Synthese und Molekülstruktur von Li[(Me2NCH2CH2CH2)4Yb]

Preparation and Structure of Li[(Me₂NCH₂CH₂CH₂)₄Yb] YbCl₃ reacts with dimethylaminopropyl lithium in tetrahydrofuran with formation of Li[(Me₂NCH₂CH₂CH₂)₄Yb]. The X-ray structure determination proves the formation of chelat rings by two of the ligands. The nitrogens of the other two ligands are coordinated to the lithium. The compound crystallizes in the monoclinic space group C2/c with the unit cell parameters a = 27.854(8) Å, b = 9.183(3) Å, c = 20.125(8) Å, β = 96.40° and Z = 8.     

Die Kristallstruktur von Diethylaluminiumhypersilanid, [(C2H5)2Al–Si{Si(CH3)3}3]2

The Crystal Structure of Diethylaluminium Hypersilanide [(C₂H₅)₂Al–Si{Si(CH₃)₃}₃]₂ [Et₂Al–Hsi]₂ (Et = C₂H₅, Hsi = –Si(SiMe₃)₃), prepared from [Et₂AlCl]₂ and equimolar amounts of base‐free Li–Hsi in n‐pentane, crystallizes in the triclinic space group P 1 with two independent dimers per unit cell. One of these molecules is disordered. The dimers consist of planar Al₂C₂‐skeletons with Al–C–Al bridging bonds of 212,9(2) and 221,2(2) pm, respectively, and with intramolecular C–H…Al contacts of 202(2) pm.     

Reaktion von Bis(trimethylsilylamino)dichlorsilan mit Titantetrachlorid ‐ Synthese und Kristallstruktur von [μ‐ClTiCl2N(SiMe3)SiCl2NH2]2

TiCl₄ reacts quantitatively with Cl₂Si(NHSiMe₃)₂ in n‐pentane under evolution of Me₃SiCl yielding [μ‐ClTiCl₂N(SiMe₃)‐SiCl₂NH₂]₂ ( 1 ), which is obtained as a yellow, crystalline solid forming small intergrown needles, that rapidly hydrolyse. The product 1 shows a thermal stability up to 80?C. The molecular structure of 1 has been solved by X‐ray powder diffraction methods and it could be confirmed by single‐crystal X‐ray structure determination at ‐70 ?C. Accordingly, in the solid 1 is a dimer ([μ‐ClTiCl₂N(SiMe₃)SiCl₂NH₂]₂, P2₁/n (no. 14), Z = 2, a = 1504.89(6), b = 1296.33(6), c = 710.90(4) pm, and β = 91.276(2)?).     

Bildung und Molekülstruktur von [{(CH3)3Si}3C(nC3H7)In(μ‐OH)]3

Formation and Structure of [{(CH₃)₃Si}₃C(ⁿC₃H₇)In(μ‐OH)]₃ The title compound has been prepared in low yield by the reaction of [(THF)₂LiC(SiMe₃)₃]₂with humid di(n‐propyl) indium bromide and purified by sublimation at 110–115 °C/10^–3 hPa. This organo indium hydroxo compound forms a trimer via In–OH–In bridges and crystallizes in the triclinic space group P 1 with two trimers and one toluene molecule per unitcell. The In₃O₃ heterocycle has chair‐, the n‐propyl ligand has trans‐conformation, respectively.     

Synthese und Molekülstruktur von [1,3-(Me3Si)2C5H3](Me3SiC5H4)ZrCl2

Synthesis and Molecular Structure of [1,3-(Me₃Si)₂C₅H₃](Me₃SiC₅H₄)ZrCl₂ . The unsymmetrically substituted zirconocene dichloride was prepared by reaction of trimethylsilylcyclopentadienyl lithium and 1,3-bis(trimethylsilyl)cyclopentadienyl lithium with ZrCl₄ · 2 THF. The molecular structure was determined (P2₁/a; a = 1 357.9, b = 1 900.0, c = 1 043.2 pm, β = 105,16°). The Zr? Cl distance are remarkably short.     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.     

