Phosphaniminato‐Komplexe von Rhenium(VII). Synthesen und Kristallstrukturen von [ReO3(NPR3)] (R = Ph,Et) sowie von [ReO(OSiMe3)3(Me3SiNPEt3)]

Phosphoraneiminato Complexes of Rhenium(VII). Syntheses and Crystal Structures of [ReO₃(NPR₃)] (R = Ph, Et) and of [ReO(OSiMe₃)₃(Me₃SiNPEt₃)] The phosphoraneiminato complexes [ReO₃(NPR₃)] with R = Ph ( 1 ) and R = Et ( 2 ) are made from dirhenium heptaoxide and the silylated phosphoraneimines Me₃SiNPR₃. The complexes 1 and 2 as well as the red silanolate [ReO(OSiMe₃)₃(Me₃SiNPEt₃)] ( 3 ), which is formed as a by‐product in the synthesis of 2 , are characterized crystallographically. 1 and 2 are monomeric molecules, in which the phosphoraneiminato ligands NPR₃^– realize short ReN bonds of 179.3 pm ( 1 ) and 178.6 pm ( 2 ), respectively, with large ReNP bond angles of 162.0° ( 1 ) and 160.6° ( 2 ), respectively. In the rhenium(V) complex 3 the oxoligand occupies the apical position of the tetragonal pyramidal coordination of the rhenium atom, while the oxygen atoms of the Me₃SiO^– groups take the basic positions along with the nitrogen atom of the phosphaneimine molecule.     

Synthese,Schwingungsspektrum und Kristallstruktur des Disiloxanato‐Chloroberyllats (Ph4P)2[Be4Cl6(OSiMe2OSiMe2O)2]

Synthesis, Vibrational Spectra, and Crystal Structure of the Disiloxanato‐chloroberyllate (Ph₄P)₂[Be₄Cl₆(OSiMe₂OSiMe₂O)₂] (Ph₄P)₂[Be₄Cl₆(OSiMe₂OSiMe₂O)₂] ( 1 ) was prepared by the reaction of (Ph₄P)₂[Be₂Cl₆] with cyclo‐hexamethyl‐trisiloxane in dichloromethane solution, forming colourless, moisture sensitive crystals, which are characterized by their vibrational spectra (IR, Raman) and by an X‐ray crystal structure determination. 1 crystallizes in the triclinic space group with Z = 1 and with the lattice dimensions at 193 K: a = 1050.0(1), b = 1248.2(1), c = 1312.5(1) pm, α = 84.37(1)°; β = 76.53(1)°; γ = 70.79(1)°; R₁ = 0.0349. 1 consists of (Ph₄P)⁺ions and centrosymmetric anions [Be₄Cl₆(OSiMe₂OSiMe₂O)₂]^2‐, in which the four beryllium atoms are connected by the terminal oxygen atoms of the (OSiMe₂OSiMe₂O)^2‐ ligands via two‐forked bonds to give Be₂O₂ four‐membered rings. The Be atoms of these units are additionally bridged by two μ‐Cl atoms. 1 is also obtained by reaction of (Ph₄P)₂[Be₂Cl₆] with Baysilon grease.     

Über Reaktionen von Hexachlorodiberyllat mit Trimethylsilyl‐N‐dimethylamid. Die Kristallstrukturen von (Ph4P)3[Be2Cl5(OSiMe3)][BeCl3(Me2NSiMe3)], (Ph4P)[BeCl3(HNMe2)] und (Ph4P)(H2NMe2)[BeCl4]

