCl₄⁺SeCl₅^?, and (PPh₄⁺)₂SeCl₄^2? · 2 CH₃CN The crystal structures of the title compounds were determined by X-ray diffraction. SeCl₃⁺SbCl₆^?: Space group P2₁/m, Z = 4, structure determination with 1795 observed unique reflections, R = 0.022. Lattice dimensions at ?80°C: a = 940.9, b = 1066.3, c = 1234.9 pm, β = 102.79°. The compound forms ion pairs with the structure of a double octahedron with linked surfaces. SeBr₃⁺GaBr₄^?: Space group Pc, Z = 2, structure determination with 1461 observed unique reflections, R = 0.058. Lattice dimensions at ?60°C: a = 660.1, b = 655.3, c = 1431.3 pm, β = 101.177°. The compound crystallizes in the SCl₃[AlCl₄] lattice type. Between the ions there are two relatively short Se … Br? Ga contacts. PCl₄⁺SeCl₅^?: Space group Ima2, Z = 8, structure determination with 1757 observed unique reflections, R = 0.029. Lattice dimensions at ?50°C: a = 1651.6, b = 1201.2, c = 1166.4 pm. The SeCl₅^? ions are associated to chains via interionic Se? Cl … Se contacts along the crystallographic c-axis. (PPh₄⁺)₂SeCl₄^2? · 2CH₃CN: Space group P2₁/n, Z = 2, structure determination with 2578 observed unique reflections, R = 0.050. Lattice dimensions at ?80°C: a = 1288.5, b = 726.0, c = 2585.8 pm, β = 101.65°. The compound includes planar-tetragonal SeCl₄^2? ions, which almost meet D_4h symmetry.     

Synthese und Kristallstrukturen der Phosphaniminato-Komplexe [SbF2(NPEt3)]2 und [SbF(NPEt3)2]2 sowie von NMe4+SbF4−

Synthesis and Crystal Structures of the Phosphoraneiminato Complexes [SbF₂(NPEt₃)]₂ and [SbF(NPEt₃)₂]₂ as well as of NMe₄⁺SbF₄^? The title compounds have been prepared from antimony trifluoride with the silylated phosphaneimine Me₃SiNPEt₃ and [NMe₄]F, respectively. They were characterized by IR spectroscopy and by crystal structure determinations. [SbF₂(NPEt₃)]₂ : Space group Pbca, Z = 8, structure determination with 1264 unique reflections, R₁ = 0.028 for reflections with I > 2σ(I). Lattice dimensions at ?80°C: a = 1284.8, b = 1162.4, c = 1380.4 pm. The compound forms centrosymmetric dimeric molecules, in which the Ψ-trigonal-bipyramidal coordinated antimony atoms are linked via μ₂-N bridges of the NPEt₃^? ligands. [SbF(NPEt₃)₂]₂ : Space group P2₁/c, Z = 4, structure determination with 2270 unique reflections, R₁ = 0.029 for reflections with I > 2μ(I). Lattice dimensions at ?75°C: a = 815.8, b = 1121.2, c = 2068.5 pm, β = 101.09°. The compound forms centrosymmetric dimeric molecules, in which the Ψ-trigonal-bipyramidal coordinated antimony atoms are linked via μ₂-N bridges of one of the two NPEt₃^? ligands. The other NPEt₃^? group is terminally connected. NMe₄⁺SbF₄^? : Space group P2₁/c, Z = 4, structure determination with 1503 unique reflections, R₁ = 0.069 for reflections with I > 2μ(I). Lattice dimensions at ?50°C: a = 539.80, b = 896.10, c = 1760.3 pm, β = 90.338°. The compound includes monomeric SbF₄^? ions with distorted Ψ-trigonal-bipyramidal environment of the antimony atoms.     

Phosphaniminato-Komplexe von Bor. Synthese und Kristallstrukturen von [BBr2(NPMe3)]2, [B2Br3(NPiPr3)2]Br, [B2(NPEt3)4]Br2, [B2Br2(NPPh3)3]BBr4 und [{B2(NMe2)2}2(NPEt3)2]Cl2

Phosphoraneiminato Complexes of Boron. Syntheses and Crystal Structures of [BBr₂(NPMe₃)]₂, [B₂Br₃(NPⁱPr₃)₂]Br, [B₂(NPEt₃)₄]Br₂, [B₂Br₂(NPPh₃)₃]BBr₄ and [{B₂(NMe₂)₂}₂(NPEt₃)₂]Cl The bromoderivatives of the title compounds are prepared from the corresponding silylated phosphoraneimines Me₃SiNPR₃ and boron tribromide. The boron subcompound [{B₂(NMe₂)₂}₂(NPEt₃)₂]Cl₂ derives from Me₃SiNPEt₃ and B₂Cl₂(NMe₂)₂. All complexes are characterized by NMR and IR spectroscopy as well as by crystal structure determinations. [BBr₂(NPMe₃)]₂ (1): Space group P2₁/n, Z = 2, R = 0.031. Lattice dimensions at ?50°C: a = 723.8, b = 894.2, c = 1305.4 pm, β = 92.35°. 1 forms centrosymmetric molecules in which the boron atoms are linked via μ₂-N bridges of the NPMe₃^? groups of from B₂N₂ four-membered rings with B? N distances of 149.9 and 150.9 pm. B₂Br₃(NPⁱPr₃)₂]Br (2): Space group P2₁, Z = 2, R = 0.059. Lattice dimensions at ?80°C: a = 817.6, b = 2198.7, c = 851.5 pm, β = 115.09°. In the cations of 2 the boron atoms are lined via the μ₂-N atoms of the NPⁱPr₃^? groups to form planar, asymmetric B₂N₂ four-membered rings with B? N distances of 143 and 156 pm. [B₂(NPEt₃)₄[Br₂·4CH₂Cl₂ (3): Space group C2/c, Z = 4, R = 0.042. Lattice dimensions at ?50°C: a = 1946.1, b = 1180.3, c = 2311.3 pm, β = 101.02°. The structure contains centrosymmetric dications in which both the boron atoms are lined by the N atoms of two of the NPEt₃^? groups to form a B₂N₂ four-membered ring with B? N distances of 149.6 pm. The remaining two NPEt₃^? groups are terminally bonded with very short B? N distances of 133.5 pm. B₂Br₂(NPPh₃)₃]BBr₄ (4): Space group P1 , Z = 2, R = 0.065. Lattice dimension at ?50°C: a = 1025.7, b = 1496.1, c = 1807.0 pm, α = 85.09°, β = 82.90°, γ = 82.72°. In the cation the boron atoms are lined via the μ₂-N atoms of two of the NPPh₃^? groups to form a nearly planer B₂N₂ four-membered ring with B? N distances of 149.3-153.1 pm. The third NPPh₃³ group is terminally connected with teh sp² hybridized boron atom and with a B? N distance of 134.1 pm along with an almost linear BNP bond angle of 173.6°. [{B₂(NMe₂)₂}₂(NPEt₂)₂]Cl₂ · 3CH₂Cl₂ (5): Space group C2/c, Z = 4, R = 0.098. Lattice dimensions at ?70°C: a = 1557.9, b = 1294.7, c = 2122.9 pm, β = 96.08°. The structure of 4 contains centrosymmetric dications in which two by two B-B dumb-bells are linked via the μ₂-N atoms of the two NEPt₃^? groups to form B₄N₂ six-membered rings with B? N distances of 150 and 156 pm and B-B distances of 173 pm. The B? N distances of the terminally bonded NMe₂^? groups correspond to 138 pm double bonds.