Preparation and Crystal Structure of the Neodymium Borohydride [Li(thf)4]2[Nd2(μ‐Cl)2(BH4)6(thf)2]

The neodymium borohydride [Li(thf)₄]₂[Nd₂(μ‐Cl)₂(BH₄)₆(thf)₂] was synthesized from neodymium chloride and lithium borohydride. The compound crystallized in the triclinic crystal system, space group (No. 2) with the cell constants a = 14.8613(11), b = 17.8715(13), c = 23.5846(18) Å, α = 100.760(6), β = 90.648(6) and γ = 103.294(6)°. Each neodymium atom is coordinated by three borohydride anions and a THF molecule whereas two neodymium cations are bridged through two chloro ligands. The charge of the [Nd₂(μ‐Cl)₂(BH₄)₆(thf)₂]²⁻ anion, which represents the first structurally characterized binuclear mixed borohydride chlorido complex, is compensated by two [Li(thf)₄]⁺ cations.     

Reaction between [MgCl2(THF)2] and [MoOCl3(THF)2]. The Crystal Structures of [Mg(THF)6][MoOCl4THF]2 and [Mg2(m̈-Cl)3(THF)6][MoOCl4THF]

Two [MoOCl₃(THF)₂] molecules are used for detachment of two Cl atoms from [MgCl₂(THF)₂]. In such reaction a green crystalline salt [Mg(THF)₆][MoOCl₄THF]₂ IV is formed. Compound IV reacts further with 3 equivalents of bis(tetrahydrofuran)magnesium dichloride, yielding a green ionic [Mg₂(m?-Cl)₃(THF)₆][MoOCl₄THF] compound V . Compound IV and V vary only in a structure of cation what indicated that the tri-m?-chlorohexakis(tetrahydrofuran)dimagnesium(II) cation in V is really formed in reaction between [Mg(THF)₆]²⁺ cation and [MgCl₂(THF)₂]. The crystal structure of compounds IV and V has been solved by X-ray diffraction method. The [Mg(THF)₆]²⁺ cation forms the tetragonally distorted octahedron with the magnesium atom in the symmetry centre. In homobimetallic di-octahedral [Mg₂(m?-Cl)₃(THF)₆]⁺ cation the magnesium atoms are surrounded by three bridging chlorine atoms and three THF molecules. The structures of [MoOCl₄THF]^? in IV and V are similar. In those anions the molybdenum atom is hexacoordinated with four chlorine atoms in equatorial plane.     

Synthesen und Strukturen der polymeren Silber‐Komplexe [Ag2Cl2(dppbp)3]∞, [Ag2(SPh)2(dppe)3]∞ und [Ag2(SPh)2(triphos)]∞ sowie der Silber‐Chalkogenido‐Cluster [Ag7(SPh)7(dppm)3], {[Ag7(TePh)7(dppp)3]2(dppp)} und [Ag22Cl(SPh)10(PhCOO)11(dmf)3]∞