On Reactions of Hexachlorodiberyllate with Trimethylsilyl‐N‐dimethylamide. Crystal Structures of (Ph₄P)₃[Be₂Cl₅(OSiMe₃)][BeCl₃(Me₂NSiMe₃)], (Ph₄P)[BeCl₃(HNMe₂)], and (Ph₄P)(H₂NMe₂)[BeCl₄] Reactions of bis‐tetraphenylphosphonium hexachlorodiberyllate, (Ph₄P)₂[Be₂Cl₆], with trimethylsilyl‐N‐dimethylamide under different conditions lead to the novel chloroberyllate derivatives (Ph₄P)₃[Be₂Cl₅(OSiMe₃)][BeCl₃(Me₂NSiMe₃)] ( 1 ), (Ph₄P)[BeCl₃(HNMe₂)] ( 2 ), and (Ph₄P)(H₂NMe₂)[BeCl₄] ( 3 ). 1 ‐ 3 were characterized by IR spectroscopy and crystal structure determinations. 1· 4CH₂Cl₂: Space group P1¯, Z = 2, lattice dimensions at 193 K: a = 1115.6(1), b = 2110.7(2), c = 2145.0(3) pm, α = 71.38(1)°, β = 85.66(1)°, γ = 85.24(1)°, R₁ = 0.0732. The [Be₂Cl₅(OSiMe₃)]^2— ion in the structure of 1 is derived from the [Be₂Cl₆]^2— ion by substitution of a μ‐Cl ligand by the oxygen atom of the (OSiMe₃)^— group. The second anion, [BeCl₃(Me₂NSiMe₃)]^—, can be described as donor acceptor complex with a short Be—N bond of 179(1) pm. 2 : Space group P1¯, Z = 2, lattice dimensions at 193 K: a = 1063.1(1), b = 1072.0(1), c = 1238.3(1) pm, α = 87.55(1)°, β = 74.86(1)°, γ = 69.73(1)°, R₁ = 0.0299. The anion of 2 forms a centrosymmetric dimer [BeCl₃(HNMe₂)]₂^2— via N—H···Cl bridges of the two donor acceptor complex units with Be—N separations of 175.2(2) pm. 3 : Space group Pbca, Z = 8, lattice dimensions at 193 K: a = 926.9(1), b = 2164.7(1), c = 2732.7(1) pm, R₁ = 0.0495. The structure of 3 contains centrosymmetric ion quadrupoles [(Me₂NH₂)(BeCl₄)]₂^2— forming by N—H···Cl bridges between (Me₂NH₂)⁺ and [BeCl₄]^2— ions.     

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.     

Kristallstruktur des Lithium‐Trimethylsilanolats [Li7(OSiMe3)7(THF)]

The lithium silanolate LiOSiMe₃ is accessible from the reaction of Me₃SiOSiMe₃ with LiMe in tetrahydrofuran. Single crystals of [Li₇(OSiMe₃)₇(THF)] were obtained from toluene at 25 °C. The structure of [Li₇(OSiMe₃)₇(THF)] (C2/c) features a capped trigonal antiprismatic arrangement of seven Li atoms. The Li atoms in [Li₇(OSiMe₃)₇(THF)] are μ₃‐bridged by seven O atoms of the silanolate ligand.     

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.     

[Co7(μ4‐O)2(O2C–CH3)8(NCO)2(HNPEt3)4] · 2 OEt2, ein siebenkerniger Komplex mit vier‐, fünf‐ und sechsfach koordinierten Cobalt‐Atomen

[Co₇(μ₄‐O)₂(O₂C–CH₃)₈(NCO)₂(HNPEt₃)₄] · 2 OEt₂, a Seven Nuclearity Complex with Four, Five, and Sixfold Coordinated Cobalt Atoms The title compound was prepared from cobalt(II) acetate with Me₃SiNPEt₃ at 180 °C and subsequent crystallization from diethylether to give blue, moisture sensitive single crystals, which were characterized by a crystal structure determination. Space group P2₁/n, Z = 2, lattice dimensions at –80 °C: a = 1544.0(1), b = 1522.1(2), c = 1702.0(1) pm, β = 103.911(10)°, R = 0.0490. [Co₇(μ₄‐O)₂(O₂C–CH₃)₈(NCO)₂ · (HNPEt₃)₄] has a centrosymmetric cluster‐like structure in which the octahedrally coordinated central cobalt atom is connected with the remaining six cobalt atoms via two μ₄‐oxygen atoms as well as via four bridging acetato groups to form a Co(Co)₆ octahedral skeleton. Four of the peripheric cobalt atoms have a distorted trigonal‐bipyramidal coordination sphere, the other two cobalt atoms are tetrahedrally coordinated. The latter are connected with the nitrogen atoms of the cyanato groups.     

