Trinuclear Anion Research Articles

Polynuclear oxomolybdates(VI): Products of inadvertent oxidation of molybdenum(V) species

Unplanned oxidation of molybdenum(V) in the presence of carboxylic acid afforded three fully-oxidized polynuclear oxomolybdates. In very similar reaction mixtures, the initial oxidation state of the metal ion was retained and species with the frequently-encountered dinuclear {MoV(O)(μ2-O)2MoV(O)}2+ core formed. The chosen carboxylic acid contained either two COOH groups or another functional group, i.e., OH moiety. The carboxylic acid was introduced with the idea that with both of its functional groups engaged in coordination discrete clusters composed of the {MoV(O)(μ2-O)2MoV(O)}2+ units and the organic linkers would form. Reaction systems with dimethylmalonic acid (dmmH2) yielded two products, (Bu4N)2[Mo3O8(dmm)2] (1) with a trinuclear anion and [{MoV2O4Py2(dmmMe)}2(OCH3)2] (2) (Py = pyridine, dmmMe− = monomethyl dimethylmalonate ester) as the non-oxidized counterpart. The dmm2− ion engaged in coordination to Mo(VI) centers both carboxylate groups, whereas the dmmMe− ion coordinated to Mo(V) centers via its carboxylate moiety in a bidentate bridging mode. Reactions with mandelic (H2man) acid resulted in {(C6H5)4P}2[Mo4O10(OCH3)4Cl2] (3) with a tetranuclear core and in (PyH)3[MoV2O4Cl4(Hman)] (4). Only the non-oxidized compound 4 contains coordinated mandelate ion, whereas the role of the acid in the synthesis of 3 became that of a templating agent. (PyH)4[Mo8O26Py2] (5) with an octanuclear anion is a fully-oxidized compound obtained from the reaction mixture with succinic acid. The compounds were characterized by X-ray structure analysis, bond valence sum (BVS) calculations, IR vibrational and 1H NMR spectroscopy. The TG and DSC experiments were performed on fully-oxidized compounds. Powder X-ray diffraction has confirmed molybdenum(VI) oxide as the end product of the thermal decomposition of (Bu4N)2[Mo3O8(dmm)2] (1) and (PyH)4[Mo8O26Py2] (5) in the air atmosphere.

Two heterometallic complexes with a new macrocyclic oxamido complex ligand

A new macrocyclic oxamido-nickle(II) complex Na2NiL was synthesized. L denotes the doubly deprotonated forms of (13Z, 19Z)-16-methyl-6,7-dioxo-5,6,7,8-tetrahydrotriben-zo[b,f,l][1,4,8,11]tetraazacyclotetradecine- 13,20-dicarboxylate. Based on the complex ligand Ni(L2–), two heterometallic complexes [Ca2(NiL)2(H2O)8] · 10H2O (I) and [Co(NiL)2(H2O)2][Co(H2O)6] · 2.8H2O (II) were prepared. X-ray single crystal analyses (CCDC nos. 914618 (I), 914616 (II)) revealed that [Ca2(NiL)2(H2O)8] in I is a molecular box and the trinuclear complex anion [Co(NiL)2(H2O)2]2–in II is centrosymmetric. Thermogravimetric analyses showed that I exhibited moderately good stability and Co(II) catalyzed the thermal decomposition of II.

Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl.

Grignard reagents RMgCl and their so-called turbo variant, the highly reactive RMgCl⋅LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity-enhancing effect. A combination of electrospray-ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion-ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgCl⋅LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron-rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents.