Syntheses and Structures of the Polymeric Silver Complexes [Ag₂Cl₂(dppbp)₃]_∞, [Ag₂(SPh)₂(dppe)₃]_∞ and [Ag₂(SPh)₂(triphos)]_∞ as well as the Silver Chalcogenido Clusters [Ag₇(SPh)₇(dppm)₃], {[Ag₇(TePh)₇(dppp)₃]₂(dppp)}, and [Ag₂₂Cl(SPh)₁₀(PhCOO)₁₁(dmf)₃]_∞ The reaction of silver carboxylate with silylated chalcogen compounds have been found to have a possibility for the synthesis of metal‐chalcogenide‐custers. Especially phosphine ligands have been found to be useful in stabilising the cluster cores. Some of the silver carboxylate phosphine complexes, which are formed in‐situ, ([Ag₂Cl₂(dppbp)₃]_∞ ( 1 )) and some silver chalcogen complexes ([Ag₂(SPh)₂(dppe)₃]_∞ ( 2 ) und [Ag₂(SPh)₂(triphos)]_∞ ( 3 )), could be isolated and characterised by X‐ray diffraction. Using special reaction conditions, it is possible to isolate cluster species like [Ag₇(SPh)₇(dppm)₃] ( 4 ), {[Ag₇(TePh)₇(dppp)₃]₂(dppp)} ( 5 ) and [Ag₂₂Cl(SPh)₁₀(PhCOO)₁₁(dmf)₃]_∞ ( 6 ) beside the complex compounds. 1: Space group P2₁/n (No. 14), Z = 2, a = 1336, 1(2), b = 2081, 2(5), c = 2015, 4(4) pm, β = 99, 87(2)°; 2: Space group P2₁/n (No. 14), Z = 2, a = 1416, 1(3), b = 1874, 7(4), c = 1444, 8(3) pm, β = 93, 26(3)°; 3: Space group P2₁/n (No. 14), Z = 4, a = 1456, 8(3, b = 1890, 2(4), c = 1916, 1(4) pm, β = 99, 11(3)°; 4: Space group P2₁/n (No. 14), Z = 4, a = 1570, 2(3), b = 2798, 5(6), c = 2752, 7(6) pm, β = 98, 02(3)°; 5: Space group P1 (No. 2), Z = 2, a = 2115, 5(4), b = 2553, 3(5), c = 3188, 7(6) pm, α = 68, 87(3)°, β = 74, 05(3)°, γ = 69, 70(3)°; 6: Space group P1 (No. 2), Z = 2, a = 1583, 0(3), b = 1709, 6(3), c = 2990, 0(6) pm, α = 80, 41(3)°, β = 88, 86(3)°, γ = 71, 10(3)°).     

Synthesis and Structure of the Clusters [Hg2(μ—SePh)2(SePh)2(PPh3)2] and [Hg3Br3(μ—SePh)3] · 2 DMSO

The compounds [Hg₂(μ—SePh)₂(SePh)₂(PPh₃)₂] ( I ) and [Hg₃Br₃(μ—SePh)₃] · 2 DMSO ( II ) are formed by reactions of [Hg(SePh)₂] with PPh₃ in THF( I ) or with HgBr₂ in DMSO ( II ) at room temperature. X—ray crystallography reveals that the cluster I consists of a distorted square built by each two Hg and Se atoms. The Hg atoms have almost tetrahedral co‐ordination environments formed by selenium atoms of two (μ‐^—SePh) ligands and Se and P atoms of terminal ^—SePh and PPh₃ ligands. The compound II is a six‐membered ring with alternating Hg and Se atoms in the chair conformation. Two DMSO molecules occupy positions below and above the [Hg₃Se₃] ring with the oxygen atoms directed to the centre of the ring.     

Synthesis and Characterization of [Hg(sulfamethoxazolato)2]·2DMSO and[Cu2(μ‐CH3CO2)4(sulfamethoxazole)2]

[Hg(sulfamethoxazolato)₂]·2DMSO ( 1 ) and [Cu₂(CH₃COO)₄(sulfa‐methoxazole)₂] ( 2 ) can be obtained by the reaction of sulfamethoxazole with mercury acetate or copper acetate in methanol. The structures of the two complexes were characterized by single crystal X—ray diffractometry. Compound 1 consists of sulfamethoxazolato ligands bridging the metal ions building an unidimensional chain. Two solvent dimethylsulfoxide molecules are involved via N‐H···O hydrogen bridges. The mercury atom shows a linear primary coordination arrangement formed by two trans deprotonated sulfonamidic nitrogen atoms. The overall coordination around the metal atom may be regarded as a strongly distorted octahedron when the interactions of mercury with four sulfonamidic oxygen atoms [bond distances of 2.761(4) Å—2.971(4) Å] are also considered to build an equatorial plane and the N1 and N1′ atoms [bond distance of 2.037(5) Å] occupy the apical positions. Compound 2 is a dinuclear complex in which the copper ions are bridged by four syn‐syn acetate ligands which are related by a symmetry centre located in the centre of the complex. Each copper atom presents a nearly octahedral coordination where the equatorial plane is formed by four oxygen atoms and an isoxazolic nitrogen atom and the second copper atom occupy the apical positions.     