A 2D Acentric Coordination Polymer, [Mn(HIDA)2(H2O)2], with a Strong Second‐Order Nonlinear Optical Effect

The crystal structure of [Mn(HIDA)₂(H₂O)₂] (Tetragonal, P4¯2₁c (no.114), a = b = 8.10(2)Å, c = 9.605(3)Å, α = β = γ = 90°, Z = 2, R = 0.051, wR² = 0.123 for 460 observed reflections) consists of infinite acentric 2D square grids with HIDA^— ions as bridging ligands. The 2D grids are interlocked(along the c axis) by hydrogen bonding. The Mn atoms are octahedrally coordinated by four O atoms of four HIDA^— ions (d(Mn—O)= 2.183(4)Å ) and two O atoms of two water molecules (d(Mn—OW) = 2.154(5)Å ). The results show that this acentric coordination polymer exhibits strong powder second harmonic generation (SHG) efficiency, ca. 1.9 times that of potassium dihydrogen phosphate, and remarkable thermal stability.     

Synthese und Kristallstrukturen der Phosphaniminato-Komplexe [AlCl2(NPEt3)]2, [GaI2(NPEt3)]2 und [GaI2(NPPh3)]2

Synthesis and Crystal Structures of the Phosphoraneiminato Complexes [AlCl₂(NPEt₃)]₂, [GaI₂(NPEt₃)]₂, and [GaI₂(NPPh₃)]₂ [AlCl₂(NPEt₃)]₂ ( 1 ) is made according to the known method by reaction of aluminium trichloride with the silylated phosphaneimine Me₃SiNPEt₃ in acetonitrile; it is isolated as colourless, moisture sensitive crystals. The phosphoraneiminato complexes [GaI₂(NPEt₃)]₂ ( 2 ) and [GaI₂(NPPh₃)]₂ ( 3 ), on the other hand, are obtained by redox reactions as pale yellow crystals; ( 2 ) of “gallium(I) iodide” with Me₃SiNPEt₃ in toluene and ( 3 ) of gallium with N-iodine triphenylphosphaneimine, INPPh₃, in tetrahydrofuran. 1 and 3 are characterized spectroscopically and by crystal structure determinations; 2 is characterized only crystallographically. 1 : Space group Pbca, Z = 4; lattice dimensions at –70 °C: a = 1232.6(2), b = 1341.1(2), c = 1393.4(3) pm, R₁ = 0.0315. 1 forms centrosymmetric molecules in which the Al atoms are linked via Al–N bonds of the two (NPEt₃^–) groups; with 185.0 and 184.4 pm these bonds are of almost the same lengths. 2 : Space group Pbca, Z = 4; lattice dimensions at –80 °C: a = 1380.0(1), b = 1311.0(1), c = 1429.1(1) pm, R₁ = 0.0273. 2 crystallizes isotypically with 1 . The gallium atoms of the centrosymmetric Ga₂N₂ four-membered ring are connected with Ga–N distances of equal length (190.9 pm). 3 · THF: Space group P2₁2₁2₁, Z = 2; lattice dimensions at –140 °C: a = 1494.6(1), b = 1536.3(1), c = 974.6(1) pm, R₁ = 0.0382. 3 forms dimeric molecules in which the gallium atoms are linked via the N atoms of the (NPPh₃^–) groups to form a non-planar Ga₂N₂ four-membered ring of C₂ symmetry with Ga–N bonds of equal lengths – within standard deviations – of 194.7 pm. The phosphoraneiminato groups are arranged in a synperiplanar way.     