Diphosphorus-bridged heterometallic anions and hydrides derived from reactions of complex [Mo2Cp2(μ-PCy2)(μ-κ2:κ2-P2)(CO)2]− with precursors of 16-electron metal carbonyl fragments

Reaction of the Li+ salt of the title anion with [Fe2(CO)9] or tetrahydrofuran adducts of formula [MLn(THF)] gave the trinuclear species Li[Mo2MCp2(μ-PCy2)(μ-κ2:κ2:κ1-P2)(CO)2Ln], (MLn = Fe(CO)4, MnCp′(CO)2, Mo(CO)5, W(CO)5; Cp′ = η5-C5H4Me), some of which could be isolated as the corresponding PPN+ salts (PPN = N(PPh3)2). These products followed from further coordination of the P2 ligand to the incoming 16-electron MLn fragment via the lone electron pair at its basal P atom, and displayed characteristically high P–P couplings (1JPP ca. 500Hz) indicative of retention of a strong P–P bond. In addition, these products underwent a fluxional process derived from the swing of the P2 unit around the Mo–Mo axis with concomitant exchange of the MLn fragment between P atoms. Reaction of the title anion with excess of the above carbonyl complexes involved further addition of a second MLn fragment to the P atom still bearing a lone electron pair, thus leading to the tetranuclear anionic derivatives Li[Mo2M2Cp2(μ-PCy2)(μ-κ2:κ2:κ1:κ1-P2)(CO)2L2n], most of which could be isolated as the corresponding PPN+ salts. For the Mo and W derivatives, this reaction also involved a trans to cis isomerisation at the Mo2(CO)2 moiety of the parent anion. All tetranuclear anions displayed fluxional behaviour in solution, comparable to that of the parent anion in the case of the Fe and Mn derivatives, but likely involving rotation of the P2 ligand in the case of the cisoid Mo and W derivatives. Protonation of the above trinuclear anions with [NH4]PF6 led to decomposition except for the Mn complex, this yielding a poorly characterized diphosphenyl derivative [MnMo2Cp2Cp′(μ-κ1,η2:κ2:κ1-HP2)(μ-PCy2)(CO)4] displaying an agostic-like P–H–Mo interaction, eventually decomposing to the known phosphide-bridged complex [MnMo2Cp2Cp′(μ3-P)(μ-PCy2)(CO)4]. In contrast, protonation of the tetranuclear anions yielded the unsaturated hydride derivatives [Mo2M2Cp2(H)(μ-PCy2)(μ-κ2:κ2:κ1:κ1-P2)(CO)L2n], (M = Mn, Mo, W), with a formal intermetallic double bond (Mo–Mo = 2.7412(6) Å for the tungsten complex) as a result of loss of a CO ligand from the Mo2(CO)2 moiety after protonation, probably favoured by the presence of excess of adducts [MLn(THF)] in these reaction mixtures.

Preparation, supramolecular self-organization and thermal behavior of polymeric complex of composition ([Au{S2CN(C3H7)2}2]3[Bi3Cl12]) n with unusual geometry of bismuth(III) complex anion

A reaction of freshly precipitated bismuth(III) N,N-dipropyldithiocarbamate (PDtc) with AuCl3 solution in 2 M HCl was studied. A heteropolynuclear gold(III)-bismuth complex of ionic type [Au{S2CN(C3H7)2}2]3[Bi3Cl12] (I) was isolated by crystallization of products of the heterogeneous reaction from acetone-chloroform (1: 1) solution. Crystal and supramolecular structure of compound I established by X-ray diffraction study includes structurally nonequivalent complex cations [Au{S2CN(C3H7)2}2]+ related to each other as conformers (hereinafter cations A, B, C, and D) in 1: 1: 2: 2 ratio. Due to secondary Au⋯S bonds (3.386–3.617 A), the isomeric cations form trinuclear species of two types: [C⋯A⋯C] and [D⋯B⋯D] that differ in the character of intercationic binding and Au-Au distances. Relatively weak aurophilic Au⋯Au bonds (3.4704(3) A) unite the neighboring cationic triads into zigzag polymeric chains of type (⋯[C⋯A⋯C]⋯[D⋯B⋯D]⋯)n oriented along the crystallographic axis b. The spatial isolation of neighboring chains is provided by discrete trinuclear anions [Bi3Cl12]3− where metal atoms bind four bridging (μ2 and μ3) chlorine atoms, while each bismuth atom forms distorted octahedral chromophore [BiCl6]. The complex tribismuth anion in the structure I is the first example of [Bi3Cl12]3− anion of angle rather than linear structure: Bi(1)Bi(2)Bi(3) angle is 72.358°. The thermal behavior of compound I was studied by simultaneous thermal analysis. The multistage process of thermal destruction includes the thermolysis of dithiocarbamate portion of the complex and [Bi3Cl12]3− accompanied by reduction of gold(III) to metal and release of BiCl3 (followed by its evaporation) and partial formation of Bi2S3. In the temperature range 680–760°C, bismuth sulfide undergoes oxidation to (BiO)2SO4, which decomposes above 760°C to give Bi2O3. Residue after thermolysis of compound I is gold metal and bismuth(III) oxide.