Synthesen und Strukturen der Titan(III)‐siloxane [Ti(OSiPh3)3(thf)2] und [Ti(OSiPh3)3(py)2]

Syntheses and Structures of the Titanium(III) Siloxanes [Ti(OSiPh₃)₃(thf)₂] and [Ti(OSiPh₃)₃(py)₂] The new titaniumtrioxysilanes [Ti(OSiPh₃)₃(thf)₂] ( 1 ) and [Ti(OSiPh₃)₃(py)₂] ( 2 ) have been obtained from the reaction of titaniumtrichloride with LiOSiPh₃ in the presence of the corresponding bases tetrahydrofurane (thf) and pyridine (py). From the crystal structures of both compounds it is evident that the titanium atoms are in the centres of trigonal‐bipyramidal coordination figures, with the donor atoms in axial positions. The compounds 1 and 2 have slightly different structures (mean values: 1 : Ti‐O(Si) 1.897(9), Ti‐O(C) 2.136(8) Å; 2 : Ti‐O 1.902(9), Ti‐N2.252(8) Å) and have a single absorption band in the visible region of the UV‐spectrum. The exchange of the thf‐ligands in 1 by pyridine (in high molar excess) seems to be hindered as deduced from UV‐spectroscopy.     

Synthese und Kristallstrukturen von [Li(thf)4]2[Bi4I14(thf)2], [Li(thf)4]4[Bi5I19] und (Ph4P)4[Bi6I22]

Synthesis and Crystal Structure of [Li(thf)₄]₂[Bi₄I₁₄(thf)₂], [Li(thf)₄]₄[Bi₅I₁₉], and (Ph₄P)₄[Bi₆I₂₂] Solutions of BiI₃ in THF or methanol react with MI (M = Li, Na) to form polynuclear iodo complexes of bismuth. The syntheses and results of X-ray structure analyses of compounds [Li(thf)₄]₂[Bi₄I₁₄(thf)₂], [Li(thf)₄]₄[Bi₅I₁₉], [Na(thf)₆]₄[Bi₆I₂₂] and (Ph₄P)₄[Bi₆I₂₂] are described. The anions of these compounds consist of edge-sharing BiI₆ and BiI₅(thf) octahedra. The Bi atoms lie in a plane and are coordinated by bridging and terminal I atoms and by THF ligands in a distorted octahedral fashion. [Li(thf)₄]₂[Bi₄I₁₄(thf)₂]: Space group P1 (No. 2), a = 1 159.9(6), b = 1 364.6(7), c = 1 426.5(7) pm, α = 114.05(3), β = 90.01(3), γ = 100.62(3)°. [Li(thf)₄]₄[Bi₅I₁₉]: Space group P2₁/n (No. 14), a = 1 653.0(9), b = 4 350(4), c = 1 836.3(13) pm, β = 114.70(4)°. [Na(thf)₆]₄[Bi₆I₂₂]: Space group P2₁/n (No. 14), a = 1 636.4(3), b = 2 926.7(7), c = 1 845.8(4) pm, β = 111.42(2)°. (Ph₄P)₄[Bi₆I₂₂]: Space group P1 (No. 2), a = 1 368.6(7), b = 1 508.1(9), c = 1 684.9(8) pm, α = 98.28(4), β = 95.13(4), γ = 109.48(4)°.     

