Cobalt(II)-organische Phosphaniminato-Komplexe mit Heterocuban-Struktur. Kristallstrukturen von [CoBr(NPR3)]4 mit R = Me,Et, [Co(C≡C–CMe3)(NPMe3)]4 und [Co(C≡C–SiMe3)(NPEt3)]4

Organo-Cobalt(II) Phosphorane Iminato Complexes with Heterocubane Structures. Crystal Structures of [CoBr(NPR₃)]₄ with R = Me, Et, [Co(C≡C–CMe₃)(NPMe₃)]₄, and [Co(C≡C–SiMe₃)(NPEt₃)]₄ The phosphorane iminato complexes [CoBr(NPR₃)]₄, which are accessible by reaction of CoBr₂ with the silylated phosphorane imines Me₃SiNPR₃ (R = Me, Et) in the melt at 180 °C and in the presence of KF, can be transformed into the alkynyl complexes [Co(C≡C–CMe₃) · (NPMe₃)]₄ and [Co(C≡C–SiMe₃)(NPEt₃)]₄ on obtaining the heterocubane structures, when caused to react with the lithium organic reagents LiC≡C–CMe₃ and LiC≡C–SiMe₃ in THF at 0 °C. According to the crystal structure analyses all four of the compounds form heterocubane structures with only slightly distorted Co₄N₄ cubic structures.     

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.     

Phosphaniminato-Komplexe von Mangan(II) und Nickel(II) mit Heterocubanstruktur. Die Kristallstrukturen von [MCl(NPEt3)]4 mit M = Mn und Ni

Phosphoraneiminato Complexes of Manganese(II) and Nickel(II) with Heterocubane Structure. Crystal Structures of [MCl(NPEt₃)]₄ with M = Mn and Ni The phosphoraneiminato complexes [MCl(NPEt₃)]₄ with M = manganese and nickel as well as [MnBr(NPEt₃)]₄ are formed from the anhydrous halides MX₂ and excess phosphoraneimine Me₃SiNPEt₃ by fusion reaction. They form paramagnetic, moisture-sensitive, orange (M = Mn) and turquoisegreen (M = Ni) crystals, respectively, which are characterized by i.r. spectroscopy and by crystal structure determinations. [MnCl(NPEt₃)]₄ ( 1 ): Space group C2/c, Z = 4, structure solution with 3 591 unique reflections, (2 811 > 2σ(I)) R = 0.036. Lattice dimensions at -50°C: a = 2104.3, b = 1100.6, c = 1966.5 pm, β = 115.87°. [NiCl(NPEt₃)]₄ ( 2 ): Space group C2/c, Z = 4, structure solution with 2 711 unique reflections, (1611 > 2σ(I)) R = 0.056. Lattice dimensions at ?50°C: a = 2051.6, b = 1099.2, c = 1954.6 pm, β = 115.80°. 1 and 2 are isostructural with one another. They form heterocubane structures in which the metal atoms are linked via μ₃-N-bridges of the phosphoraneiminato groups with M₄N₄ bridge-type bond angles close to 90°.     

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.     

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 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.     

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.     

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°.     

Phosphaniminato-Komplexe des Zinks mit Hydrido-, Alkinylo-, Alkenylo- und Amido-Liganden

