Synthese und Strukturen von Bis(amino)germa- und -stanna-Chalkogeniden

Synthesis and Structures of Bis(amino)germa and -stanna Chalcogenides The cyclic bis(amino)germylene 1 and the -stannylene 2 react with elemental S, Se and Te to yield oxydation products of the general formula Me₂Si(NtBu)₂MEl₂M(NtBu)₂SiMe₂ (M = Ge, El = S ( 4 ), El = Se ( 5 ), El = Te ( 6 ); M = Sn, El = Se ( 9 ), El = Te ( 10 )). As may be deduced from X-ray structures ( 4, 5, 6, 9, 10 ) all compounds show similar central skeletons: the three spirocyclicly connected four-membered rings SiN₂M (2x) and MEl₂M are oriented in an orthogonal way to oneanother. The germanium and the tin atoms thus are in a distorted tetrahedral coordination while the chalcogen atoms only have two neighbours in acute angles. If 1 is allowed to react with trimethylamine-N-oxide, the oxygen is transferred to germanium and [Me₂Si(NtBu)₂GeO]₃ ( 3 ) is formed. Contrarily to the other compounds 3 can be described as a trimer. There is a central almost planar Ge₃O₃ six-membered ring, the germanium atoms serving as spiro-cyclic centres to three GeN₂Si four-membered rings (X-ray structure of 3 ). In the central four-membered rings of 4, 5, 6, 9 and 10 no transanular bonding between the chalcogen atoms have to be considered although these atoms have small distances to oneanother. The mean M-El distances have been found to be: Ge? O 1.762(5), Ge? S 2.226(3), Ge? Se 2.363(3), Ge? Te 2.592(5), Sn? Se 2.536(3), Sn? Te 2.741(3) Å.     

Zur Reaktion eines Bis(amino)germylens mit Germaniumaziden: Abfangreaktionen von instabilen Germa-Iminen

Reaction of a Cyclic Bis(amino)germylene with Germaniumazides: Trapping-Reactions of Unstable Germa-Imines . The cyclic bis(amino)germylene 1 reacts with different germaniumazides of the type Me₂Si(NtBu)₂Ge(R)N₃ (R = Me ( 2 ), tBu ( 3 ), N(SiMe₃)₂ ( 4 ), R = N₃ ( 5 )). With the exception of 4 all azides lose dinitrogen when treated with 1 and the Ge^II center coordinates the α-nitrogen of the azide group. It seems to be reasonable to assume a transient germaimine (nitride) which is trapped by further reaction with the azide molecules 2 and 5 or by reaction with the solvent pyridine ( 3 ). In the case of 2 the germatetrazole [Me₂Si(NtBu)₂]GeN₄[Ge(NtBu)₂SiMe₂]₂ ( 6 ) is formed, the tetrazole nitrogens being exclusively substituted by germanium atoms (point symmetry of the molecule C_s(m)). When 1 is treated with 5 a tris(germa)amine [Me₂Si(NtBu)₂Ge(N₃)]₃N ( 8 ) is formed, which has an azide group attached to each Ge-atom. X-ray analysis reveals that the nine nitrogen atoms of the azide groups are coplanar with the trigonal planar Ge₃N moiety (crystallographic symmetry: 3/m). The reaction of 1 with 3 is very surprising: the pyridine in the product Me₂Si(NtBu)₂Ge(C₅H₄N)? N(H)Ge(tBu)(NtBu)₂SiMe₂ ( 7 ) is bonded via an α-carbon atom while the remaining hydrogen has added to the nitride-nitrogen. 6 crystallizes in the monoclinic system space group C2/m, a = 24.306(9), b = 10.933(6), c = 19.420(9) Å, β = 91.81(2)° and Z = 4. 7 crystallizes in the hexagonal system space group P6₃/m with a = b = 16.73(1), c = 11.006(8) Å, γ = 120° and Z = 2, and 8 crystallizes in the monoclinic system space group P2₁/n, a = 11.341(6), b = 26.086(9), c = 13.244(7) Å, β = 98. I2(2)° mit Z = 4.     