Synthese und Struktur eines Molybdän–Gadolinium-Heterometall-Komplexes Die Struktur von [Li(thf)4]2[Cp2MoSGdBr4(thf)]2

Synthesis and structure of a Molybdenum–Gadolinium Heterometallic Complex. The Structure of [Li(thf)₄]₂[Cp₂MoSGdBr₄(thf)]₂ [Cp₂MoHLi] reacts in THF with S and GdBr₃ to yield the tetranuclear heterobimetallic complex [Li(thf)₄]₂[Cp₂MoSGdBr₄(thf)]₂. The bonding situation and the structure of this compound were characterized by X-ray structure analysis (space group P1 (No. 2), Z = 1, a = 10.845(2) Å, b = 12.166(2) Å, c = 15.881(2) Å, α = 101.74(2)°, β = 97.62(2)°, γ = 103.97(2)°). Each S atom of the central Mo₂S₂-ring is coordinated by a GdBr₄(thf) fragment. Additionally each Mo atom is connected to two Cp ligands. This leads to a tetrahedral coordination of the Mo atoms and a octahedral coordination of the Gd ions.     

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.     

Synthesen und Strukturen der phosphor- und stickstoffverbrückten Übergangsmetallkomplexe [Pd(NPhPPh2)(PPh3)]2, [Pd(NPhPPh2)2 · Li(thf)]2, [Pd(NPhPPh2)Cl · Li(thf)3]2, [M(NPhPPh2)(HNPhPPh2)]2 (M  Pd,Pt), [M{Ph2P(NPh)2}2] (M  Co,Ni), [Ni(PPh2){Ph2P(NPh)2}]2 und [Ni2(PPh2)(NPhPPh2)(HNPhPPh2)3]

Syntheses and Structures of the Phosphorus and Nitrogenbridged Transition Metal Complexes [Pd(NPhPPh₂)(PPh₃)]₂, [Pd(NPhPPh₂)₂ · Li(thf)]₂, [Pd(NPhPPh₂)Cl · Li(thf)₃]₂, [M(NPhPPh₂)(HNPhPPh₂)]₂ (M?Pd, Pt), [M{Ph₂P(NPh)₂}₂] (M?Co, Ni), [Ni(PPh₂){Ph₂P(NPh)₂}]₂ and [Ni₂(PPh₂)(NPhPPh₂)(HNPhPPh₂)₃] . From the reaction of LiNPhPPh₂ with Palladium-Nickel- and Cobaltcomplexes, depending on the reaction conditions, different monomeric and dimeric complexes can be isolated. In these compounds the (NPhPPh₂)^?-group acts as both a bridging and as a terminal ligand. [Pd(NPhPPh₂)(PPh₃)]₂ ( 1 ), [Pd(NPhPPh₂)₂ · Li(thf)]₂ ( 2 ) and [Pd(NPhPPh₂)Cl · Li(thf)₃]₂ ( 3 ) are formed from the reaction of [PdCl₂(PPh₃)₂] or [PdCl₂(COD)] with LiNPhPPh₂. In contrast to this from the reaction of Pd(Ac)₂ and HNPhPPh₂ (in the presence of zinc-dust) or [PtCl₂(py)₂] and LiNPhPPh₂.     

Synthesis,Structures and Reactivity of Lanthanoid(II) Formamidinates of Varying Steric Bulk