[Li7(CHPMe2NSiMe3)3(OSiMe2nBu)]2, ein Gemischtligand-Li14-Cluster mit dem Carbdianion (CHPMe2NSiMe3)2−

[Li₇(CHPMe₂NSiMe₃)₃(OSiMe₂ⁿBu)]₂, a Mixed-Ligand-Li₁₄ Cluster with the Carbdianion (CHPMe₂NSiMe₃)^2? The title compound is formed as colourless moisture and oxygen sensitive crystals by the reaction of [LiCH₂PMe₂NSiMe₃]₄ with zinc or cobalt chloride in a toluene suspension in the presence of silicongrease (–OSiMe₂–)_n and n-butyllithium. It is characterized by multinucleus NMR spectroscopy and by crystal structure determinations of two different crystal individuals. 1. Space group P1 , Z = 1, lattice dimensions at ?70 °C: a = 1272.0, b = 1392.6, c = 1417.6 pm, α = 115.33°, β = 96.75°, σ = 106.81°; R = 0.042. 2. Space group P2₁/n, Z = 2, lattice dimensions at ?50 °C: a = 1424.8, b = 1457.1, c = 1997.0 pm, β = 90.32, R = 0.069.     

A Tetrameric Neodymium Silanolate: [Nd(OSiMe3)3]4

The title compound [Nd(OSiMe₃)₃]₄ ( 1 ) was prepared by reaction of [Nd{N(SiMe₃)₂}₃] with Me₃SiOH in toluene at room temperature. Compound 1 crystallized from a concentrated toluene solution in the monoclinic space group P2₁/n with the lattice constants a = 15.144(1) Å, b = 25.142(1) Å, c = 20.391(1) Å and β = 103.755(2)°. In the solid state a tetramer is observed which shows Nd‐O bond distances in the range 2.129(2)‐2.675(2) Å.     

Die Kristallstrukturen von trans‐[NiBr2(Pyridin)4] und [Ni(HNPEt3)4]I2

Crystal Structures of trans ‐[NiBr₂(pyridine)₄] and [Ni(HNPEt₃)₄]I₂ Turquoise single crystals of trans‐[NiBr₂(pyridine)₄] have been obtained by the reaction of excess pyridine with nickel(II) bromide/diacetonealcohol. According to the crystal structure determination the nickel atom is octahedrally coordinated by the two bromine atoms in trans‐position and by the nitrogen atoms of the pyridine molecules. Space group Pna2₁, Z = 4, lattice dimensions at 20 °C: a = 1592.9(2), b = 943.8(1), c = 1413.0(2) pm, R₁ = 0.0492. Dark blue single crystals of the phosphoraneimine complex [Ni(HNPEt₃)₄]I₂ have been obtained from NiI₂/H₂O with excess Me₃SiNPEt₃ and subsequent recrystallization from acetonitrile. According to the crystal structure determination the nickel atom is tetrahedrally coordinated by the nitrogen atoms of the HNPEt₃ molecules. The iodide ions are connected via N–H…I contacts with the cation to form an ion triple. Space group P2₁/c, Z = 4, lattice dimensions at –80 °C: a = 1934.9(2), b = 1078.3(1), c = 1966.3(2) pm, β = 111.040(8)°; R₁ = 0.043.     

