Umsetzung von C(NMe2)4 mit Ni(CO)4 – Synthesen und Strukturen von [C(NMe2)3][(CO)3NiC(O)NMe2], [C(NMe2)3]2[Ni5(CO)12] und [C(NMe2)3]3[Ni6(CO)12][O2CNMe2]

Reaction of C(NMe₂)₄ with Ni(CO)₄ – Syntheses and Structures of [C(NMe₂)₃][(CO)₃NiC(O)NMe₂], [C(NMe₂)₃]₂[Ni₅(CO)₁₂], and [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] The reaction of C(NMe₂)₄ with Ni(CO)₄ in THF produces the carbamoyl complex [C(NMe₂)₃][(CO)₃NiC(O)NMe₂] ( 1 ); side products are the purple cluster compound [C(NMe₂)₃]₂[Ni₅(CO)₁₂] · THF ( 2 · THF) and the red cocristallization product [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] ( 3 ). All compounds were studied by X‐ray diffraction analyses. The cations of 3 are all disordered but not those of 1 and 2 . The unit cell of 1 contains two crystallographically independent anions (I and II) which differ in the dihedral angle between the plane of the carbamoyl ligand and the plane defined by the atoms C_Carbamoyl–Ni–CO amounting 0° in the anion I and 18° in the anion II.     

Darstellung,Kristallstruktur und quantenchemische Berechnung von [C(NMe2)3]2[(CO)4FeInCl3]

Preparation, Structure, and Quantum Chemical Calculation of [C(NMe₂)₃]₂[(CO)₄FeInCl₃] The title compound ( 1 ) has been obtained as colorless crystals by reacting InCl₃ with [C(NMe₂)₃][(CO)₄FeC(O)NMe₂] in THF solution. The crystal structure determination (monoclinic, C2/c) shows the presence of separate ions with one disordered and one non disordered cation. In the dianion the CO groups of the trigonal bipyramidal coordinated iron atom and the Cl atoms of the tetrahedral coordinated indium atom form a staggered conformation with a relatively short In–Fe bond distance of 252 pm. Quantum Chemical DFT calculations of [CO)₄FeInCl₃]^2– show that the Fe–In bond has a strong ionic character and that it should be considered as an adduct of [Fe(CO)₄]^2– and InCl₃.     

Syntheses,Crystal Structures,and Properties of the Isotypic Pair [Cr(H2O)6]2[B12H12]3·15H2O and [In(H2O)6]2[B12H12]3·15H2O

Single crystals of [Cr(H₂O)₆]₂[B₁₂H₁₂]₃ · 15H₂O and [In(H₂O)₆]₂[B₁₂H₁₂]₃ · 15H₂O were obtained by reactions of aqueous solutions of the acid (H₃O)₂[B₁₂H₁₂] with chromium(III) hydroxide and indium metal shot, respectively. The title compounds crystallize isotypically in the trigonal system with space group R$\bar{3}$ c (a = 1157.62(3), c = 6730.48(9) pm for the chromium, a = 1171.71(3), c = 6740.04(9) pm for the indium compound, Z = 6). The arrangement of the quasi‐icosahedral [B₁₂H₁₂]^2– dianions can be considered as stacking of two times nine layers with the sequence …ABCCABBCA… and the metal trications arrange in a cubic closest packed …abc… stacking sequence. The metal trications are octahedrally coordinated by six water molecules of hydration, while another fifteen H₂O molecules fill up the structures as zeolitic crystal water or second‐sphere hydrating species. Between these free and the metal‐bonded water molecules, bridging hydrogen bonds are found. Furthermore, there is also evidence of hydrogen bonding between the anionic [B₁₂H₁₂]^2– clusters and the free zeolitic water molecules according to B–H^δ– ··· ^δ+H–O interactions. Vibrational spectroscopy studies prove the presence of these hydrogen bonds and also show slight distortions of the dodecahydro‐closo‐dodecaborate anions from their ideal icosahedral symmetry (I_h). Thermal decomposition studies for the example of [Cr(H₂O)₆]₂[B₁₂H₁₂]₃ · 15H₂O gave no hints for just a simple multi‐stepwise dehydration process.     

Darstellung und Kristallstrukturen von [P(C6H5)4][1-(NH3)B10H9] und Cs[(NH3)B12H11] · 2CH3OH

Synthesis and Crystal Structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH The reduction of [1-(NO₂)B₁₀H₉]^2? with aluminum in alkaline solution yields [1-(NH₃)B₁₀H₉]^? and by treatment of [B₁₂H₁₂]^2? with hydroxylamine-O-sulfonic acid [(NH₃)B₁₂H₁₁]^? is formed. The crystal structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] (triclinic, space group P1 , a = 7.491(2), b = 13.341(2), c = 14.235(1) Å, α = 68.127(9), β = 81.85(2), γ = 86.860(3)°, Z = 2) and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH (monoclinic, space group P2₁/n, a = 14.570(2), b = 7.796(1), c = 15.076(2) Å, β = 111.801(8)°, Z = 4) reveal for both compounds the bonding of an ammine substituent to the cluster anion.     