Phosphoraneiminato Complexes of Zinc with Hydrido, Alkynylo, Alkenylo, and Amido Ligands Synthesis and properties of the phosphoraneiminato complexes [ZnCl(NPMe₃)]₄ ( 1 ), [ZnH(NPMe₃)]₄ ( 2 ) as well as of the alkynylo derivatives [Zn(C≡C–SiMe₃)(NPMe₃)]₄ ( 3 ), [Zn(C≡C–C≡C–SiMe₃)(NPR₃)]₄ [R = Me ( 4 a ), R = Et ( 4 b )], [Zn(C≡C–Ph)(NPMe₃)]₄ ( 5 ) and of the alkenylozinc complexes [Zn(CH=CHMe)(NPR₃)]₄ [R = Me ( 6 a ), R = Et ( 6 b )] are described. According to crystal structure analyses of 1 , 3 , and 4 b these complexes possess heterocubane structures with only slightly distorted Zn₄N₄ cubic skeletons. Experiments to substitute the terminal ligands at the zinc atoms by bis(trimethylsilyl)amido groups lead to disintegration of the heterocubanes and formation of the dimeric complex [Zn(μ₂-NPEt₃){N(SiMe₃)₂}]₂ ( 7 ) and of the trinuclear derivative [Zn₃(μ₂-NPMe₃)₄{N(SiMe₃)₂}₂] ( 8 ), in which the central zinc atom is surrounded by the four N atoms of the NPEt₃^– groups in a spiro-cyclic fashion. 7 and 8 are also characterized by crystal structure analyses.     

Phosphaniminato‐Acetato‐Cluster von Kupfer und Zink. Kristallstrukturen von [Cu4(NPEt3)2(O2CCH3)6] und [Zn4(NPEt3)2(O2CCH3)6]

Phosphoraneiminato Acetate Cluster of Copper and Zinc. Crystal Structures of [Cu₄(NPEt₃)₂(O₂CCH₃)₆] and [Zn₄(NPEt₃)₂(O₂CCH₃)₆] The anhydrous acetates of copper(II) and zinc react with the silylated phosphaneimine Me₃SiNPEt₃ in dichloromethane at 20 °C forming the mixed phosphoraneiminato acetate clusters [Cu₄(NPEt₃)₂(O₂CCH₃)₆] ( 1 ), which forms emerald crystals, and colourless [Zn₄(NPEt₃)₂ · (O₂CCH₃)₆] ( 2 ). In spite of analogous composition the structures of 1 and 2 are completely different. In the asymmetric unit of 1 three copper atoms of an almost isosceles triangle are linked via two nitrogen atoms of the NPEt₃^– groups to form a trigonal bipyramidal aggregate. One of these three copper atoms is chelated by an acetate group, another one is connected with the fourth copper atom via three μ₂‐O₂C–CH₃ groups. The asymmetric units are associated via a μ₂‐O₂C–CH₃ group and a μ₃‐OC(O)CH₃ group at a time so that infinite chains result. In 2 two zinc atoms are linked via the nitrogen atoms of the two NPEt₃^– groups to form an almost centrosymmetric four‐membered ring. Both nitrogen atoms of the four‐membered ring are connected with another zinc atom each. These zinc atoms again are linked with the zinc atoms of the Zn₂N₂ four‐membered ring via two μ₂‐O₂C–CH₃ groups each and additionally coordinated with a terminal acetate ligand each.     

Phosphaniminato-Komplexe von Nickel(II) mit Heterocubanstruktur

Phosphoraneiminato Complexes of Nickel(II) with Heterocubane Structure The phosphoraneiminato complexes [NiBr(NPR₃)]₄ (R = CH₃, C₂H₅) and [NiI(NPEt₃)]₄ were obtained from NiBr₂ and NiI₂, respectively, with excess Me₃SiNPR₃ in the melt (R = CH₃, C₂H₅) in the presence of sodium fluoride. They form dark-green, moisture sensitive crystalline powders. They were characterized by IR spectroscopy, mass spectrometry, magnetic behaviour as well as by crystal structure analyses. The compounds possess heterocubane structures, in which the nickel atoms are linked via μ₃–N-bridges of the phosphoraneiminato groups.     

