Strukturen und intramolekulare Bewegungen spezieller polycyclischer Germanium(II)-amide

Structures and Intramolecular Motions of Special Polycyclic Germanium(II) Amides Compounds of the general formula MeSi(NtBu)₃Ge₂X (X = Cl ( 1 ), N(SiMe₃)₂ ( 2 ), P(C₆H₅)₂ ( 3 )) have been synthesized and characterized by X-ray structure analyses and multinuclear NMR-spectroscopy. The temperature dependent NMR investigations of 2 in solution show bond fluctuations concerning the metal-nitrogen bonds and ElMe₃ (El = C, Si) rotations. Some of these intramolecular motions also occur in the solid state as detected by means of temperature dependent ¹³C CP/MAS NMR spectroscopy. The special nature of these NMR spectroscopically detected movements in solution are compared with the results of the X-ray structure analyses. A model of the dynamical behaviour of 2 in solution suggests a quasi circular movement of the two germanium atoms within the molecular cage. After the phase transition from solution to the solid state at ambient temperature this special metal fluctuation is stopped. In the solid state the rotations of the SiMe₃ groups in 2 are only hindered at low temperatures.     

Darstellung und Strukturen von Chlorostannaten(II). I. Neue Trichlorostannate(II) einwertiger Kationen

Preparation and Structures of Chlorostannates(II). I. Some New Trichlorostannates of Monovalent Cations KSnCl₃ · 1/2 CH₃CN is obtained by recrystallizing KSnC1₃ from acetonitrile. The compound forms monoclinic crystals, space group P2₁/c (a = 4.525(6), b = 20.34(2), c = 8.061(7) Å, β = 90.93(9)°). [Cu(CH₃CN)₃]SnCl₃ is prepared by reacting equimolar amounts of CuCl and SnCl₂ in acetonitrile. It crystallizes in the monoclinic space group P2₁/n (a = 7.984(9), b = 20.77(2), c = 8.34(2) Å, β = 101.6(1)°). Whereas in KSnCl₃ · l/2 CH₃CN there is a three dimensional connection of the SnCl₃^? ions, in which the potassium ions participate, the trichlorostannate ions in [Cu(CH₃CN)₃]SnCl₃ are linked to one dimensional chains by Sn…?Cl bridges.     

Die Kristallstruktur von Pentacarbonyl(tri-tert-butylphosphin)wolfram und Tricarbonyl(tri-tert-butylphosphin)nickel

The Crystal Structure of Pentacarbonyl(tri-tert-butylphosphine)tungsten and of Tricarbonyl(tri-tert-butylphosphine)nickel The crystal structures of pentacarbonyl(tri-tert-butylphosphine)tungsten and of tricarbonyl(tri-tert-butylphosphine)nickel have been determined from single crystal X-ray data. Both complexes crystallize with four molecules in an unit cell of symmetry P2₁/n for the tungsten complex and P2₁/a for the nickel compound. Parameters: (CO)₅WP[C(CH₃)₃]₃: monoclinic system, a = 14.514(12), b = 16.439(6), c = 8,957(2), β = 102.16(5)°; (CO)₃NiP[C(CH₃)₃]₃ monoclinic system, a = 14.708(10), b = 15.594(10), c = 8.327(9), β = 105.02(5)°.     

Uber die Reaktionen der Hexacarbonyle der VI. Nebengruppe mit Zinn (II)- und Germanium (II)-halogeniden

On Reactions of Subgroup. VI. Hexacarbonyls with Tin(II) and Germanium (II) Halides The neutral complexes M(CO)₅SnX₂ and M(CO)₅GeCl₂ (M = Cr, Mo, W; X = Cl, Br, J) have been prepared by a photochemical reaction between M(CO)₆ and SnX₂, or CsGeCl₃ in THF. The reaction of these compounds with [N(CH₃)₄]X (X = Cl, Br, J) in THF was found to lead to a series of anions [M(CO)₅SnX₃]^? or [M(CO)₅GeCl₃]^? (M = Cr, Mo, W; X = Cl, Br, J), some of which have previously been prepared. The physical properties and IR-spectra of the above compounds are discussed.     

Tris(triphenylphosphan)nickel(0)-Komplexe mit Nitril-Liganden

Tris(triphenylphosphane)nickel(0) Complexes with Nitrile Ligands . Synthesis, properties and reaction behaviour of (Ph₃P)₃Ni(η¹-NCR) (R = PhCH₂, 2-MeC₆H₄, Me₃Si) complexes as well as the X-ray structure of (Ph₃P)₃Ni(η¹-NCSiMe₃) are described. With NC(CH₂)_nBr (n = 1, 2) instead of the analogous nitrile complexes (Ph₃P)₂NiBr₂ and CH₃CN or C₂H₅CN respectively are formed.     