Synthesis and Structure of 1,2-Diphenyl-1,2-disila-closo-dodecaborane(12), Reaction with [Zr(NMe2)4] and [Ta(NMe2)5]

Diphenyl-o-silaborane ( 1 ) can be obtained by sublimation as colourless crystalline material in a yield of 23%. The disilaborane 1 was characterized by NMR spectroscopy, mass spectrometry and X-ray structure analysis. The neutral closo cluster 1 reacts with [Zr(NMe₂)₄] or [Ta(NMe₂)₅] to give the dimethylamide adduct [(Me₂N)(PhSi)₂B₁₀H₁₀]^– of the disilaborane.     

羟化三苯基锡和(双三苄基锡)氧化物的合成及晶体结构研究

在乙醇钠存在下三苯基氯化锡或三苄基氯化锡水解得羟化三苯基锡 (1)或 (双三苄基锡 )氧化物 (2 )。其结构经元素分析、IR和1HNMR表征 ,X 射线单晶衍射测定了其晶体结构。 1为正交晶系 ,空间群P2 1/n,a =0 .830 0 0 (19)nm ,b =1.0 36 5 (2 )nm ,c =1.80 2 6 (4 )nm ,β =95 .4 72 (7)°,Z =4 ,V =1.5 5 0 7(6 )nm3 ,Dc=1.5 72g·cm -3 ,μ=1.6 4 0mm -1,F(0 0 0 ) =72 8,R1=0 .0 30 9,WR2 =0 .0 70 6 ,中心锡原子为五配位的三角双锥构型 ,且通过配位氧原子连成无限链状。 2为正交菱面体晶系 ,空间群R3 ,a =b =c =0 .96 36 (3)nm ,α =β =γ =84 .0 85 (3)° ,Z =1,V =0 .8812 (4 )nm3 ,Dc=1.5 0 8g·cm -3 ,μ =1.4 4 8mm -1,F(0 0 0 ) =4 0 2 ,R1=0 .0 36 0 ,WR2 =0 .0 5 4 2 ,由两个中心锡原子组成一个结构单元的四配位线性聚合体。     

Triple linking of the decaboranyl cluster. Structure of [(SMe2)2B10H10(B10H13)2] as determined by synchrotron X-ray diffraction analysis

In an attempt to find generic routes to multiple inter-cluster sigma-linking, mild thermolysis of [6,9-(SMe2)2-arachno-B10H12] 1 in inert hydrocarbon solution gives the tridecaboranyl species [6,9-(SMe2)2-arachno-B10H(10)-1,5-(6'-nido-B10H13)2] 3 (23%).     

Crystal and molecular structure of 6,9-bis(trimethylamino)-nido-decaborane(12) B10H12[N(CH3)3]2

Institute for Inorganic Chemistry, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 4, pp. 116–121, July–August, 1989.     

Thermal transformations of B10H12(NH3)2, B10H12(C5H5N)2, and B10H12(C9H7N)2

Conclusions For B₁₀H₁₂L₂, where L=NH₃, C₅H₅N, or C₉H₇N, features of thermal transformations in the range 25–850°C and the composition of the pyrolysis products are determined. The latter are x-ray amorphous phases, containing nitride, carbide, boron carbide, boron, and carbon.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2481–2484, November, 1988.     

Preparation and Structure of [Me3N(CF3)2BCCB(CF3)2NMe3]

Bis‐trimethylamine‐ethynyl‐di‐bis(trifluoromethyl)borane [Me₃N(CF₃)₂BCCB(CF₃)₂NMe₃] ( 1 ) has been prepared from trimethylamine‐ethynyl‐bis(trifluoromethyl)borane, [HCCB(CF₃)₂NMe₃], and dimethylamino‐bis(trifluoromethyl)borane, (CF₃)₂BNMe₂. The structure of 1 has been determined by x‐ray crystallography. In the solid state the molecule possesses crystallographic C_i symmetry. The acetylenic attachment to the boron atom is characterized by a short B–C bond length of 1.565(4) Å and an essentially linear B–C–C′ bond angle of 178.1(4)°.     

Synthesis,Characterization, and Crystal Structures of [N(CH3)4]2[B12H12] and [N(CH3)4]2[B12H12] · CH3CN

Bis(tetramethylammonium) dodecahydrododecaborate, [(CH₃)₄N]₂[B₁₂H₁₂], and bis(tetramethylammonium) dodecahydrododecaborate acetonitrile, [(CH₃)₄N]₂[B₁₂H₁₂] · CH₃CN, were synthesized and characterized via Infrared, ¹H and ¹¹B NMR spectroscopy. [(CH₃)₄N]₂[B₁₂H₁₂] crystallizes isopunctual to the alkali metal dodecaborates. The crystal structure of [(CH₃)₄N]₂[B₁₂H₁₂] · CH₃CN was determined from single crystal data and refined in the orthorhombic crystal system (Pcmn, no. 62, a = 898.68(8), b = 1312.85(9) c = 1994.5(1) pm, R(|F| , 4σ) = 5.9%, wR(F²) = 18.3%). Here, the geometry of the dodecaborate anion is that of an almost ideal icosahedron, less distorted than most other dodecaborates known. By low‐temperature Guinier‐Simon diffractometry phase transitions were detected for [(CH₃)₄N]₂[B₁₂H₁₂] and [(CH₃)₄N]₂[B₁₂H₁₂] · CH₃CN at –70 and –15 °C, respectively.