Phosphaniminato-Komplexe von Cobalt und Zink mit Heterocubanstruktur. Die Kristallstrukturen von [CoI(NPMe3)]4 und [ZnI(NPMe3)]4

Phosphoraneiminato Complexes of Cobalt and Zinc with Heterocubane Structure. Crystal Structures of [CoI(NPMe₃)]₄ and [ZnI(NPMe₃)]₄ The title compounds have been prepared from CoI₂ and ZnI₂, respectively, and Me₃SiNPMe₃ by fusion reactions at 180°C in the presence of sodium fluoride. They crystallize from dichloromethane as dark green (Co) or colourless (Zn) single crystals including three molecules CH₂Cl₂ per formula unit, which were characterized by crystal structure determinations. [CoI(NPMe₃)]₄ · 3 CH₂Cl₂: Space group P3m1, Z = 2, structure solution with 2376 independent reflections, R = 0.033. Lattice dimensions at ?50°C: a = b = 1455.8, c = 1270.5 pm. [ZnI(NPMe₃)]₄ · 3 CH₂Cl₂: Space group P3m1, Z = 2, structure solution with 2197 independent reflections, R = 0.043. Lattice dimensions at ?60°C: a = b = 1454.9, c = 1270.5 pm. Both complexes are isostructural with one another. They form heterocubane structures in which the metal atoms are linked via μ₃-N-bridges of the phosphoraneiminato groups with M₄N₄ bridge-type bond angles close to 90°.     

[Cu12(NPEt3)8]4+ and [Ag12(NPEt3)8]4+: Cubane Structures

Unusual, highly symmetrical cubes are formed by the dodecameric cationic phosphoraneiminato complexes of copper(I ) and silver(I ) [M₁₂(NPEt₃)₈]⁴⁺, in which the metal atoms occupy the edges and the N atoms of NPEt ³⁻₃ groups the corners of the cube (see figure). The structures can be understood as molecular sections of the Cu₃N structure, which is inverse to the ReO₃‐type structure.     

Phosphaniminato‐Acetato‐Komplexe von Cobalt und Cadmium mit M4N4‐Heterocuban‐Struktur

Phosphoraneiminato‐Acetato Complexes of Cobalt and Cadmium with M₄N₄ Heterocubane Structure The phosphoraneiminato‐acetato complexes [M(NPEt₃)(O₂C–CH₃)]₄ with M = Co and Cd are formed from the anhydrous metal(II) acetates with excess Me₃SiNPEt₃ at 180 °C. By crystallization from diethyl ether blue, moisture sensitive single crystals of [Co(NPEt₃) · (O₂C–CH₃)]₄ can be obtained, while colourless single crystals of [Cd(NPEt₃)(O₂C–CH₃)]₄ · 2 CH₂Cl₂ originate from dichloromethane solution. In vacuo the intercalary CH₂Cl₂ is released. The complexes are characterized by their IR spectra and by crystal structure analyses. In both complexes the metal atoms are associated via μ₃–N bridges of the (NPEt₃^–) groups to form heterocubanes. In the cobalt complex the acetato ligands are bonded in a semichelate fashion with a short Co–O and a long Co–O bond each (Co–O distances in average 199.5 and 257.4 pm). In the cadmium complex the acetato groups form almost symmetrical chelates (Cd–O distances in average 232.1 and 237.8 pm); this leads to a distorted trigonal‐bipyramidal arrangement at the cadmium atoms. [Co(NPEt₃)(O₂C–CH₃)]₄: Space group P 1, Z = 4, lattice dimensions at –60 °C: a = 1110.1(2), b = 2051.3(5), c = 2169.5(4) pm, α = 100.03(2)°, β = 103.404(15)°, γ = 97.63(2)°, R = 0.0480. [Cd(NPEt₃)(O₂C–CH₃)]₄ · 2 CH₂Cl₂: Space group C2/c, Z = 4, lattice dimensions at –80 °C: a = 1550.2(1), b = 2101.1(1), c = 1706.1(1) pm, β = 91.09(1)°, R = 0.0311.     