Synthese und Struktur eines Molybdän–Gadolinium-Heterometall-Komplexes Die Struktur von [Li(thf)4]2[Cp2MoSGdBr4(thf)]2

Synthesis and structure of a Molybdenum–Gadolinium Heterometallic Complex. The Structure of [Li(thf)₄]₂[Cp₂MoSGdBr₄(thf)]₂ [Cp₂MoHLi] reacts in THF with S and GdBr₃ to yield the tetranuclear heterobimetallic complex [Li(thf)₄]₂[Cp₂MoSGdBr₄(thf)]₂. The bonding situation and the structure of this compound were characterized by X-ray structure analysis (space group P1 (No. 2), Z = 1, a = 10.845(2) Å, b = 12.166(2) Å, c = 15.881(2) Å, α = 101.74(2)°, β = 97.62(2)°, γ = 103.97(2)°). Each S atom of the central Mo₂S₂-ring is coordinated by a GdBr₄(thf) fragment. Additionally each Mo atom is connected to two Cp ligands. This leads to a tetrahedral coordination of the Mo atoms and a octahedral coordination of the Gd ions.     

Lithiierte Phosphanimin‐Komplexe. Die Kristallstrukturen von [LiCH(Me)PEt2NSiMe3]4 und des Cuprats [Li{Me3SiNPMe2CH2–Cu–CH(SiMe2OLi)PMe2NSiMe3}]2

Lithiated Phosphoraneimine Complexes. Crystal Structures of [LiCH(Me)PEt₂NSiMe₃]₄ and of Cuprate [Li{Me₃SiNPMe₂CH₂–Cu–CH(SiMe₂OLi)PMe₂NSiMe₃}]₂ [LiCH(Me)PEt₂NSiMe₃]₄ ( 1 ) has been obtained as colorless, oxygen and moisture sensitive crystals from the reaction of the silylated phosphoraneimine Me₃SiNPEt₃ with ⁿbutyllithium in ⁿhexane at 0 °C. 1 crystallizes in the tetragonal space group I4₁/acd with eight formula units per unit cell. Lattice dimensions at –80 °C: a = b = 1505.2(1), c = 4747.4(6) pm, R₁ = 0.0278. 1 forms a Li₄ tetrahedron, the faces of which are capped with the carbon atoms of the carbanionic ‐CH(Me)‐ groups. The nitrogen atoms occupy the corners of the Li₄ tetrahedron by means of “inner solvation”. The cuprate [Li{Me₃SiNPMe₂CH₂–Cu–CH(SiMe₂OLi)PMe₂NSiMe₃}]₂ ( 4 ) has been obtained from the known [LiCH₂PMe₂NSiMe₃]₄ and copper(I) iodide in the presence of silicon grease (‐OSiMe₂‐)_n in diethylether, forming colorless oxygen and moisture sensitive crystals. 4 crystallizes in the triclinic space group P 1 with one formula unit per unit cell. Lattice dimensions at –50 °C: a = 1025.4(2), b = 1145.5(2), c = 1261.0(2) pm, α = 65.19(1)°, β = 79.55(1)°, γ = 77.94(1)°, R₁ = 0.039. 4 forms a centrosymmetric dimeric molecule with a central Li₂O₂ four‐membered ring, the oxygen atoms of which are connected by ‐SiMe₂‐ bridges with the cuprate fragment > CH–Cu–CH₂‐.     

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°.     

Die Kristallstrukturen der Phosphanimin‐Komplexe [NaI(HNPPh3)3] und [SrI2(HNPPh3)2(THF)2] sowie des Natrium‐triphenylphosphaniminats [NaNPPh3]6