Chemie und Strukturchemie von Phosphiden und Polyphosphiden. 53. Darstellung,Eigenschaften und Schwingungsspektren der Käfiganionen P113− und As113−

Chemistry and Structural Chemistry of Phosphides and Polyphosphides. 53. Preparation, Properties, and Vibrational Spectra of the Cage Anions P₁₁^3? and As₁₁^3? The Zintl-phases M₃X₁₁ (M = Na, K, Rb, Cs; X = P, As) are prepared from the elements or from M₃X₇ and X. The compounds undergo a first-order phase transition from the crystalline to the plastically crystalline state. Unit cell and space group of both modifications and the transition temperature T_c are determined. The vibrational spectra of the crystalline compounds and the Raman spectrum of the P₁₁^3? anion in en-solution as well are measured. The assignment of the frequencies is given, based on the 32-D₃ symmetry of the X₁₁^3? cage anion. Normal coordinate analysis is carried out in terms of Cartesian coordinates to avoid the problem of redundancies in using internal coordinates. The force constants [mdyn Å^?1] obtained for the characteristic bonds r, s, and t are: f = 1.34, f = 1.20, f = 1.08; f = 1.1, f = 0.91. Normal vibrations and the potential energy distribution (PED) are discussed.     

Metallderivate von Molekülverbindungen. IV. Synthese,Struktur und Reaktivität des Lithium-[tris-(trimethylsilyl)silyl]tellanids · DME

Metal Derivatives of Molecular Compounds. IV Synthesis, Structure, and Reactivity of Lithium [Tris(trimethylsilyl)silyl]tellanide · DME Lithium tris(trimethylsilyl)silanide · 1,5 DME [3] and tellurium react in 1,2-dimethoxyethane to give colourless lithium [tris(trimethylsilyl)silyl]tellanide · DME ( 1 ). An X-ray structure determination {-150 · 3·C; P2₁/c; a = 1346.6(4); b = 1497.0(4); c = 1274.5(3) pm; β = 99.22(2)·; Z = 2 dimers; R = 0.030} shows the compound to be dimeric forming a planar Li? Te? Li? Te ring with two tris(trimethylsilyl)silyl substituents in a trans position. Three-coordinate tellurium is bound to the central silicon of the tris(trimethylsilyl)silyl group and to two lithium atoms; the two remaining sites of each four-coordinate lithium are occupied by the chelate ligand DME {Li? Te 278 and 284; Si? Te 250; Li? O 200 pm (2X); Te? Li? Te 105°; Li? Te? Li 75°; O? Li? O 84°}. The covalent radius of 154 pm as determined for the DME-complexed lithium in tellanide 1 is within the range of 155 ± 3 pm, also characteristic for similar compounds. In typical reactions of the tellanide 1 [tris(trimethylsilyl)silyl]tellane ( 2 ), methyl-[tris(trimethylsilyl)silyl]tellane ( 4 ) and bis[tris(trimethylsilyl)silyl]ditellane ( 5 ) are formed.     

Schwefeldioxid als Ligand und Synthon. XII. Synthese und Reaktivität von Nickel(II)-Komplexen dreizähniger anionischer Liganden des Typs (C6H3{CH2NR1R2}2-2,6)−

Sulfur Dioxide as Ligand and Synthon. XII. Synthesis and Reaction Behaviour of Nickel(II) Complexes with Terdendate Anionic Ligands of the Type (C₆H₃{CH₂NR¹R²}₂?2,6)^? Organonickel(II) complexes of the type [NiX{C₆H₃(CH₂NR¹R²)₂?2,6}] (X = halide OH₂⁺/CF₃SO₃^?; R¹?R²?Et 1 ; R¹?R²?i? Pr 2 ; R¹ = Me, R² = Cy 3 ; (NR¹R²) = piperidino 4 ; (NR¹R²) = pyrrolidino 5 ) are described. ¹H and ¹³C NMR and UV/Vis spectra were recorded, and the X-ray crystal structure of 1 a (X = Br) was determined. This complex crystallizes orthorhombically in the space group Pbca with a = 1 335.8(2) pm, b = 1 903.3(3) pm, c = 1 365.4(3) pm and Z = 8, and has an approximately square-planar geometry. 4 and 5 show a reversible binding of SO₂ which has been detected by means of IR photoacoustic spectroscopy. The reactions of 1 – 5 with CS₂ and PhNSO are discussed.     