An ion pair scandium hydride supported by a dianionic (NNNN)-type macrocycle ligand

A scandium hydride supported by a (NNNN)-type macrocycle consists of a trinuclear cation and a trinuclear anion. The anion shows significantly higher reactivity.

A W(V)–Mn(III) bimetallic assembly built by manganese(III) Schiff-base and octacyanotungstate(V) building blocks: Structure and magnetic property

A new cyano-bridged bimetallic complex [Mn(5-Clsaltmen) (H2O)(CH3OH)]{[Mn(5-Clsaltmen)(H2O)] W(CN)8[Mn(5-Clsaltmen)(CH3OH)]}·3.5H2O·2CH3OH [5-Clsaltmen=N,N′-(1,1,2,2-tetramethylethylene) bis(5-chlorosalicylideneiminato) dianion] (1) was synthesized and structurally characterized by X-ray single-crystal diffraction. The structure of 1 consists of the asymmetric V-shaped Mn–W–Mn trinuclear anions, in which W(V) coordinates with [Mn(5-Clsaltmen)(H2O)]+ and [Mn(5-Clsaltmen)(CH3OH)]+ through the neighboring cyano bridges, isolated cations [Mn(5-Clsaltmen) (H2O)(CH3OH)]+ and lattice water and methanol molecules. The magnetic studies for 1 reveal that antiferromagnetic interactions (J=−4.6cm−1) between WV and MnIII centers is operating within the trimer.

Synthesis and characterization of cobalt(II) and manganese(II) xylaratogermanates: The molecular and crystal structures of the [M(H2O)6][Ge(μ3-L)2{M(H2O)2}2] · 4H2O · nCH3CN Complexes (M = Co, n = 0; M = Mn, n = 1)

A synthetic procedure was developed, and heteropolynuclear coordination compounds—the products of the interaction of germanium tetrachloride with xylaric (trihydroxyglutaric) acid HOOC-CH(OH)-CH(OH)-CH(OH)-COOH (H5L) and the acetates of the 3d metals Mn(II) and Co(II)—were prepared. The compounds were characterized by elemental analysis, thermogravimetry, and IR spectroscopy. The X-ray diffraction analysis of the [M(H2O)6][Ge(μ3-L)2{M(H2O)2}2] · 4H2O · nCH3CN complexes, where M = Co, n = 0 (I) and M = Mn, n = 1 (II), was performed. The crystals of I are monoclinic, a = 10.752(2) A, b = 11.830(2) A, and c = 10.772(2) A, β = 94.741(3)°, V = 1365.4(5) A3, Z = 2, space group P21/n, R1 = 0.0309 for 3200 reflections with I > 2σ(I). The crystals of II are triclinic, a = 9.5330(17) A, b = 9.7415(17) A, and c = 10.3935(18) A, α = 115.024(2)°, β = 97.580(3)°, γ = 111.535(3)°, V = 764.9(2)A3, Z = 1, space group $$P\bar 1$$ , R1 = 0.0621 for 3028 reflections with I > 2σ(I). The bimetallic anions [Ge(μ3-L)2{M(H2O)2}2]2−, the cations [M(H2O)6]2+, and crystal water molecules form the basis of compounds I and II (the acetonitrile molecule is also a constituent of compound II). In the centrally symmetrical trinuclear complex anion, the Ge(1) atom is bound to two M(1) atoms through two completely deprotonated bridging ligands. The Ge(1) atom is coordinated to the six alcohol oxygen atoms of two ligands L5− at the apexes of a distorted octahedron (the average Ge(1)-O distances in I and II are 1.8858(14) and 1.892(3)A, respectively). The coordination polyhedron of the M(1) atom in the complex anion is a strongly distorted octahedron. The base of the coordination polyhedron is formed by the two bridging alcohol oxygen atoms (the average M(1)-O distances in I and II are 2.1756(14) and 2.255(3) A, respectively) of two L5− ligands and by the oxygen atoms of two water molecules (the average M(1)-O distances in I and II are 2.0693(17) and 2.175(4) A, respectively). In the centrally symmetrical complex cation, the coordination polyhedron of the M(2) atom is a somewhat distorted octahedron. The M(2)-O(H2O) bond lengths in I and II vary in the ranges of 2.0137(17)-2.1555(17) and 2.140(5)-2.172(4) A, respectively (the average lengths are 2.0375(17) and 2.166(4) A, respectively). The cations and anions are joined by a branched system of hydrogen bonds.