New reactive, divalent lanthanoid formamidinates [Yb(Form)₂(thf)₂] (Form=[RNCHNR]; R=o‐MeC₆H₄ (o‐TolForm; 1 ), 2,6‐Me₂C₆H₃ (XylForm; 2 ), 2,4,6‐Me₃C₆H₂ (MesForm; 3 ), 2,6‐Et₂C₆H₃ (EtForm; 4 ), o‐PhC₆H₄ (o‐PhPhForm; 5 ), 2,6‐iPr₂C₆H₃ (DippForm; 6 ), o‐HC₆F₄ (TFForm; 7 )) and [Eu(DippForm)₂(thf)₂] ( 8 ) have been prepared by redox transmetallation/protolysis reactions between an excess of a lanthanoid metal, Hg(C₆F₅)₂ and the corresponding formamidine (HForm). X‐ray crystal structures of 2 – 6 and 8 show them to be monomeric with six‐coordinate lanthanoid atoms, chelating N,N′‐Form ligands and cis‐thf donors. However, [Yb(TFForm)₂(thf)₂] ( 7 ) crystallizes from THF as [Yb(TFForm)₂(thf)₃] ( 7 a ), in which ytterbium is seven coordinate and the thf ligands are “pseudo‐meridional”. Representative complexes undergo C? X (X=F, Cl, Br) activation reactions with perfluorodecalin, hexachloroethane or 1,2‐dichloroethane, and 1‐bromo‐2,3,4,5‐tetrafluorobenzene, giving [Yb(EtForm)₂F]₂ ( 9) , [Yb(o‐PhPhForm)₂F]₂ ( 10) , [Yb(o‐PhPhForm)₂Cl(thf)₂] ( 11) , [Yb(DippForm)₂Cl(thf)] ( 12) and [Yb(DippForm)₂Br(thf)] ( 16) . X‐ray crystallography has shown 9 to be a six‐coordinate, fluoride‐bridged dimer, 12 and 16 to be six‐coordinate monomers with the halide and thf ligands cis to each other, and 11 to have a seven‐coordinate Yb atom with “pseudo‐meridional” unidentate ligands and thf donors cis to each other. The analogous terbium compound [Tb(DippForm)₂Cl(thf)₂] ( 13 ), prepared by metathesis, has a similar structure to 11 . C? Br activation also accompanies the redox transmetallation/protolysis reactions between La, Nd or Yb metals, Hg(2‐BrC₆F₄)₂, and HDippForm, yielding [Ln(DippForm)₂Br(thf)] complexes (Ln=La ( 14 ), Nd ( 15 ), Yb ( 16 )).     

Synthesis and Crystal Structure of [Fe(Cp)2]3(Bi2Cl9)·thf

Single crystals of [Fe(Cp)₂]₃(Bi₂Cl₉)·thf were obtained from a thf solution containing ferrocene and BiCl₃. The structure shows disorder at room temperature which disappears upon cooling, coupled with a decrease in symmetry. The title compound crystallizes in the orthorhombic space group P2₁2₁2₁ [a = 1698.64(2), b = 2318.69(3), c = 1085.66(2) pm] with three ferrocenium ions, one nonachlorodibismutate ion and one molecule of thf in the asymmetric unit.     

Syntheses and Molecular Structures of [(thf)4Li] [{(thf)Li}M(C4H8)3] (M = Zr,Hf) and Their Solution Behavior

The reaction of MCl₄(thf)₂ (M = Zr, Hf) with 1,4-dilitiobutane in diethyl ether at –25 °C or at 0 °C with a molar ratio of 1 : 3 yields the homoleptic “ate” complexes [(thf)₄Li] [{(thf)Li}M(C₄H₈)₃] 1 - Zr (M = Zr) and 1 - Hf (M = Hf). The crystalline compounds form ion lattices with solvent-separated [(thf)₄Li]⁺ cations and [{(thf)Li}M(C₄H₈)₃]^– anions. The NMR spectra at –20 °C show magnetic equivalence of the M–CH₂ and of the β-CH₂ groups of the butane-1,4-diide ligands on the NMR time scale. Analogous reactions of MCl₄(thf)₂ with 1,4-dilithiobutane with a molar ratio of 1 : 2 proceed unclear. However, single crystals of [Li(thf)₄] [HfCl₅(thf)] ( 2 ) can be isolated with the hafnium atom in a distorted octahedral coordination sphere of five chloro and one thf ligand. NMR spectra allow to elucidate the time-dependent degradation of 1-Hf and 1-Zr in THF and toluene at 25 °C via THF cleavage. Addition of tmeda to a solution of 1-Zr allows the isolation of intermediately formed [{(tmeda)Li}₂Zr(nBu)₂(C₄H₈)₂] ( 3 ).     