Crystal Structures of the Phosphaneimine Complexes [NaI(HNPPh₃)₃] and [SrI₂(HNPPh₃)₂(THF)₂], as well as of Sodium Triphenylphosphoraneiminate [NaNPPh₃]₆ [NaI(HNPPh₃)₃] ( 1 ) has been obtained as yellow, moisture sensitive crystals as an intermediate product of the synthesis of sodium triphenylphosphoraneiminate, [NaNPPh₃]₆ ( 2 ) from Ph₃PI₂ and sodium amide in liquid ammonia. Correspondingly, colourless crystals of [SrI₂(HNPPh₃)₂(THF)₂] ( 3 ) are formed from strontium amide and Ph₃PI₂ in liquid ammonia and subsequent recrystallisation of the primary product [SrI₂(HNPPh₃)₄] from thf solution. The complexes 1 – 3 are mainly characterized by crystal structure determinations. 1 · 0,5 thf: space group P3c1, Z = 4, lattice dimensions at 193 K: a = b = 1533.2(1); c = 2545.6(1) pm, R = 0.0417. 1 has a molecular structure in which the sodium atom is tetrahedrally coordinated by the iodine atom with a distance of 315.9 pm and by the nitrogen atoms of the three HNPPh₃ molecules with a distance of 238.9 pm. 2 · C₇H₈: space group P1, Z = 1, lattice dimensions at 213 K: a = 1457.1(1), b = 1484.9(1), c = 1502.7(1) pm; α = 116.32(1)°, β = 115.358(10)°, γ = 93.585(14)°; R = 0.0520. 2 has a molecular structure in which the six sodium atoms and the six nitrogen atoms of the (NPPh₃^–) groups form a hexagonal prism with approximate D_3d symmetry. 3 · 2 thf: space group P1, Z = 2, lattice dimensions at 193 K: a = 1042.9(1), b = 1337.4(1), c = 2095.1(1) pm; α = 90.130(8)°, β = 96.310(8)°, γ = 111.985(8)°; R = 0.0310. 3 has a molecular structure in which the strontium atom is octahedrally coordinated by the iodine atoms, by the nitrogen atoms of the HNPPh₃ molecules and by the oxygen atoms of the thf molecules, all ligands being in trans‐position to one another.     

Neue Benzylkomplexe der Lanthanoiden. Darstellung und Kristallstrukturen von [(C5Me5)2Y(CH2C6H5)(thf)], [(C5Me5)2Sm(CH2C6H5)2K(thf)2]∞ und [(C5Me5)Gd(CH2C6H5)2(thf)]

New Benzyl Complexes of the Lanthanides. Synthesis and Crystal Structures of [(C₅Me₅)₂Y(CH₂C₆H₅)(thf)], [(C₅Me₅)₂Sm(CH₂C₆H₅)₂K(thf)₂]_∞, and [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] YBr₃ reacts with potassium benzyl and [K(C₅Me₅)] in THF to give KBr and the monobenzyl compound [(C₅Me₅)₂ · Y(CH₂C₆H₅)(thf)] 1 . The analogous reaction with SmBr₃ in THF leads to the polymeric product [(C₅Me₅)₂Sm(CH₂C₆H₅)₂ ∞ K(thf)₂]_∞ 2 , with GdBr₃ to [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] 3 . The structures of 1–3 were determined by X-ray single crystal structure analysis:

• Space group P1 , Z = 2, a = 851.2(4) pm, b = 952.7(4) pm, c = 1858.6(8) pm, α = 79.90(4)°, β = 77.35(4)°, γ = 73.30(3)°.
• Space group P1 , Z = 2, a = 903.3(2) pm, b = 1375.9(3) pm, c = 1801.1(4) pm, α = 100.92(3)°, β = 100.77°, γ = 98.25(3)°.
• Space group P2₁/n, Z = 8, a = 1458.2(5) pm, b = 927.8(3) pm, c = 3792.9(15) pm, β = 96.83(3)°.

     

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

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

CoSm(SeO3)2Cl,CuGd(SeO3)2Cl,MnSm(SeO3)2Cl,CuGd2(SeO3)4 und CuSm2(SeO3)4: Übergangsmetallhaltige Selenite von Samarium und Gadolinum

