Neue mehrkernige Indium–Stickstoff‐Verbindungen – Synthese und Kristallstrukturen von [In4X4(NtBu)4] (X = Cl,Br, I) und [In3Br4(NtBu)(NHtBu)3]

New Polynuclear Indium Nitrogen Compounds – Synthesis and Crystal Structures of [In₄X₄(N^tBu)₄] (X = Cl, Br, I) and [In₃Br₄(N^tBu)(NH^tBu)₃] The reaction of the indium trihalides InX₃ (X = Cl, Br, I) with LiNH^tBu in THF leads to the In₄N₄‐heterocubanes [In₄X₄(N^tBu)₄] (X = Cl 1 , Br 2 , I 3 ). Additionally [In₃Br₄(N^tBu)(NH^tBu)₃] ( 4 ) was obtained as a by‐product in the synthesis of 2 . 1 – 4 have been characterized by x‐ray crystal structure analysis. 1 – 3 consist of In₄N₄ heterocubane cores with an alternating arrangement of In and N atoms. The In atoms are coordinated nearly tetrahedrally by three N‐atoms and a terminal halogen atom. 4 contains a tricyclic In₃N₄ core which can be formally derived from an In₄N₄‐heterocubane by removing one In atom.     

Synthese und Kristallstruktur von [Na3(H2O)6,5(EtOH)][PhSnS3] · 3 EtOH

Synthesis and Crystal Structure of [Na₃(H₂O)_6,5(EtOH)][PhSnS₃] · 3 EtOH Ph₄Sn₄S₆ reacts with Na₂S · 5 H₂O in aqueous acetone to form Na₃[PhSnS₃]. Recrystallization of the crude product from ethanol leads to colourless needles of [Na₃(H₂O)_6,5(EtOH)][PhSnS₃] · 3 EtOH 1 . The crystal structure of 1 was determined by X-ray diffraction. 1 consists of [PhSnS₃]^3– anions and sodium cations which are coordinated by water, ethanol and sulfur atoms of the [PhSnS₃]^3– anions. The [PhSnS₃]^3– anion contains a tin atom which is coordinated nearly tetrahedrally by a phenyl group and three sulfur atoms. The Sn–S bonds are 237,4(2)–238,4(2) pm.     

Aktivierung von Schwefelkohlenstoff an Trirutheniumclustern: Synthese und Kristallstruktur von [Ru3(CO)5(μ‐H)2(μ‐PCy2)(μ‐Ph2PCH2PPh2){μ‐η2‐PCy2C(S)}(μ3‐S)] und [Ru3(CO)5(CS)(μ‐H)(μ‐PtBu2)(μ‐PCy2)2(μ3‐S)]

Activation of Carbon Disulfide on Triruthenium Clusters: Synthesis and X‐Ray Crystal Structure Analysis of [Ru₃(CO)₅(μ‐H)₂(μ‐PCy₂)(μ‐Ph₂PCH₂PPh₂){μ‐η²‐PCy₂C(S)}(μ₃‐S)] and [Ru₃(CO)₅(CS)(μ‐H)(μ‐P^tBu₂)(μ‐PCy₂)₂(μ₃‐S)] [Ru₃(CO)₆(μ‐H)₂(μ‐PCy₂)₂(μ‐dppm)] ( 1 ) (dppm = Ph₂PCH₂PPh₂) reacts under mild conditions with CS₂ and yields by oxidative decarbonylation and insertion of CS into one phosphido bridge the opened 50 VE‐cluster [Ru₃(CO)₅(μ‐H)₂(μ‐PCy₂)(μ‐dppm){μ‐η²‐PCy₂C(S)}(μ₃‐S)] ( 2 ) with only two M–M bonds. The compound 2 crystallizes in the triclinic space group P 1 with a = 19.093(3), b = 12.2883(12), c = 20.098(3) Å; α = 84.65(3), β = 77.21(3), γ = 81.87(3)° and V = 2790.7(11) ų. The reaction of [Ru₃(CO)₇(μ‐H)(μ‐P^tBu₂)(μ‐PCy₂)₂] ( 3 ) with CS₂ in refluxing toluene affords the 50 VE‐cluster [Ru₃(CO)₅(CS)(μ‐H)(μ‐P^tBu₂)(μ‐PCy₂)₂(μ₃‐S)] ( 4 ). The compound cristallizes in the monoclinic space group P 2₁/a with a = 19.093(3), b = 12.2883(12), c = 20.098(3) Å; β = 104.223(16)° and V = 4570.9(10) ų. Although in the solid state structure one elongated Ru–Ru bond has been found the complex 4 can be considered by means of the ³¹P‐NMR data as an electron‐rich metal cluster.     