Tris(tris(trimethylsilyl)silyl)gallium,Ga{Si(Si(CH3)3)3}3

The title compound has been prepared in good yield by the reaction of gallium trichloride with base‐free hypersilyl lithium (Li–Si(SiMe₃)₃, Me = CH₃) in a 1 : 3 molar ratio. Ga(Si(SiMe₃)₃)₃ is monomeric in solution and in the solid state. The compound has been characterized with NMR, IR and Raman techniques as well as by an X‐ray structure determination (planar GaSi₃‐skeleton, monoclinic space group P2₁/c, Z = 4, d(Ga–Si) = 249,8 ± 0,2 pm).     

Synthese und Molekülstruktur von [{Cp′(μ‐η1 : η5‐C5H3Me)Mo(μ‐AlRH)}2] (Cp′ = C5H4Me,R = iBu,Et)

Synthesis and Molecular Structure of [{Cp′(μ‐η¹ : η⁵‐C₅H₃Me)Mo(μ‐AlRH)}₂] (Cp′ = C₅H₄Me, R = ⁱBu, Et) [Cp′₂MoH₂] reacts with HAlR₂ to give [{Cp′(μ‐η¹ : η⁵‐C₅H₃Me)Mo(μ‐AlRH)}₂] (Cp′ = C₅H₄Me, R = ⁱBu ( 1 ), Et ( 2 )). Crystal structure determinations were carried out on [Cp′₂MoH₂] and 1 . 1 exhibits a direct Mo–Al bond (2.636(2) Å).     

Aktivierung von Schwefelkohlenstoff an Trirutheniumclustern: Synthese und Kristallstruktur von [Ru3(CO)4(μ‐PCy2)2(μ‐Ph2PCH2PPh2)(μ3‐S){μ3‐η2‐CSC(S)S}]

Activation of Carbon Disulfide on Triruthenium Clusters: Synthesis and X‐Ray Crystal Structure Analysis of [Ru₃(CO)₄(μ‐PCy₂)₂(μ‐Ph₂PCH₂PPh₂)(μ₃‐S){μ₃‐η²‐CSC(S)S}] [Ru₃(CO)₄(μ‐H)₃(μ‐PCy₂)₃(μ‐dppm)] ( 2 ) (dppm = Ph₂PCH₂PPh₂) reacts with CS₂ at room temperature and yields the open 50 valence electron cluster [Ru₃(CO)₄(μ‐PCy₂)₂(μ‐dppm)(μ₃‐S){μ₃‐η²‐CSC(S)S}] ( 3 ) containing the unusual μ₃‐η²‐C₂S₃ mercaptocarbyne ligand. Compound 3 was characterized by single crystal X‐ray structure analysis.     

Synthese und Kristallstruktur von [C(NMe2)3]2[(CO)4Fe(μ‐InCl2)2Fe(CO)4]

Synthesis and Crystal Structure of [C(NMe₂)₃]₂[(CO)₄Fe(μ‐InCl₂)₂Fe(CO)₄] Treatment of [C(NMe₂)₃]₂[(CO)₄FeInCl₃] ( 1 ) with hot water produces the dinuclear complex [C(NMe₂)₃]₂[(CO)₄Fe(μ‐InCl₂)₂Fe(CO)₄] ( 2 ) which could be crystallized from dichloromethane/pentane. 2 crystallizes in the monoclinic space group P2₁/n with a = 835.7(1), b = 1187.8(1), c = 1902.7(1) pm, β = 91.877(5)° and Z = 2. The anion contains a four‐membered Fe—In—Fe—In ring with octahedral environment at the iron atom and tetrahedral coordination at the In atom.     

Darstellung,Eigenschaften und Molekülstrukturen von Dimethylmetallalkoxiden und ‐amiden des Aluminiums und Galliums

Preparation, Properties, and Molecular Structures of Dimethylmetal Alkoxides and Amides of Aluminium and Gallium Dimethylaluminium‐ ( 1 ) and Dimethylgallium‐o‐methoxyphenyl‐1‐ethoxide ( 2 ) were obtained by reaction of Me₃Al and Me₃Ga respectively with o‐Methoxyphenyl‐1‐ethanol in n‐pentane. Dimethylaluminium‐ ( 3 ) and dimethylgallium‐o‐methoxyphenyl‐2‐ethylamide ( 4 ) were prepared by treatment of Me₂AlCl and Me₂GaCl respectively with Lithium‐o‐methoxyphenyl‐2‐ethylamide. Trimethylgallium‐o‐methoxyphenylmethylamine‐Adduct ( 5 ) was isolated using reaction of Me₃Ga with the corresponding amine. The compounds were characterised by ¹H‐, ¹³C‐, and ²⁷Al n.m.r. spectroscopy. The molecular structures of 2 and 5 were determined by X‐ray diffraction. Compounds 1 – 4 form brigded dimeric molecules. The bond distances of the central Ga₂O₂ ring in 2 correspond to those of compounds of similar structure.     