CoSm(SeO₃)₂Cl, CuGd(SeO₃)₂Cl, MnSm(SeO₃)₂Cl, CuGd₂(SeO₃)₄ and CuSm₂(SeO₃)₄: Transition Metal containing Selenites of Samarium and Gadolinum The reaction of CoCl₂, Sm₂O₃, and SeO₂ in evacuated silica ampoules lead to blue single crystals of CoSm(SeO₃)₂Cl (triclinic, , Z = 4, a = 712.3(1), b = 889.5(2), c = 1216.2(2) pm, α = 72.25(1)°, β = 71.27(1)°, γ = 72.08(1)°, R_all = 0.0586). If MnCl₂ is used in the reaction light pink single crystals of MnSm(SeO₃)₂Cl (triclinic, , Z = 2, a = 700.8(2), b = 724.1(2), c = 803.4(2) pm, α = 86.90(3)°, β = 71.57(3)°, γ = 64.33(3)°, R_all = 0.0875) are obtained. Green single crystals of CuGd₂(SeO₃)₂Cl (triclinic, , Z = 4, a = 704.3(4), b = 909.6(4), c = 1201.0(7) pm, α = 70.84(4)°, β = 73.01(4)°, γ = 70.69(4)°, R_all = 0.0450) form analogously in the reaction of CuCl₂ and Gd₂O₃ with SeO₂. CoSm(SeO₃)₂Cl contains [CoO₄Cl₂] octahedra, which are connected via one edge and one vertex to infinite chains. The Mn²⁺ ions in MnSm(SeO₃)₂Cl are also octahedrally coordinated by four oxygen and two chlorine ligands. The linkage of the polyhedra to chains occurs exclusively via edges. Both, the cobalt and the manganese compound show the Sm³⁺ ions in eight and ninefold coordination of oxygen atoms and chloride ions. In CuGd(SeO₃)₂Cl the Cu²⁺ ions are coordinated by three oxygen atoms and one Cl^— ion in a distorted square planar manner. One further Cl^— and one further oxygen ligand complete the [CuO₃Cl] units yielding significantly elongated octahedra. The latter are again connected to chains via two common edges. For the Gd³⁺ ions coordination numbers of ?8 + 1”? and nine were found. Single crystals of the deep blue selenites CuM₂(SeO₃)₄ (M = Sm/Gd, monoclinic, P2₁/c, a = 1050.4(3)/1051.0(2), b = 696.6(2)/693.5(1), c = 822.5(2)/818.5(2) pm, β = 110.48(2)°/110.53(2)°, R_all = 0.0341/0.0531) can be obtained from reactions of the oxides Sm₂O₃ and Gd₂O₃, respectively, with CuO and SeO₂. The crystal structure contains square planar [CuO₄] groups and irregular [MO₉] polyhedra.     

Untersuchungen über Iodoferrate: Die Kristallstrukturen von Fe(THE)6(FeI3THF)2 · THF und Fe(Ch2O)6(FeI4)2 · I2(THF = C4H8O)

Investigations about Iodoferrates: The Crystal Structures of Fe(thf)₆(FeI₃thf)₂ · thf and Fe(CH₂O)₆(FeI₄)2 · I₂(thf = C₄H₈O) The crystal structures of FeI₂ · 3 thf (i.e. Fe(thf)₆(FeI₃thf)₂ · thf) ( 1 ) and Fe(CH₂O)₆(FeI₄)₂ · I₂ ( 2 ) were determined from single crystal X-ray data. 1 crystallizes in the cubic space group Pa3, a = 1759.8 pm, Z = 4, 2 in the monoclinic space group P2₁/n, a = 997.4, b = 1669.4, c = 1082.6 pm, β = 93.11°, Z = 2. The structure of 1 is composed of octahedral Fe(thf)₆²⁺ cations and distorted tetrahedral [FeI₃(thf)]-anions (Fe? I distance 261.1 pm). In 2 two tetrahedral tetraiodoferrate (III) anions are linked by an iodine molecule. The Fe? I distance was found to be 253.9 pm (mean, the I? I distance between FeI₄^? and I₂ 356.1 pm. The decomposititon of 1 in vacuum at elevated temperatures and the resulting formation of 2 from 1 are discussed.