Zur Oxydation von Nickel(0)-Komplexen mit Halogenverbindungen des Kobalt(II), Kupfer(II) und Zink(II)

Oxidation of Nickel(0) Complexes by Halogen Compounds of Cobalt(II), Copper(II), and Zine(II) In aceton as a solvent Ni(PPh₃)₄ is oxidized by; cobalt(II) complexes of the type (Ph₃P)₂CoX₂ to nickel(I) compounds. In the case of X = Cl (Ph₃P)₃NiCl and (Ph₃P)₃CoCl separately crystallize, while for X = Br the lattice compound CoNi(PPh₃)₆Br₂ and for X = I CoNi(PPh₃)₅I₂ are formed. CuBr₂ and Ni(PPh₃)₄ react to (Ph₃P)₂NiBr and (Ph₃P)_nCuBr. With (Ph₃P)₂ZnCl₂ also (Ph₃P)₃NiCl is formed But in this case the oxidant is hydrogen chloride originating from hydrolysis. The magnetic moments of the new compounds were measured and their vis and fir spectra compared with those of the simple compounds (Ph₃P)_nNiX (n = 2, 3) and (Ph₃P)₃CoX. The M–X stretching frequencies are assigned. The cobalt (I) complexes (Ph₃P)₃CoCl have identical (distorted tetrahedral) structures, but most probably the nickel (I) complexes have not.     

Neue anorganische Ringsysteme. XXIII. Hetero-Spirosilazane mit Germanium,Zinn und Zirkonium als spiralem Zentrum

Novel Inorganic Ring Systems. XXIII. Hetero Spirosilazanes with Ge, Sn, and Zr in the Spiral Center Symmetrical SiN-spiro[4,4]-nonanes of the skeleton composition Si₅N₄, Si₄N₄Ge, Si₄N₄Sn and Si₄N₄Zr and with the hetero atoms in the spiral center could be prepared for the first time in shape of their permethylated derivatives A 1 to E 1 via equations (1/2) as well as (3/4/5/6) respectively. They were confirmed in their structure by elemental analysis, proton n.m.r., mass, i.r., and Raman spectra.     

Schwefeldioxid als Ligand und Synthon. XIII. Reaktionen von Isocyanid-tris(triphenylphosphan)nickel(0)-Komplexen mit Schwefeldioxid und N-p-Tolylsulfinylamin

Sulfur Dioxide as Ligand and Synthon. XIII. Reactions of Isocyanide-tris(triphenylphosphane)nickel(0) Complexes with Sulfur Dioxide and N-p-tolylsulfinylamine Reactions of the isocyanide-tris(triphenylphosphane)-nickel(0) complexes [(RNC)Ni(PPh₃)₃] (R = ^tBu, Cy, PhCH₂, p-TosCH₂) with SO₂ and p-TolNSO are described. The sulfur dioxide and N-p-tolylsulfinylamine complexes obtained by PPh₃ ligand substitution have been characterized by means of i.r. and ³¹P n.m.r. spectra. The X-ray crystal structure of [(Ph₃P)₂(CyNC)Ni(SO₂)] · 0.5 PhMe and (Ph₃P)(^tBuNC)Ni(η²-p-TolNSO) have been determined.     

Die Extraktion von Zinn(IV) und Germanium(IV) als Jodide mit Benzol

Ohne Zusammenfassung     

Komplexe des m-Methylbenzamidoxims mit Co(II) und Ni(II)

The complex formation of Co²⁺ and Ni²⁺ with m-methyl benzamide oxime was studied spectrophotometrically in 60% methanol. The complexes [Co(mMB)₂] and [Ni(mMB)₂] appear in alkaline solution. The formation constants are lgK=4.15±±0.04 for [Co(mMB)₂] and lgK=4.08±0.04 for [Ni(mMB)₂] at 25°. The decadic molar extinction coefficients are ε=5000 for [Co(mMB)₂] and ε=560 for [Ni(mMB)₂], resp.     

Neue Rheniumkomplexe mit Trichalkogenido- und Tetrachalkogenido-Chelatliganden

New Rhenium Complexes Containing Trichalcogenido and Tetrachalcogenido Chelate Ligands The reactions of Cp*ReCl₄ with polychalcogenide salts such as Na₂S₄ or (NEt₄)₂Se₆ lead initially to the violet trichalcogenido chelate complexes Cp*ReCl₂(E₃) (E = S ( 3a ), Se ( 3b )) which, due to their functional chloro ligands, can be used as intermediates for further reactions. Upon hydrolysis in moist solvents or aminolysis with tert. butylamine 3a, b are converted into the tetrachalcogenido chelate complexes Cp*Re(O)(E₄) (E = S ( 4a ), Se ( 4b )) and Cp*Re(N^tBu)(E₄) (E = S ( 5a ), Se ( 5b )), respectively. X-Ray structure analyses were carried out for the three mononuclear cyclo-oligoselenido compounds 3b–5b . It appears that the size of the Se^2?_n chelate ring (n = 3 or 4) essentially depends on steric factors within the coordination sphere of rhenium.     

Sigma-borane coordinated to nickel(0) and some related nickel(II) trihydride complexes

The reactions of the complexes [(dcype)NiH]2, 1, [(dippe)NiH]2, 2, and [(dtbpe)NiH]2, 3, with a mixture of BEt3 and Super-Hydride (LiHBEt3) afforded sigma-borane nickel(0) compounds of the type [(dcype)Ni(sigma-HBEt2)], 4, [(dippe)Ni(sigma-HBEt2)], 5, [(dtbpe)Ni(sigma-HBEt2)], 6, respectively, with the concomitant formation in each case of [(dcype)2Ni2)(H)3][BEt4], 7, [(dippe)2Ni2(H)3][BEt4], 8 and [(dtbpe)2Ni2(H)3][BEt4], 9, respectively. X-ray crystal structures are reported for 4 and 8.The reaction of BEt3 and LiHBEt3 was also reviewed in detail.