Neue viergliedrige GaE‐ und InE‐Ringverbindungen: Synthese und Kristallstruktur von [Et2InE(SiMe3)2]2 und [GaCl(PtBu2Me)E(SiMe3)]2 (E = P,As)

New GaE and InE Four Membered Ring Compounds: Syntheses and Crystal Structures of [Et₂InE(SiMe₃)₂]₂ and [GaCl(P t Bu₂Me)E(SiMe₃)]₂ (E = P, As) Et₃In · PR₃ (R = Et, iPr) reacts with H₂ESiMe₃ under liberation of C₂H₆ and EH₃ to form the cyclic compounds [Et₂InE(SiMe₃)₂]₂ ( 1 a : E = P, 1 b : E = As). 1 consists of a planar four membered In₂E₂ ring in which the indium and phosphorus or arsenic atoms are four coordinated. In contrast, the phosphorus/arsenic atoms in [GaCl(PtBu₂Me)E(SiMe₃)]₂ ( 2 a : E = P, 2 b : E = As) only have the coordination number three. 2 results from the reaction of GaCl₃ · PtBu₂Me with As(SiMe₃)₃ or Li₂PSiMe₃ respectively, and displays a folded four membered Ga₂E₂ ring as central structural motif. 1 and 2 have been characterised by single crystal X‐ray diffraction analysis as well as ¹H and ³¹P{¹H} NMR spectroscopy.     

Bipy,Phen und P(C6H4CH2NMe2‐2)3 in der Synthese kationischer Silber(I)‐Komplexe; die Festkörperstrukturen von [P(C6H4CH2NMe2‐2)3]AgOTf und [Ag(phen)2]OTf

Bipy, Phen, and P(C₆H₄CH₂NMe₂‐2)₃ in the Synthesis of Cationic Silver(I) Complexes; the Solid‐State Structures of [P(C₆H₄CH₂NMe₂‐2)₃]AgOTf and [Ag(phen)₂]OTf The reaction of [P(C₆H₄CH₂NMe₂‐2)₃]AgX ( 1a , X = OTf; 1b , X = OClO₃) with equimolar amounts of L^capL ( 2a , L^capL = 2, 2′‐bipyridine, bipy; 2b , L^capL = 4, 4′‐dimethyl‐2, 2′‐bipyridine, bipy′; 2c , L^capL = 1, 10‐phenanthroline, phen) leads to the formation of the cationic complexes {[P(C₆H₄CH₂NMe₂‐2)₃]Ag(L^capL)}⁺X^— (L^capL = bipy: 3a , X = OTf; 3b , X = ClO₄; L^capL = bipy′: 3c , X = OTf; 3d , X = ClO₄; L^capL = phen: 3e , X = OTf; 3f , X = ClO₄) in which the building blocks L^capL and P(C₆H₄CH₂NMe₂‐2)₃ act as bidentate chelating ligands and are datively‐bound to the silver atom. Spectroscopic studies reveal that on the NMR time‐scale the phosphane group is dynamic with exchanging the respective Me₂NCH₂ built‐in arms. While complex 3e is stable in the solid‐state, it appeared that solutions of 3e start to decompose upon precipitation of colloidal silver when they are heated or irradiated with light, respectively. Appropriate work‐up of the reaction mixture allows the isolation of the phosphane P(C₆H₄CH₂NMe₂‐2)₃ ( 5 ) along with [Ag(phen)₂]OTf ( 4 ). The solid‐state structures of neutral 1a and cationic 4 are reported. Mononuclear 1a crystallizes in the monoclinic space group P2₁/c with the cell parameters a = 16.7763(2), b = 14.7892(2), c = 25.44130(10)Å, β = 106.1260(10), V = 6063.83(11)ų and Z = 4 with 8132 observed unique reflections (R₁ = 0.0712), while 4 crystallizes in the monoclinic space group C2/c with the cell parameters a = 26.749(3), b = 7.1550(10), c = 26.077(3)Å, β = 113.503(2), V = 4576.8(10)ų and Z = 4 with 6209 observed unique reflections (R₁ = 0.0481). The unit cell of 1a consists of two independent molecules. In both molecules the silver atom possesses a distorted tetrahedral coordination sphere and a boat‐like conformation for the six‐membered AgPNCH₂C_2/phenyl cycles is found. In 4 , as typical for 1a , the silver atom possesses the coordination number 4. The two phen ligands are tilted by 40.63°. The OTf group is acting as non‐coordinating counter ion.     