Organic cations controlling the nuclearity of copper(ii) 2,5-pyridinedicarboxylates

Depending on the organo-cation mononuclear or polynuclear copper(II) 2,5-pyridinedicarboxylates (L) are formed. Mononuclear complexes with [ML2(H2O)] anions are formed when the cations are derived from ethylenediamine (en), N,N,N′,N′-tetramethylethylenediamine (tmen), 1,5-diaminopentane (dap) and 1,4-diazabicyclo[2.2.2]octane (dabco). The use of 4-amino-benzylamine (4aba) as the cation source leads to the hexa-coordinated mononuclear complex [CuL2(H4aba)2]·8H2O. The use of 1,8-diaminooctane (dao) results in a trinuclear complex with the [Cu3L6]6− anion. The trinuclear anion has copper ions in a square pyramidal and square planar geometry. The use of diethylenetetramine (deta) led to a coordination polymer which had unique hexa and penta coordinated copper ions. It is comprised of dinuclear copper 2,5-pyridinedicarboxylates bridged by mononuclear [ML2]2− units through side on contacts between the carbonyls on the dinuclear part. The 8-aminoquinolinium cations act as counter ions of the coordination polymer with [CuL2]2− repeat units. In this coordination polymer, the cations are π-stacked in one dimension. The variation in coordination numbers and the types of chains in the coordination polymers are described.

Four new spin-crossover salts of [Fe(3-bpp)2]2+ (3-bpp = 2,6-bis[1H-pyrazol-3-yl]pyridine)

Four new salts of the well-known spin-crossover centre [Fe(3-bpp)2]2+ are described: [Fe(3-bpp)2][M(CN)2]2 (M=Ag, 1; M=Au, 2), [Fe(3-bpp)2][Au(SCN)2]2 (3) and [Fe(3-bpp)2][BPh4]2 (4) are reported. Monohydrate crystals of 1 and 2 are isostructural, and are better formulated as [Fe(3-bpp)2]2[M(CN)2][M3(CN)6]·2H2O (M=Ag or Au) with the mononuclear and trinuclear anion sites being disordered within each anion dyad. These groups are linked into a 2D network topology through N–H⋯X (X=N or O) hydrogen bonding between the cations and the cyanometallate anions, and the lattice water. In contrast, the complex cations in the solvate 4·2CH3NO2·(C2H5)2O are completely encapsulated by phenyl groups from the BPh4− anions. Dried powder samples of 1–4 all exhibit very gradual thermal spin-state transitions centred at 198⩽T½⩽291K. ES mass spectrometry of 1–3 implies that extensive ligand exchange between the iron and coinage metal ions occurs in solution. Solid 1 and 2 are not emissive at room temperature upon irradiation in the UV.