Formation of Unusual Complexes from the Reaction of [C(NMe2)3][(CO)4Fe{C(O)NMe2}] with InMe3; Crystal Structures of [C(NMe2)3]3[Fe2(CO)6(μ‐CO){μ‐InFe(CO)4(μ‐O2CNMe2)InFe(CO)4}] and [C(NMe2)3]2[{(CO)4Fe}2In(O2CNMe2)]·THF

The carbamoyl complex [C(NMe₂)₃][(CO)₄Fe{C(O)NMe₂}] ( 1 ) reacts with InMe₃ under loss of the methyl groups to produce a variety of compounds from which only the anionic cluster complexes [C(NMe₂)₃]₃[Fe₂(CO)₆(μ‐CO){μ‐InFe(CO)₄(μ‐O₂CNMe₂)InFe(CO)₄}] ([C N ₃]₃[ 2 ]) and [C(NMe₂)₃]₂[{(CO)₄Fe}₂In(O₂CNMe₂)]·THF ([C N ₃]₂[ 3 ]·THF) could be crystallized and characterized by X‐ray analyses. The anion [ 2 ]^3? has a Fe₂(CO)₉‐like structure and both anions contain the carbaminato ligand either in a bridging or in a chelating function.     

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.     

Phosphaniminato‐ und Phosphanimin‐Komplexe von Nickel(II). Die Kristallstrukturen von [Ni(O3SCF3)(NPMe3)]4, [Ni4Br5{NP(NMe2)3}3], [NiBr2{HNP(NMe2)3}2] und [Ni(PMePh2)4]

Phosphoraneiminato‐ and Phosphaneimine Complexes of Nickel(II). Crystal Structures of [Ni(O₃SCF₃)(NPMe₃)]₄, [Ni₄Br₅{NP(NMe₂)₃}₃], [NiBr₂{HNP(NMe₂)₃}₂], and [Ni(PMePh₂)₄] Black‐violet single crystals of [Ni(O₃SCF₃)(NPMe₃)]₄ ( 1 ) have been prepared from [NiBr(NPMe₃)]₄ and copper(I)triflate by metathesis reaction. The nickel atoms are associated via μ₃‐N bridges of the (NPMe₃^–) groups to form a heterocubane. The triflate ions are bonded to the Ni atoms in a chelate fashion. Blue single crystals of [Ni₄Br₅{NP(NMe₂)₃}₃] ( 2 ) are obtained by the reaction of NiBr₂ with Me₃SiNP(NMe₂)₃ in boiling toluene in the presence of sodium fluoride. The Ni atoms in 2 are associated with three μ₃‐bridged nitrogen atoms of the (NP(NMe₂)₃^–) groups as well as by a μ₃‐Br atom to give a distorted heterocubane. Deep blue single crystals of the phosphaneimine complex [NiBr₂{HNP(NMe₂)₃}₂] ( 3 ) are formed from Me₃SiNP(NMe₂)₃ and NiBr₂ in boiling dichloromethane. In 3 the Ni atom is tetrahedrally coordinated by the bromine atoms and by the nitrogen atoms of the phosphane imine molecules. Pale red crystals of [Ni(PMePh₂)₄] ( 4 ) have been obtained by the reaction of [NiBr(NPMe₃)]₄ with lithium phenylacetilyde in the presence of PMePh₂. In 4 the Ni atom is distorted tetrahedrally coordinated by the phosphorus atoms of the phosphane molecules with Ni–P distances of 219.9 pm in average. 1 – 4 have been characterized by crystallographic X‐ray analyses. 1 : Space group P2₁/n, Z = 4, lattice dimensions at 193 K: a = 1566.7(2); b = 1479.9(1); c = 1960.6(2) pm; β = 105.908(9)°; R = 0.0443. 2 · 3 CH₂Cl₂: Space group P2₁/c, Z = 4, lattice dimensions at 293 K: a = 1226.0(3); b = 1614.0(3); c = 2406.0(5) pm; β = 92.34(3)°; R = 0.0703. 3 : Space group C2/c, Z = 4, latttice dimensions at 203 K: a = 1840.7(1); b = 810.1(1); c = 1607.2(2) pm; β = 94.74(1)°, R = 0.0340. 4 : Space group P1, Z = 2, lattice dimensions at 223 K: a = 1053.1(2); b = 1315.0(3); c = 1674.5(3) pm; α = 81.55(1)°; β = 79.15(2)°; γ = 84.91(2)°; R = 0.0497.     