Neuartige Synthese eines Lanthanoidtrialkyls – Charakterisierung und Kristallstruktur von Yb(CH2tBu)3(thf)2

Novel Synthesis of a Lanthanide Trialkyl – Characterization and Crystal Structure of Yb(CH₂ t Bu)₃(thf)₂ The solvated ytterbium alkyl Yb(CH₂tBu)₃(thf)₂ ( 1 ) was obtained in moderate yield from the reaction of ytterbium metal with neopentyl iodide. Ruby‐red air‐sensitive crystals of 1 were characterized by melting point, elemental analysis, IR, NMR, and UV/Vis spectroscopy and by X‐ray crystallography. In the solid state the ytterbium atom shows a trigonal bipyramidal coordination with the neopentyl groups and the THF ligands occupying equatorial and axial positions, respectively.     

Synthese und Kristallstruktur von [(PhCH2)2GaF(tBuNH2)]2 · 2 THF

Synthesis and Crystal Structure of [(PhCH₂)₂GaF(^tBuNH₂)]₂ · 2 THF (PhCH₂)₂GaF reacts with ^tBuNH₂ to the adduct [(PhCH₂)₂GaF(^tBuNH₂)] ( 1 ). 1 was characterized by NMR, IR and MS techniques. 1 can be recrystallized from THF forming crystals of [ 1 ]₂ · 2 THF. According to an X-ray structure analysis [ 1 ]₂ · 2 THF consists of dimers of 1 formed by hydrogen bridges. The THF molecules are coordinated to [ 1 ]₂ by hydrogen bridges, too.     

Das Hexagallan [Ga6{SiMe(SiMe3)2}6] und das closo‐Hexagallanat [Ga6{Si(CMe3)3}4(CH2C6H5)2]2— — der Übergang zu einem ungewöhnlichen precloso‐Cluster

The Hexagallane [Ga₆{SiMe(SiMe₃)₂}₆] and the closo‐Hexagallanate [Ga₆{Si(CMe₃)₃}₄ (CH₂C₆H₅)₂]^2— — the Transition to an Unusual precloso‐Cluster The closo hexagallanate [Ga₆R₄(CH₂Ph)₂]^2— (R = Si^tBu₃) as well as the hexagallane Ga₆R₆ (R = SiMe(SiMe₃)₂) with only six cluster electron pairs were isolated from reactions of “GaI” with the corresponding silanides. The structure of the latter is derived from an octahedron by a Jahn‐Teller‐distortion and is different from the capped trigonal bipyramidal one expected by the Wade‐Mingos rules. Both compounds were characterized by X‐ray crystallography. The bonding is discussed with simplified Ga₆H₆ and Ga₆H₆^2— models via DFT methods.     

Darstellung und Strukturen neuartiger Triphenylsilylund Triphenylgermyl‐substituierter Gallane und Oligogallane – [Ga3(GePh3)6]–, das erste lineare Trigallan

Chemistry of Gallium. 20. Synthesis and Structures of Novel Triphenylsilyl and Triphenylgermyl Substituted Gallanes and Oligogallanes – [Ga₃(GePh₃)₆]^–, the First Linear Trigallane From the raction of sonochemically prepared “GaI” with LiEPh₃ (E = Si, Ge) the compounds [Li(THF)₂][GaI(EPh₃)₃] (E = Si: 22 , E = Ge: 24 ), [Li(THF)₄][GaI(SiPh₃)₃] ( 23 ), [Li(THF)₄][Ga₂(SiPh₃)₅] ( 21 ) and [Li(THF)₄][Ga₃(GePh₃)₆] ( 25 ) as well as polymeric Li(THF)I ( 20 ) were obtained and structurally characterized. 21 is a monoanionic digallane, exhibiting a trigonal planar and a tetrahedrally coordinated gallium centre. 25 has a linear Ga₃ core, where the terminal gallium atoms bear three GePh₃‐groups, each. The central Ga atom is only 2‐coordinated. Thus, 25 may be a valuable hint to the formation of larger gallium clusters with “naked” gallium atoms. Derivatives of 21 and 25 have been studied by DFT methods.     