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,Kristallstruktur und thermischer Abbau von Mg(H2O)6[B12H12] · 6 H2O

Synthesis, Crystal Structure, and Thermal Decomposition of Mg(H₂O)₆[B₁₂H₁₂] · 6 H₂O By reaction of an aqueous solution of the free acid (H₃O)₂[B₁₂H₁₂] with MgCO₃ and subsequent isothermic evaporation of the resulting solution to dryness, colourless, bead‐shaped single crystals of the dodecahydrate of magnesium dodecahydro closo‐dodecaborate Mg(H₂O)₆[B₁₂H₁₂] · 6 H₂O (cubic, F4₁32; a = 1643.21(9) pm, Z = 8) emerge. The crystal structure is best described as a NaTl‐type arrangement in which the centers of gravity of the quasi‐icosahedral [B₁₂H₁₂]^2— anions (d(B—B) = 178—180 pm, d(B—H) = 109 pm) occupy the positions of Tl^— while the Mg²⁺ cations occupy the Na⁺ positions. A direct coordinative influence of the [B₁₂H₁₂]^2— units at the Mg²⁺ cations is however not noticeable. The latter are octahedrally coordinated by six water molecules forming isolated hexaaqua complex cations [Mg(H₂O)₆]²⁺ (d(Mg—O) = 206 pm, 6×). In addition, six “zeolitic” water molecules are located in the crystal structure for the formation of a strong O—H^δ+···^δ—O‐hydrogen bridge‐bonding system. The evidence of weak B—H^δ—···^δ+H—O‐hydrogen bonds between water molecules and anionic [B₁₂H₁₂]^2— clusters is also considered. Investigations on the dodecahydrate Mg[B₁₂H₁₂] · 12 H₂O (≡ Mg(H₂O)₆[B₁₂H₁₂] · 6 H₂O) by DTA/TG measurements showed that its dehydration takes place in two steps within a temperature range of 71 and 76 °C as well as at 202 °C, respectively. Thermal treatment eventually leads to the anhydrous magnesium dodecahydro closo‐dodecaborate Mg[B₁₂H₁₂].     

Synthese und Kristallstrukturen der Nitrido‐Chloro‐Molybdate [Mg(THF)4{NMoCl4(THF)}2] · 4 CH2Cl2 und [Li(12‐Krone‐4)(NMoCl4)]2 · 2 CH2Cl2

Syntheses and Crystal Structures of the Nitrido‐chloro‐molybdates [Mg(THF)₄{NMoCl₄(THF)}₂] · 4 CH₂Cl₂ and [Li(12‐Crown‐4)(NMoCl₄)]₂ · 2 CH₂Cl₂ Both the title compounds as well as [Li(12‐crown‐4)₂]⁺MoNCl₄^– were made from MoNCl₃ and the chlorides MgCl₂ and LiCl, respectively, in dichloromethane suspensions in the presence of tetrahydrofuran and 12‐crown‐4, respectively. They form orange‐red moisture‐sensitive crystals, which were characterized by their IR spectra and partly by crystal structure analyses. [Mg(THF)₄{NMoCl₄(THF)}₂] · 4 CH₂Cl₂ ( 1 ): space group C2/m, Z = 2, lattice dimensions at –50 °C: a = 1736.6(1), b = 1194.8(1), c = 1293.5(2) pm; β = 90.87(1)°; R₁ = 0.037. In 1 the magnesium ion is coordinated octahedrally by the oxygen atoms of the four THF molecules and in trans‐position by the nitrogen atoms of the two [N≡MoCl₄(THF)]^– ions. [Li(12‐crown‐4)(NMoCl₄)]₂ · 2 CH₂Cl₂ ( 2 ): space group P 1, Z = 1, lattice dimensions at –70 °C: a = 930.4(1), b = 957.9(1), c = 1264.6(1) pm; α = 68.91(1)°, β = 81.38(1)°, γ = 63.84(1)°; R₁ = 0.0643. 2 forms a centrosymmetric ion ensemble in the dimeric cation of which, i. e. [Li(12‐crown‐4)]₂²⁺, the lithium ions on the one hand are connected to the four oxygen atoms each of the crown ether molecules in a way not yet known; and in addition, each of the lithium ions enters into a intermolecular Li–O bond with neighboring crown ether molecules under formation of a Li₂O₂ four‐membered ring. The two N≡MoCl₄^– counterions are loosely coordinated to one oxygen atom each of the crown ether molecules with Mo–O distances of 320.2 pm.     