Synthese und Kristallstrukturen der Phosphanimin-Komplexe [Cu(μ-HNPEt3)]4(O3S–CF3)4 und [Pt2Me6(μ-I)2(μ-HNPMe3)]

Synthesis and Crystal Structures of the Phosphaneimine Complexes [Cu(μ-HNPEt₃)]₄(O₃S–CF₃)₄ and [Pt₂Me₆(μ-I)₂(μ-HNPMe₃)] The title compounds have been prepared by the reaction of copper(I)triflate with [NiBr(NPEt₃)]₄ in CH₂Cl₂ suspension in the presence of water, and by the reaction of [PtMe₃I]₄ with Me₃SiNPMe₃ in boiling toluene in the presence of cesium fluoride, respectively. According to the crystal structure determinations the cation of the copper complex forms tetrameric units [Cu(HNPEt₃)]₄⁴⁺ with S₄ symmetry with Cu–N bond lengths of 191.6 and 192.1 pm. In the platinum complex the platinum atoms are linked by two μ-I bridging atoms as well as by the μ-N atom of the HNPMe₃ ligand with Pt–N bond lengths of 228.1 and 229.5 pm.     

[Ag12F(NPEt3)8]3+: Ein durch Fluorid gefüllter Metalla‐Cryptand

[Ag₁₂F(NPEt₃)₈]³⁺: A Metalla‐Cryptand filled with a Fluoride Ion [Ag₁₂F(NPEt₃)₈](SiF₆)_1,5 ( 1 ) was obtained from the reaction of silver(I) fluoride with the silylated phosphaneimine Me₃SiNPEt₃ in acetonitrile. It forms colorless, light‐ and hydrolysis‐sensitive crystals, which incorporate acetonitrile that is lost in vacuo. 1 · 2,4 CH₃CN was characterized by its IR spectrum and by X‐ray crystal structure analysis. Space group Pa 3, Z = 8, a = 2734.8(1) pm at 153 K, R = 0.059. The compound consists of cations [Ag₁₂F(NPEt₃)₈]³⁺ (point group C₃), SiF₆^2– counter‐ions and acetonitrile molecules which show no interactions. In the cation the silver atoms are located on the edges of a nearly undistorted cube and the N atoms of the phosphoraneiminato groups (NPEt₃^–) occupy the vertices. A fluoride ion in the center of the cube has contacts of nearly similar length to the 12 silver atoms (mean distance 304.7 pm).     

[Mn4Br(CH=CMe2)3(μ3‐NPEt3)4] — ein 2‐Methyl‐prop‐1‐enyl‐Phosphaniminato‐Komplex von Mangan(II) mit Heterokubanstruktur

[Mn₄Br(CH=CMe₂)₃(μ₃‐NPEt₃)₄] — a 2‐Methyl‐prop‐1‐enyl‐Phosphoraneiminato Complex of Manganese(II) with Heterocubane Structure [Mn₄Br(CH=CMe₂)₃(μ₃‐NPEt₃)₄] ( 1 ) has been prepared from [MnBr(μ₃‐NPEt₃)]₄ and BrMg(CH=CMe₂) in thf solution and subsequent extraction of the solvent‐free residue with n‐hexane. 1 forms red single crystals from diethylether solution, which are characterized by a crystal structure determination. Space group P1¯, Z = 2, lattice dimensions at —80 °C: a = 1144.7(1), b = 1411.3(2), c = 1521.8(2) pm, α = 91.581(14), β = 90.163(14), γ = 91.947(14)°, R₁ = 0.0448. 1 exhibits a Mn₄N₄ heterocubane core, a terminally coordinated bromine ligand and three Mn—CH=CMe₂ groups with M—C bond lengths of 213.8 pm on average.