Claas Sudbrake  Bodo Müller  Heinrich Vahrenkamp 《欧洲无机化学杂志》1999,1999(11):2009-2012

Hexakis(methanol) and hexakis(ethanol) complexes of zinc were prepared under strictly anhydrous conditions and crystallized as perchlorate or hexafluorosilicate salts in space groups of high symmetry. All their OH functions are engaged in hydrogen-bonded cation–anion networks. Their Zn–O distances correspond to those in [Zn(H₂O)₆]²⁺. Their water sensitivity can be explained by a gain in entropy and by a gain in polar interactions upon replacement of alcohol by water ligands.  相似文献   

    

Wolfgang Beck  Thomas M. Klapötke  Jörg Knizek  Heinrich Nöth  Thomas Schütt 《欧洲无机化学杂志》1999,1999(3):523-526

Palladium(II) azide (1) was synthesized by reaction of palladium nitrate and sodium azide. 1 was characterized by AAS, IR, and ¹⁴N-NMR spectroscopy. Bis(azido)bis(pyridine)palladium(II) ( 2 ) and tetramminepalladium tetraazidopalladate(II) ( 3 ) were synthesized by a high-yield reaction. Both were characterized by X-ray structural analysis, IR, Raman, and NMR spectroscopy.  相似文献   

    

Tassilo Habereder  Anton Hammerl  Gerhard Holl  Thomas M. Klapötke  Jörg Knizek  Heinrich Nöth 《欧洲无机化学杂志》1999,1999(5):849-852

tert-Butylhydrazinium azide [tBuNH₂NH₂]⁺[N₃]⁻ ( 1 ) was prepared in a high yield reaction from tert-butylhydrazine and HN₃. N,N,N-Trimethylhydrazinium azide [NH₂N(CH₃)₃]⁺[N₃]⁻ ( 2 ) was prepared from the reaction of silver azide with N,N,N-trimethylhydraziniumiodide. Both were characterized by X-ray structural analysis, IR, Raman, and multinuclear (¹H, ¹³C, ¹⁴N) NMR spectroscopy.  相似文献   

    

Heinrich Nöth  Wolfgang Beck  Klaus Burger 《欧洲无机化学杂志》1998,1998(1):93-99

The molecular structures of nine transition metal tetrazolethiolates have been determined by X-ray structure determinations. The ligand is invariably coordinated through its sulfur atom to the metal center [M = Pd^II, Cu^I, Ag^I, Au^I, Au^III, and Hg]. The M−S−C bond angles vary considerably, but this cannot be correlated with variations in the C−S bond lengths. Intermolecular association occurs for Ph₃PAu(SCN₄Me) via Au−S contacts, leading to dimeric strands in the solid state. The copper compound (Ph₃P)₃Cu₄(SCN₄Me)₄ ( 5 ), possesses a rather asymmetric structure: one Cu atom is tricoordinated by 3 sulfur atoms, the other three are tetracoordinated by P and N as well as by S atoms.  相似文献   

    

Karl Weis  Michael Rombach  Michael Ruf  Heinrich Vahrenkamp 《欧洲无机化学杂志》1998,1998(2):263-270

Five different (pyrazolylborate)zinc hydroxide complexes Tp*Zn−OH ( 1 ) were used as hydrolytic reagents towards esters of various acids of phosphorus. Trimethyl phosphate and trimethyl phosphite could not be cleaved. Dimethyl and diphenyl phosphite yielded Tp^tBu,MeZn−OPHO(OR) ( 2 , 3 ). Triphenyl phosphate reacted slowly producing moderate yields of Tp*Zn−OPO(OPh)₂ ( 4 ). Tris(p-nitrophenyl) phosphate was cleaved rapidly, forming Tp*Zn−OPO(OC₆H₄NO₂)₂ ( 5 ) and Tp*Zn−OC₆H₄NO₂ ( 6 ). Alkylbis(p-nitrophenyl) phosphates showed intermediate reactivity, losing p-nitrophenolate upon hydrolysis and producing Tp*Zn−OPO(OR)(OC₆H₄NO₂) ( 7 , 8 ). When phosphorus acid diesters were employed, condensation between the Zn−OH and P−OH functions occurred. This proved to be the convenient way of preparing the organophosphate complexes Tp*Zn−OPO(Ph)₂ ( 9 ), Tp*Zn−OPO(OPh)₂ ( 4 ), and Tp*Zn−OPO(OC₆H₄NO₂)₂ ( 5 ). Six structure determinations showed the structural variability of the resulting complexes.  相似文献   

    

Heinrich Lang  Marion Leschke 《Heteroatom Chemistry》2002,13(6):521-533

The reaction of cis‐(2,2′‐bipyridine) Pt(CCPh)₂ cis‐(4,4′‐dimethyl‐2,2′‐bipyridine) Pt‐(CCPh)₂ and trans‐(Ph₃P)₂Pt(CCPh)₂ towards different group 11 transition‐metal salts [M′X] (M′ = Cu, Ag; X = inorganic ligand) to give heterobimetallic or linear oligomeric and polymeric transition metal complexes is described. Different coordination modes for M′, PhCC, PPh₃, and X were found in these species. The structural aspects as well as the preference for one coordination mode over another is discussed. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:521–533, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10097  相似文献   