Synthese und Charakterisierung von 2‐O‐funktionalisierten Ethylrhodoximen und ‐cobaloximen

Synthesis and Characterization of 2‐O‐Functionalized Ethylrhodoximes and ‐cobaloximes 2‐Hydroxyethylrhodoxime and ‐cobaloxime complexes L—[M]—CH₂CH₂OH (M = Rh, L = PPh₃, 1 ; M = Co, L = py, 2 ; abbr.: L—[M] = [M(dmgH)₂L] (dmgH₂ = dimethylglyoxime, L = axial base) were obtained by reaction of L—[M]^— (prepared by reduction of L—[M]—Cl with NaBH₄ in methanolic KOH) with BrCH₂CH₂OH. H₂O—[Rh]^—, prepared by reduction of H[RhCl₂(dmgH)₂] with NaBH₄ in methanolic KOH, reacted with BrCH₂CH₂OH followed by addition of pyridine yielding py—[Rh]—CH₂CH₂OH ( 3 ). Complexes 1 and 3 were found to react with (Me₃Si)₂NH forming 2‐(trimethylsilyloxy)ethylrhodoximes L—[Rh]—CH₂CH₂OSiMe₃ (L = PPh₃, 4 ; L = py, 5 ). Treatment of complex 1 with acetic anhydride resulted in formation of the 2‐(acet oxy)ethyl complex Ph₃P—[Rh]—CH₂CH₂OAc ( 6 ). All complexes 1 — 6 were isolated in good yields (55—71 %). Their identities were confirmed by NMR spectroscopic investigations ( 1 — 6 : ¹H, ¹³C; 1 , 4 , 6 : ³¹P) and for [Rh(CH₂CH₂OH)(dmgH)₂(PPh₃)]·CHCl₃·1/2H₂O ( 1 ·CHCl₃·1/2H₂O) and py—[Rh]—CH₂CH₂OSiMe₃ ( 5 ) by X‐ray diffraction analyses, too. In both molecules the rhodium atoms are distorted octahedrally coordinated with triphenylphosphine and the organo ligands (CH₂CH₂OH and CH₂CH₂OSiMe₃, respectively) in mutual trans position. Solutions of 1 in dmf decomposed within several weeks yielding a hydroxyrhodoxime complex “Ph₃P—[Rh]—OH”. X‐ray diffraction analysis exhibited that crystals of this complex have the composition [{Rh(dmg)(dmgH) (H₂O)(PPh₃)}₂]·4dmf ( 7 ) consisting of centrosymmetrical dimers. The rhodium atom is distorted octahedrally coordinated. Axial ligands are PPh₃ and H₂O. One of the two dimethylglyoximato ligands is doubly deprotonated. Thus, only one intramolecular O—H···O hydrogen bridge (O···O 2.447(9)Å) is formed in the equatorial plane. The other two oxygen atoms of dmgH^— and dmg^2—, respectively, act as hydrogen acceptors each forming a strong (intermolecular) O···H′—O′ hydrogen bridge to the H′₂O′ ligand of the other molecule (O···O′ 2.58(2)/2.57(2)Å).     

Synthesis and Crystal Structure of a Tetranuclear Molybdenum(II) Silylamido Cluster

Treatment of molybdenum(II) chloride with the difunctional silylamide Li₂Me₂Si(NPh)₂ led to the formation of the tetranuclear cluster compound [Mo₄{Me₂Si(NPh)₂}₄]. According to the X-ray crystal structure determination, the central core of the cluster consists of four molybdenum atoms in a nearly rectangular arrangement. There are two μ₄-κ-N,N,N',N'-Me₂Si(NPh)₂^2– ligands capping the Mo₄ rectangle and two μ₂-Me₂Si(NPh)₂^2– ligands located at opposite edges. The alternating Mo–Mo distances of 218.1(1) and 279.5(1) pm indicate the presence of a cyclobutadiyne type cluster with alternating Mo–Mo triple and single bonds.     