Synthesis and structure of antimony iodide complexes: [Ph3MeP] + 2 [SbI5]2−, [Ph3MeP] + 3 [Sb3I12]3−·Me2C=O, [Ph3MeP] + 3 [Sb3I12]3−, and [Ph3MeP] + 3 [Sb2I9]3−

Complexes with antimony-containing anions, [Ph3MeP]+2[SbI5]2− (I), [Ph3MeP]+2[Sb3I12]3− (II), [Ph3MeP]+3[Sb3I12]3− · Me2C=O (III), and [Ph3MeP]+3[Sb2I9]3− (IV), were synthesized by reacting triphenylmethylphosphonium iodide with antimony iodide. The central atom in the cations of the complexes has a distorted tetrahedral coordination. In the trinuclear anions of complexes II and III, each of the terminal SbI3 groups is bound to the central Sb atom through two μ2- and one μ3 iodine bridges (SbSbSb angles are 103.0° and 102.2°, respectively). In the binuclear anion of complex IV, antimony atoms are linked with each other via three bridging iodine atoms.

Synthesis, properties, and molecular and crystal structure of hexaaquacopper(IV) bis(diaquacuprato-μ3-trihydroxyglutarato)germanate(IV) dihydrate [Cu(H2O)6][Ge(μ3-Thgl)2{Cu(H2O)2}2] · 2H2O

A procedure for the synthesis of the heteropolymetallic germanium(IV) and copper(II) complex with trihydroxyglutaric acid (H5Thgl) [Cu(H2O)6][Ge(μ3-Thgl)2{Cu(H2O)2}2] · 2H2O (I) was developed and the complex was isolated for the first time in the solid state. The product was characterized by elemental analysis, powder X-ray diffraction, thermogravimetry, and IR spectroscopy. Compound I was studied by X-ray crystallography. The crystals are monoclinic, a = 10.216(2)A, b = 12.272(3)A, c = 10.679(2)A, β = 93.13(3)°, V = 1336.9(5)A3, Z = 2, space group P21/n, R1 = 0.0261 for 3616 reflections with I > 2σ(I). Compound I is composed of bimetallic [Ge(μ3-Thgl)2{Cu(H2O)2}2]2− anions, [Cu(H2O)6]2+ cations, and water molecules of crystallization. In the centrosymmetric trinuclear complex anion, the Ge(1) atom is bound by two fully deprotonated bridging ligands to two Cu atoms. The Ge(1) atom is coordinated at distorted octahedron vertices by six hydroxyl oxygen atoms of two Thgl5− ligands (average Ge(1)-O distance is 1.8874(13)A). The Cu coordination polyhedron in the anion is an extended square pyramid (4 + 1) formed by the bridging hydroxyl oxygen atom (Cu(1)-O(3), 2.0039(12) A), two carboxyl oxygen atoms (average CU(1)-O distance is 1.9674(14)A) of two Thgl5− ligands, and two water oxygen atoms in equatorial and axial positions (Cu(1)-O, 1.9761(13) and 2.3643(14)A, respectively). In the centrosymmetric cation, the Cu coordination polyhedron is an extended square bipyramid (4 + 2). The equatorial Cu-O bond length is 1.9428(14) A (average), the axial Cu-O bond is elongated to 2.5151(14)A. The cations and anions are combined by H-bonds.