Die Kristallstrukturen der Phosphanimin‐Komplexe [NaI(HNPPh3)3] und [SrI2(HNPPh3)2(THF)2] sowie des Natrium‐triphenylphosphaniminats [NaNPPh3]6

Crystal Structures of the Phosphaneimine Complexes [NaI(HNPPh₃)₃] and [SrI₂(HNPPh₃)₂(THF)₂], as well as of Sodium Triphenylphosphoraneiminate [NaNPPh₃]₆ [NaI(HNPPh₃)₃] ( 1 ) has been obtained as yellow, moisture sensitive crystals as an intermediate product of the synthesis of sodium triphenylphosphoraneiminate, [NaNPPh₃]₆ ( 2 ) from Ph₃PI₂ and sodium amide in liquid ammonia. Correspondingly, colourless crystals of [SrI₂(HNPPh₃)₂(THF)₂] ( 3 ) are formed from strontium amide and Ph₃PI₂ in liquid ammonia and subsequent recrystallisation of the primary product [SrI₂(HNPPh₃)₄] from thf solution. The complexes 1 – 3 are mainly characterized by crystal structure determinations. 1 · 0,5 thf: space group P3c1, Z = 4, lattice dimensions at 193 K: a = b = 1533.2(1); c = 2545.6(1) pm, R = 0.0417. 1 has a molecular structure in which the sodium atom is tetrahedrally coordinated by the iodine atom with a distance of 315.9 pm and by the nitrogen atoms of the three HNPPh₃ molecules with a distance of 238.9 pm. 2 · C₇H₈: space group P1, Z = 1, lattice dimensions at 213 K: a = 1457.1(1), b = 1484.9(1), c = 1502.7(1) pm; α = 116.32(1)°, β = 115.358(10)°, γ = 93.585(14)°; R = 0.0520. 2 has a molecular structure in which the six sodium atoms and the six nitrogen atoms of the (NPPh₃^–) groups form a hexagonal prism with approximate D_3d symmetry. 3 · 2 thf: space group P1, Z = 2, lattice dimensions at 193 K: a = 1042.9(1), b = 1337.4(1), c = 2095.1(1) pm; α = 90.130(8)°, β = 96.310(8)°, γ = 111.985(8)°; R = 0.0310. 3 has a molecular structure in which the strontium atom is octahedrally coordinated by the iodine atoms, by the nitrogen atoms of the HNPPh₃ molecules and by the oxygen atoms of the thf molecules, all ligands being in trans‐position to one another.     