Crystallographic report: 1,3,5,7‐Tetraisopropyl‐2,4,6,8,9,10‐hexathia‐1,3,5,7‐tetrastanna‐adamantane

The crystal structure of ⁱPr₄Sn₄S₆ consists of isolated molecules that contain an adamantane‐like Sn₄S₆ core. The tin atoms are coordinated nearly tetrahedrally, with Sn–S distances ranging from 2.397(1) to 2.411(1) Å. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthese,Struktur und Reaktivität von Tris‐, Bis‐ und Mono(2,4‐dimethylpentadienyl)‐Komplexen des Neodyms,Lanthans und des Yttriums

The tris(2,4‐dimethylpentadienyl) complexes [Ln(η⁵‐Me₂C₅H₅)₃] (Ln = Nd, La, Y) are obtained analytically pure by reaction of the tribromides LnBr₃·nTHF with the potassium compound K(Me₂C₅H₅)(thf)_n in THF in good yields. The structural characterization is carried out by X‐ray crystal structure analysis and NMR‐spectroscopically. The tris complexes can be transformed into the dimeric bis(2,4‐dimethylpentadienyl) complexes [Ln₂(η⁵‐Me₂C₅H₅)₄X₂] (Ln, X: Nd, Cl, Br, I; La, Br, I; Y, Br) by reaction with the trihalides THF solvates in the molar ratio 2:1 in toluene. Structure and bonding conditions are determined for selected compounds by X‐ray crystal structure analysis and NMR‐spectroscopically in general. The dimer‐monomer equilibrium existing in solution was investigated NMR‐spectroscopically in dependence of the donor strength of the solvent and could be established also by preparation of the corresponding monomer neutral ligand complexes [Ln(η⁵‐Me₂C₅H₅)₂X(L)] (Ln, X, L: Nd, Br, py; La, Cl, thf; Br, py; Y, Br, thf). Finally the possibilities for preparation of mono(2,4‐dimethylpentadienyl)lanthanoid(III)‐dibromid complexes are shown and the hexameric structure of the lanthanum complex [La₆(η⁵‐Me₂C₅H₅)₆Br₁₂(thf)₄] is proved by X‐ray crystal structure analysis.     

Die Kristallstrukturen von (NBu4)[(Ph3Sn)3(MoO4)2] und (NBu4)[(Ph3Sn)3(MoO4)2]·CH3CN: Organozinnmolybdate mit neuartigen 3D‐Netzwerken

The Crystal Structures of (NBu₄)[(Ph₃Sn)₃(MoO₄)₂] and (NBu₄)[(Ph₃Sn)₃(MoO₄)₂]·CH₃CN: Organotin Molybdates with Novel 3D Networks The reaction of (NBu₄)₂[Mo₆O₁₉] with Ph₃SnCl and NBu₄OH in acetonitrile as solvent leads to the formation of (NBu₄)[(Ph₃Sn)₃(MoO₄)₂] ( 5 ). 5 and (NBu₄)[(Ph₃Sn)₃(MoO₄)₂]· CH₃CN 6 have been characterized by single crystal structure analysis at 220 K. 5 crystallizes monoclinic with a = 1429.5(4) pm, b = 2292.2(3) pm, c = 2269.7(5) pm, β = 107.42(3)°, space group Cc, 6 crystallizes orthorhombic with a = 1820.5(1) pm, b = 1848.6(2) pm and c = 2143.9(1) pm, space group P2₁2₁2₁. The crystal structures of 5 and 6 consist of isolated (NBu₄)⁺ cations and anionic 3D networks of Ph₃SnO₂ trigonal bipyramides and MoO₄ tetrahedra which are linked by common oxygen atoms.     

Synthese und Kristallstruktur von [{(tBu2P)2InCl}2]

Synthesis and Crystal Structure of [{(tBu₂P)₂InCl}₂] The reaction of InCl₃ with tBu₂PSiMe₃ leads to [{(tBu₂P)₂InCl}₂] ( 1 ). 1 crystallizes in the space group P2₁/c. The lattice constants (at 216 K) are: a = 945.9(5) pm, b = 1 604.1(9) pm, c = 1 636.8(8) pm, β = 100.55(4)°. 1 contains a planar In₂P₂ ring. Each In atom is coordinated by two bridging tBu₂P groups, a terminal tBu₂P group and a terminal Cl atom. The coordination geometry of the In atoms is roughly tetrahedral.