Heterometallic coordination compounds of dipicolinic acid with Ce(III, IV) and Cu(II): Synthesis, crystal structure and spectral studies

Reaction of pyridine-2,6-dicarboxylic acid (dipicH 2) with ammonium ceric nitrate and Cu(II) salts yielded three heterometallic compounds all of which contain [Ce(dipic) 3] 2− linked to aquo-Cu(II) complex units. Part of the Ce(IV) gets reduced by solvent during the reaction leading to [(Ce(dipic) 3Ce(H 2O) 8) 2Cu(H 2O) 4][Ce(dipic) 3] 2·12H 2O ( 1). Other lanthanide(III) ions could take the place of Ce(III) as demonstrated by the preparation of [(Ce(dipic) 3La(H 2O) 8) 2Cu(H 2O) 4][Ce(dipic) 3] 2·12H 2O ( 4), which is isomorphous with compound 1. [Ce(dipic) 3Cu(H 2O) 4]·8H 2O ( 2) is a one-dimensional coordination polymer in which two types of aquo-Cu(II) complex units which differ in the orientation of the tetragonal axis alternate along the chain. The central Cu(H 2O) 2 2+ unit in the trinuclear anion of [Cu(H 2O) 6][Ce(dipic) 3Cu(H 2O) 2Ce(dipic) 3]·8H 2O ( 3) is chelated by two carboxylate groups in trans positions in off-axis mode. In all the four complexes, the Cu(II) centres are magnetically isolated leading well-resolved EPR spectra in polycrystalline samples.

Tris(tetramethylammonium) tetra-μ2-sulfido-tetrasulfidocopper(I)dimolybdenum(VI)N,N-dimethylformamide solvate

The title compound, (C4H12N)3[CuMo2S8]·C3H7NO, was obtained from the self-assembly of tetra­thio­molybdate, tetra­methyl­ammonium nitrate and cuprous sulfide in dimethyl­formamide (DMF). The asymmetric unit contains three (NMe4)+ cations, one [Mo2S8Cu]3− anion and one DMF solvent mol­ecule, and no obvious inter­actions are observed between these species. The trinuclear anion can be viewed as fused [MoS4Cu]− units sharing a copper center. The geometric parameters of the trivalent anion are comparable to those reported for other related salts including isomorphous anions, namely (NEt4)2(PPh4)[Mo2S8Cu] (a) and (Ph3P=N=PPh3)2(NEt4)[W2S8Cu]·2CH3CN (b). However, the Mo—Cu—Mo angle is found to be 160.24 (3)° for the title salt, while this angle is 162.97 (2)° in (a) and the W—Cu—W angle is 170.3 (2)° in (b), indicating that the largest deviation from linearity is in the title compound.

Reactivity and kinetic studies of (NH 4) 2(MoS 4) in acidic aqueous solution: Possible relevance to the angiostatic function of the [formula omitted] ligand

Although addition of mineral acids to WS 4 2 - in water is known to lead to aggregation and formation of various polynuclear thiotungstate anions, acid hydrolysis of the MoS 4 2 - anion is reported to give mainly MoS 3 or MoS 2 as hydrolysis products. Knowledge of the resulting product(s) from such reactions has implications on the use of tetrathiomolybdate ( MoS 4 2 - ) as both a potential anti-tumor drug and for the treatment of Wilson’s disease. In this investigation, reaction of HCl with MoS 4 2 - in water was monitored as a function of time. Reaction mixtures of both 1:1 and 2:1 mole ratios of the acid to MoS 4 2 - were examined, as well as MoS 4 2 - reactions in simulated human stomach fluids at pH of ∼2 and 3. Monitoring by electrospray mass spectrometry (ESMS), Fourier transform infrared (FTIR), and UV–visible spectroscopy clearly has revealed the formation of complex mixtures of polynuclear thiomolybdates (Mo 2–Mo 18). Generally, a two-stage consecutive reaction sequence occurs. A faster stage ( k = 7.0–7.9 × 10 −2 min −1), which seems to extend to trinuclear thiomolybdate species, followed by a slower second stage ( k = 5.4–15.2 × 10 −4 min −1) to higher polynuclear thiomolybdates. Under acidic conditions (e.g. pH ∼ 3) that could also mimic some human stomach fluids, and under anaerobic atmosphere where the generated hydrogen sulfide is prevented from escaping from the reaction vessel, Mo 3 S 9 2 - predominates over an extended reaction period. In similar reactions under aerobic conditions and where the hydrogen sulfide is irretrievably lost from the reaction mixture the binuclear ( Mo 2 O a S 10 - a 2 - ; a = 0 – 3 ) and trinuclear ( Mo 3 O b S 9 - b 2 - ; b = 1 – 3 ) anions predominate.