VII Zwei Oxidationsstufen und vier verschiedene Koordinationen von Eisen in einer Verbindung. Synthese,Kristallstruktur und spektroskopische Charakterisierung von 1,4‐Dimethylpiperazinium‐Chloroferrat(II,III), (dmpipzH2)6[FeIICl4]2[FeIIICl4]2[FeIICl5] [FeIIICl6]

Halogeno Metallates of Transition Elements with Cations of Nitrogen‐containing Heterocyclic Bases. VII Two Oxidation States and Four Different Iron Coordinations in one Compound. Synthesis, Crystal Structure, and Spectroscopic Characterization of 1,4‐Dimethylpiperazinium Chloroferrate(II, III), (dmpipzH₂)₆[Fe^IICl₄]₂[Fe^IIICl₄]₂[Fe^IICl₅] [Fe^IIICl₆] The title compound being stable on air crystallizes from aqueous hydrochloric acid solutions in the trigonal space group R3 with a = 13,197(1), c = 38,405(6) Å. Besides the cations in chair form, the structure contains six discrete, mononuclear chloroferrate anions arranged on a threefold axis. Tetrahedral, octahedral, and, for the first time with iron(II), trigonal bipyramidal metal coordinations occur. Four sub‐spectra contributing to the ⁵⁷Fe Mössbauer spectrum can be distinguished and have been attributed to all four types of chloroferrate anions in the structure. The Raman spectroscopic investigation of orientated single crystals allows to recognize polarized and non‐polarized vibrations as well as to attribute all observed frequencies.     

Komplexchemie P-reicher Phosphane und Silylphosphane. XI [1]. Bildung,Reaktionen und Strukturen von Chromcarbonylkomplexen aus Reaktionen von Li(THF)2[η2-(tBu2P)2P] mit Cr(CO)5 · THF und Cr(CO)4 · NBD

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. XI. Formation, Reactions, and Structures of Chromium Carbonyl Complexes from Reactions of Li(THF)₂[η₂-(^tBu₂P)₂P] with Cr(CO)₅ · THF and Cr(CO)₄ · NBD Reactions of Li(THF)₂[η²-(^tBu₂P)₂P] 1 with Cr(CO)₅ · THF yield Li(THF)₂Et₂O[Cr(CO)₄{η²-(^tBu₂P)₂P}η¹-Cr(CO)₅] 2 and the compounds [Cr(CO)₄{η²-(^tBu₂P)₂PH}] 3 , [Cr(CO)₅{η¹-(^tBu₂P)₂PH}] 4 , (^tBu₂P)₂PH 5 and ^tBu₂PH · Cr(CO)₅ 6 . The formation of 3, 4, 5 and 6 is due to byproducts coming from the synthesis of 1. 2 reacts with CH₃COOH under formation of 3 . After addition of 12-crown-4 1 with NBD · Cr(CO)₄ in THF forms Li(12-crown-4)₂[Cr(CO)₄-{η²-(^tBu₂P)₂P}] 7 (yellow crystals). 7 reacts with CH₃COOH to 3 – which regenerates 7 with LiBu – with Cr(CO)₅THF to compound 2 , with NBD · Cr(CO)₄ in THF to 2 and 3 (ratio 1 : 1). With EtBr, 7 forms [Cr(CO)₄{η²-(^tBu₂P)₂PEt}] 8 , and [Cr(CO)₄{η²-(^tBu₂P)₂PBr}] 9 with BrCH₂? CH₂Br. The compounds were characterized by means of ¹H, ¹³C, ³¹P, ⁷Li NMR spectroscopy, IR spectroscopy, elementary analysis, mass spectra, and 2, 3 and 4 additionally by means of X-ray diffraction analysis. 2 crystallizes in the space group P1 with 2 formula units in the elementary cell; a = 10.137(9), b = 15.295(12), c = 15.897(14) Å; α = 101.82(7), β = 91.65(7), γ = 98.99(7)°; 3 crystallizes in the space group P2_t/n with 4 molecules in the elementary unit; a = 11.914(6), b = 15.217(10), c = 14.534(10) Å; α = 90, β = 103.56(5), γ = 90°. 4 : space group P1 with 2 molecules in the elementary unit; a = 8.844(4), b = 12.291(6), c = 14.411(7) Å, α = 66.55(2), β = 89.27(2), γ = 71.44(2)°.     