Die Kristallstruktur von cis‐ und trans‐N‐iso‐Propylamidodimethylindium, [(CH3)2In‐N(H)iC3H7]2

The Crystal Structure of cis‐ and trans‐N‐iso‐Propylamidodimethyl Indium, [(CH₃)₂In‐N(H)ⁱC₃H₇]₂ According to the X‐ray structure determination [(CH₃)₂In‐N(H)ⁱC₃H₇]₂ (prepared from InMe₃ (Me = CH₃) and H₂NⁱPr (ⁱPr = CH(CH₃)₂) crystallizes in the monoclinic space group P2₁/n with 3 dimeric trans as well as 3 dimeric cis isomers per unit cell. The centrosymmetric form has a planar In₂N₂ core with In—N bonds of 222.1(4) and 222.9(5) pm, respectively, the skeleton of the cis isomer with In—N bonds of 221.4(4) pm is slightly folded (13.7°). Some ¹H, ¹³C NMR, IR, and Raman data are reported.     

Synthese,Kristallstruktur und Eigenschaften von Tetranatrium‐bis(trimetaphosphimato)cuprat(II)‐Decahydrat,Na4{Cu[(PO2NH)3]2} · 10 H2O

Synthesis, Crystal Structure, and Properties of Tetrasodium Bis(trimetaphosphimato)cuprate(II) Decahydrate, Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O Tetrasodium bis(trimetaphosphimato)cuprate(II) decahydrate, Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O, was obtained by the reaction of an aqueous solution of Na₃(PO₂NH)₃ · 4 H₂O with Cu(NO₃)₂ · 3 H₂O (molar ratio 2 : 1). The structure of Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O ( 1 ) was solved by single‐crystal X‐ray methods (P 1, a = 912.51(6), b = 932.14(6), c = 966.10(6) pm, α = 94.840(5), β = 108.652(6), γ = 118.588(6)°, Z = 1). The P₃N₃ rings of the trimetaphosphimate ions exhibit a slightly distorted sofa conformation. The conformation of the anions have been analysed using torsion angles, displacement asymmetry parameters, and puckering parameters. The trimetaphosphimate ions act as bidentate ligands of Cu²⁺. With additionally coordinated water molecules, anionic complexes {Cu[(PO₂NH)₃]₂ · 2 H₂O}^4– are formed. In the crystal these complexes are interconnected by N–H…O und O–H…O hydrogen bonds and they coordinate the Na⁺. Thus, a three‐dimensional network is formed.     

Einfache Synthese von Alkylaluminium‐ und Alkylgalliumhydriden – Kristallstrukturen von [(Me3C)2GaH]3 und den neuartigen Sesquihydriden [(Me3C)2EH]2[EH2CMe3]2 (E = Al,Ga)

Facile Syntheses of Alkylaluminium and Alkylgallium Hydrides – Crystal Structures of [(Me₃C)₂GaH]₃ and the Novel Sesquihydrides [(Me₃C)₂EH]₂[EH₂CMe₃]₂ (E = Al, Ga) The facile syntheses of some important, sterically highly shielded dialkylaluminium hydrides R₂AlH [R = CMe₃, CH(SiMe₃)₂] succeeded by the reaction of the corresponding trialkylaluminium compounds with the alane adduct AlH₃ × NMe₂Et in a 2 to 1 molar ratio. This route is not suitable for the synthesis of monoalkylaluminium dihydrides. An excess of AlH₃ yielded the novel sesquihydride [(Me₃C)₂AlH]₂[AlH₂CMe₃]₂ ( 3 ) as the hydride richest compound which possesses an unprecedented heterocycle comprising four aluminium and four hydrogen atoms in the solid state. The dialkylgallium hydride (Me₃C)₂GaH ( 4 ) was formed on a similar route by the treatment of tri(tert‐butyl)gallane with the adduct GaH₃ · NMe₂Et. As shown by a crystal structure determination, compound 4 is a trimer in the solid state possessing a Ga₃H₃ heterocycle. A gallium sesquihydride analogous to compound 3 , [(Me₃C)₂GaH]₂[GaH₂CMe₃]₂ ( 5 ), was formed on employing an excess of GaH₃.