    

György Túrós  Antal Csámpai  Tamás Lovász  Attila Györfi  Heinrich Wamhoff  Pál Sohár 《European journal of organic chemistry》2002,2002(22):3801-3806

The ferrocene-containing N-BOC-protected 1-allyl-2-(allylamino)imidazolones 5 and 13 were transformed into mono- and bis(2,5,8,9-tetrahydro-3H-imidazo[1,2-a][1,3]diazepin-3-ones) 7 and 15 in a ring-closing metathesis (RCM) reaction using Grubbs’ catalyst [RuCl₂(CHPh){P(cyclo-C₆H₁₁)₃}₂]. The structures of the novel compounds were identified by IR and multinuclear NMR spectroscopy. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)  相似文献   

    

Nils Wiberg  Thomas Blank  Heinrich Nöth  Max Suter  Markus Warchhold 《欧洲无机化学杂志》2002,2002(4):929-934

Thermolysis of the trigallanyl radical R*₄Ga₃^· in heptane at 60 °C leads to the dark blue octagallane R*₆Ga₈ (R* = supersilyl SitBu₃), as well as the digallanyl radical R*₃Ga₂^· and the tetrahedro-tetragallane R*₄Ga₄. In addition, supersilyl radicals R* ^· are formed which stabilize themselves either by dimerization or by addition of hydrogen atoms. R*₆Ga₈ can be reduced in THF with NaC₁₀H₈ to the dark-red octagallanediide Na₂Ga₈R*₆·2THF. According to an X-ray structure analysis of R*₆Ga₈ and R*₆Ga₈²⁻ one finds that the Ga atoms of four R*Ga moieties, together with two “naked” Ga atoms, occupy the corners of a distorted octahedron; the “naked” Ga atoms themselves are located, along with Ga atoms of two further R*Ga moieties, at the corners of a distorted square. The reduction of R*₆Ga₈ leads only to a negligible shortening of the Ga−Ga distances from 2.64 to 2.61 Å (mean values) in R*₆Ga₈²⁻. Both the octagallanes possess Ga₈ frameworks previously unknown for group 13 clusters. They are isomeric to the recently described Ga₈ framework of the octagallane Tsi₆Ga₈ [Tsi = trisyl C(SiMe₃)₃]. Hence, not only boron but also the heavier group 13 atoms form isomeric clusters.  相似文献   

    

Tassilo Habereder  Heinrich Nth 《无机化学与普通化学杂志》2001,627(4):789-796

New stannylboranes were prepared from tetramethylpiperidino dichloroborane or B‐bromo‐pentamethylborazine with lithium triorganylstannides LiSnR₃. Only double stannylation was possible with tmpBCl₂ and LiSnMe₃, while tmpBCl(SnPh₃) was obtained by employing LiSnPh₃. This chloride reacted with LiGePh₃ to the stannyl germyl borane tmpB(GePh₃)(SnPh₃). On the other hand, PhMeNBCl₂ and an excess of LiSnMe₃ gave the borate Li[B(NMePh)(SnMe₃)₃], which was isolated as a solvate with 4 molecules of THF. The compound is present in the solid state as a solvent separated ion pair. The borate Li(H₃BSnMe₃) · 2 THF is dimeric in the solid state. Dimerization occurs via two single Li–H–B bridges and a Li–H(B)–Li bridge. The B–Sn bonds in the borates are practically of the same lengths as those in the boranes. In solution all BH bonds of this trihydridoborate are equivalent.  相似文献   

    

Tassilo Habereder  Heinrich Nth 《无机化学与普通化学杂志》2001,627(5):1003-1012

The B‐(triphenylgermyl)borazines 4 a and 4 b , the 1,2‐bis(dimethylamino)‐1,2‐bis(triphenylgermyl)‐diborane(4), 5 , and the (2,2,6,6‐tetramethylpiperidino)(triphenylgermyl)‐boranes 6 and 7 were prepared by allowing LiGePh₃ to react with the corresponding B‐bromoborazines and aminochloroboranes, respectively. BH₃ dissolved in thf readily adds to LiGePh₃ generating Li(H₃BGePh₃), 8 a , in thf solution. Addition of N‐bases to the solution of 8 a produced (tmen · thf)Li(H₃BGePh₃), 8 b , and dimeric (py)₂Li(H₃BGePh₃), 8 c . The borazine ring in 4 b is distorted into a boat shape. In 5 the NBGe planes are twisted against each other by 85°. Comparison with analogous (triphenylstannyl)boranes points to a more pronounced steric effect of the Ph₃Ge group over the Ph₃Sn group due to the shorter B–Ge bond. A fairly short B–Ge bond is found for the (triphenylgermyl)trihydroborates. The molecular structure of (Et₂O)₃LiGePh₃ shows compressed C–Ge–C bond angles. Its molecular parameters fit well into the series L_nLiEPh₃ (E = Si, Sn, Pb).  相似文献