Mono- und Di-t-butylcyclopentadienyl-Carbonyl-Komplexe des Eisens und Molybdäns. Die Kristallstruktur von [Cp″Mo(Co)2]2 (Cp″ = n5-C5H3t-Bu2-1,3)

Mono- and Di-t-Butylcyclopentadienyl Carbonyl Complexes of Iron and Molybdenum — Crystal Structure of [Cp″Mo(CO)₂]₂ (Cp″ = n⁵-C₅H₃-t-Bu₂-1,3) Cothermolysis of M(CO)_m (M = Fe, m = 5; M = Mo, m = 6) with t-Bu-substituted cyclopentadienyls constitutes a simple synthesis of complexes of the type [Cp*M(CO)_n]₂ (CP* = n⁵-C₅H₃ (t-Bu), R, R = H, t-Bu; M = Fe, Mo; n = 2, 3). Each synthesis has an optimal temperature. The yield of Fe complexes decreases at temperatures above 130°C because of decomposition of the product. Optimal yields of [Cp*Mo(CO)₃]₂ are obtained at 130–140°C, whereas at 160°C complexes of the type [Cp*Mo(CO)₂]₂ with formal Mo? Mo triple bonds are obtained. The structure of the complexes is discussed on the basis of ¹H-, ¹³C-NMR, IR, and mass spectrometry. The structure of [Cp″Mo(CO)₂]₂ (Cp″ = n⁵-C₅H₃t-Bu₂-1,3) was determined by X-ray crystallography at ?95°C. It crystallises in the space group Pbca, with cell constants a = 1808.6(6), b = 1308.5(4), c = 2507.9(9) pm, Z = 8, R = 0.031 for 3794 reflections. The Mo? Mo bond length of 253.3 pm is very long for a formal triple bond. The Cp″? Mo? Mo? Cp″ axis is non-linear.     

Polysulfonylamine. LXIX. Neuartige Pniktogendisulfonylamide: Synthese von Bismutdimesylamiden und Kristallstrukturen des zwölfgliedrigen Cyclodimers [Ph2BiN(SO2Me)2]2 und des ionischen Komplexes [H(OAsPh3)2]⊕(MeSO2)2N⊖

Polysulfonyl Amines. LXIX. Novel Pnictogen Disulfonylamides: Synthesis of Bismuth Dimesylamides and Crystal Structures of the Twelve-Membered Cyclodimer [Ph₂BiN(SO₂Me)₂]₂ and of the Ionic Complex [H(OAsPh₃)₂]^⊕(MeSO₂)₂N^? The novel bismuth(III or V) disulfonylamides Ph₂BiN(SO₂Me)₂ ( 1 ), PhBi[N(SO₂Me)₂]₂ ( 2 ), PhBi[N(SO₂Me)₂]Br ( 3 ), Bi[N(SO₂Me)₂]₂Cl ( 4 ), Bi[N(SO₂Me)₂]Cl₂ · 12-crown-4 ( 5 ) and Ph₃Bi[N(SO₂Me)₂]Cl ( 6 ) were obtained by acidolysis of Ph₃Bi with HN(SO₂Me)₂ (→ 1 ), by metathesis of AgN(SO₂Me)₂ with Ph₂BiCl (→ 1 ) or PhBiBr₂ (→ 2, 3 ), by condensation of BiCl₃ with Me₃SiN(SO₂Me)₂ (→ 4 ; in presence of 12-crown-4: → 5 ), or by oxidative addition of ClN(SO₂Me)₂ to Ph₃Bi (→ 6 ). Independently of the molar ratio employed, triphenylarsane oxide and dimesylamine form the crystalline 2/1 complex [H(OAsPh₃)₂]^⊕(MeSO₂)₂N^? ( 7 ). The crystal packing of 7 (monoclinic, space group C2/c) consists of discrete cations displaying crystallographic C_i symmetry and a strong O …? H …? O hydrogen bond (H atom located on a centre of symmetry, O …? O′ 241.2 pm, As? O …? O′ 120°, As? O 168.3 pm), and chiral anions with crystallographic C₂ symmetry (N? S 157.3 pm, S? N? S 122,9°). In the solid state, the bismuth(III) compound 1 (triclinic, space group P1 ) is a cyclodimer with crystallographic C_i symmetry, in which two Ph₂Bi^⊕ cations are connected through two (α-O, ω-O)-donating dimesylamide ligands to form a roughly twelve-membered [BiOSNSO]₂ ring (Bi? O 239.7 and 246.6, O? S 148.0 and 145.4, S? N 157.7 and 159.2 pm, Bi? O? S 126.6 and 127.5°). The bismuth atom adopts a pseudo-trigonal-bipyramidal geometry (O? Bi? O 165.4, C? Bi? C 93.0, O? Bi? C 83.8 to 86.5°). The essentially similar conformations of the discrete anion in 7 and of the bidentate bridging ligand in 1 are discussed in detail.     