Replacement of the Common Chromium Source CrCl3(thf)3 with Well-Defined [CrCl2(μ-Cl)(thf)2]2

CrCl₃(thf)₃ is a common starting material in the synthesis of organometallic and coordination compounds of Cr. Deposited as an irregular solid with no possibility of recrystallization, it is not a purity guaranteed chemical, causing problems in some cases. In this work, we disclose a well-defined form of the THF adduct of CrCl₃ ([CrCl₂(μ-Cl)(thf)₂]₂), a crystalline solid, that enables structure determination by X-ray crystallography. The EA data and XRD pattern of the bulk agreed with the revealed structure. Moreover, its preparation procedure is facile: evacuation of CrCl₃·6H₂O at 100 °C, treatment with 6 equivalents of Me₃SiCl in a minimal amount of THF, and crystallization from CH₂Cl₂. The ethylene tetramerization catalyst [iPrN{P(C₆H₄-p-Si(nBu)₃)₂}₂CrCl₂]⁺[B(C₆F₅)₄]⁻ prepared using well-defined [CrCl₂(μ-Cl)(thf)₂]₂ as a starting material exhibited a reliably high activity (6600 kg/g-Cr/h; 1-octene selectivity at 40 °C, 75%), while that of the one prepared using the impure CrCl₃(thf)₃ was inconsistent and relatively low (~3000 kg/g-Cr/h). By using well-defined [CrCl₂(μ-Cl)(thf)₂]₂ as a Cr source, single crystals of [(CH₃CN)₄CrCl₂]⁺[B(C₆F₅)₄]⁻ and [{Et(Cl)Al(N(iPr)₂)₂}Cr(μ-Cl)]₂ were obtained, allowing structure determination by X-ray crystallography, which had been unsuccessful when the previously known CrCl₃(thf)₃ was used as the Cr source.     

Structural and Solution Studies of two Mercury(II) Complexes with [1,3‐Bis(2‐ethoxy)benzene]triazene

The reaction of [1,3‐bis(2‐ethoxy)benzene]triazene, [ HL ], with Hg(SCN)₂ and Hg(CH₃COO)₂, resulted in the formation of the complexes [Hg L (SCN)] ( 1 ) and [Hg L ₂] · CH₃OH ( 2 ). They were characterized by means of X‐ray crystallography, CHN analysis, FT‐IR, ¹H NMR, and ¹³C NMR spectroscopy. The structure of compound 1 consists of two independent complexes in which the Hg^II atoms are stacked along the crystallographic a axis to form infinite chains. Each Hg^II atom is chelated by one L ligand and one SCN ligand, whereas in compound 2 , the Hg^II atom is surrounded by two L ligands. In addition, 1D chains formed by metal–π interactions are connected to each other by C–H ··· π stacking interactions in the structure of 1 , which results in a 2D architecture. An interesting feature of compound 2 is the presence of C–H ··· π edge‐to‐face interactions.     

Cobalt Chalcogenide Clusters. Synthesis,Characterization and DFT Calculations of [Co4Se2(CO)10] and [Co4Te2(CO)11]. Crystal Structure of [Co8Se4(CO)16(μ‐dppa)2]

The reactions of [Co₂(CO)₈] with E(SiMe₃)₂ (E = Se, Te) in CH₂Cl₂ result in the formation of the compounds [Co₄Se₂(CO)₁₀]> ( 1 ) and [Co₄Te₂(CO)₁₁] ( 2 ), respectively. Both cluster complexes have similar molecular structures in which the cobalt atoms form four‐membered rings with μ₄‐bridging chalcogen atoms (Se and Te) above and below the plane of the metal atoms and the carbonyl ligands as either terminal or μ₂‐bridging ligands. DFT‐calculations for both compounds have been carried out in order to obtain some more information about their electronic distribution. In the presence of the phosphine Ph₂PC≡CPPh₂ (dppa), the reaction of [Co₂(CO)₈] with Se(SiMe₃)₂ leads to the formation of [Co₈Se₄(CO)₁₆(μ‐dppa)₂] ( 3 ). During the reaction two molecules of [Co₂(CO)₈] have been added to the acetylene groups of the dppa ligands, whilst the remaining cobalt atoms coordinate to the phosphorus atoms of the phosphine. In this compounds the selenium atoms act as μ₃‐ligands, bridging the metal atoms bonded to the phosphorus with those bonded to the acetylene groups.