Polysulfonylamine. LXXXIV [1]. Zur Isotypie in den Dimesylamid-Komplexreihen [M(H2O)4{(CH3SO2)2N}2] (MMg,Ca, Ni,Cu, Zn,Cd) und [M(py)4{(CH3SO2)2N}2] (MNi,Cu, Zn,Cd)

Polysulfonylamines. LXXXIV. Isotypic Structures in the Dimesylamide Complex Series [M(H₂O)₄{(CH₃SO₂)₂N}₂] (M?Mg, Ca, Ni, Cu, Zn, Cd) and [M(py)₄{(CH₃SO₂)₂N}₂] (M?Ni, Cu, Zn, Cd) The crystal structures of the trans-octahedral complexes [M(H₂O)₄{(CH₃SO₂)₂N}₂] (M?Ca, Cd), in which the dimesylamide anion acts as a monodentate O-ligand and a tetrafunctional hydrogen bond acceptor, were determined by low-temperature X-ray diffraction. Both belong to an isotypic series (triclinic, space group P1 , Z = 1) that had previously been characterized for M?Mg, Ni, Cu and Zn (Z. Anorg. Allg. Chem. 1996 , 622, 1065). In this structure there exists an extended network of strong hydrogen bonds which is probably the underlying reason why the structure type surprisingly persists across the whole series. To support this explanation by indirect evidence from comparison with suitable structures devoid of strong hydrogen bonding, the analogous trans-octahedral complexes [M(py)₄{(CH₃SO₂)₂N}₂] (M?Mn, Co, Ni, Cu, Zn, Cd) were prepared by treating M[(CH₃SO₂)₂N]₂ with pyridine, and the crystal structures of the Ni, Cu, Zn and Cd compounds were studied by low-temperature X-ray crystallography. As anticipated, the four pyridine complexes do not form an isotypic series but instead two isotypic pairs consisting of the Ni and Zn compounds (monoclinic, space group P2₁/n, Z =2) and of the Cu and Cd complexes (triclinic, space group P1, Z = 1). All molecules of the aqua and the pyridine complexes display crystallographic centrosymmetry. In the hydrates, the mean M? OH₂ and the M? O(anion) distances are 232.6 and 232.7 pm for M ? Ca, 225.5 and 230.3 pm für M ? Cd. The mean M? N and the M? O(anion) bond lengths of the pyridine species amount to 211.8 and 213.1 pm for M ? Ni, 217.0 and 218.5 pm for M ? Zn, 232.8 and 234.4 pm for M ? Cd; the corresponding values for the severely Jahn-Teller distorted Cu complex are 203.6 and 254.5 pm. In the crystals of the pyridine complexes, each methyl group is connected through a weak C? H…?O bond to a sulfonyl oxygen atom of an adjacent molecule.