Me4N]3[(WOS3)2Ag]×MeCN — An Acetonitrile Solvate with Linear Complex Anions.

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Me4N]3[(WOS3)2Ag]·MeCN – An Acetonitrile Solvate with Linear Complex Anions

The title compound was prepared by the reaction of [Me4N]2WOS3 with AgCN in MeCN at room temperature and slow crystallisation in the refrigerator. It was characterized by IR and mass spectroscopy. It crystallizes in the orthorhombic space group Pnma (No. 62) with unit cell dimensions a = 19.648(7), b = 27.878(12), c = 11.494(3) Å , Z = 8. The crystal structure was determined from single crystal diffractometer data (Mo-Kα radiation) and refined to R = 0.077. The structure is composed of mixed double layers containing the linear trinuclear anion [(WOS3)2Ag]3− and cations separated by a layer formed by cations and solvating acetonitrile molecules.

Morpholin als ambidenter Ligand

AbstractMorpholine as Ambident LigandThe reaction of MeInCl2 with Li‐morpholinate [Li(Morph)] at 20 °C in THF gave after work‐up and recrystallization from diglyme the salt [Li(Diglyme){In3Me2Cl4(Morph)4}]·Diglyme (1). The treatment of the reaction mixture of MesInCl2/Li(Morph) with wet THF yield as only isolated compound the coordination polymer [Li6Cl6(HMorph)3] (2). Under similar conditions the reaction of InCl3 with Li(Morph) led after work‐up in wet THF to [Li(Diglyme)2][InCl4(HMorph)2] (3). 1 – 3 were characterized by NMR and IR spectroscopy as well as by X‐ray analysis. According to this, 1 contains the trinuclear anion [In3Me2Cl4(Morph)4]− in which one of the morpholinate ligands is coordinated via N atom to the In3+ ions, while the O atom belongs to the coordination sphere of the Li+ ion. In 2, LiCl forms a hexagonal heteroprismn, in which the morpholine molecules are responsible for a 3d network via coordination of both Lewis‐basic heteroatoms. 3 contains trans‐[InCl4(Hmorph)2]− ions, connected by hydrogen bonding along [011].

The preparation and structural characterisation of thiolato anions of bismuth(III)

The preparation and structures of the bismuth thiolato anions [Bi 2(SC 6F 5) 6(μ-SC 6F 5)] − and [Bi 2(SC 6F 5) 6(μ-SC 6F 5) 2] 2− and the halothiolato anions [Bi 2(SC 6F 5) 6(μ-Br)] −, [Bi 2(SC 6F 5) 6(μ-Cl) 2] 2− and [Bi 3(SC 6F 5) 9(μ-Br) 2] 2− are described. All compounds have been isolated from reactions between Bi(SC 6F 5) 3 and ammonium or phosphonium halides. The basic structural units in the dinuclear species are of two types namely [Bi 2(SR) 6(μ-X)] − and [Bi 2(SR) 6(μ-X) 2] 2−, where X=thiolate or halide. In the former case the single bridging groups occupy an axial site within the disphenoidal (equatorially vacant, trigonal bipyramidal) geometry around the bismuth centres whereas in the latter the two bridging groups occupy cis basal sites in square based pyramidal bismuth environments. The trinuclear anion [Bi 3(SC 6F 5) 9(μ-Br) 2] 2− has features in common with the basic [Bi 2(SC 6F 5) 6(μ-Br)] − unit.

Bis(tetraethylammonium) μ-tetrathiomolybdato(VI)-bis[chlorocopper(I)

The title compound, (Et4N)2[MoS4(CuCl)2], consists of tetraethyl­ammonium cations of expected geometry, and trinuclear anions in which two opposite edges of an MoS42− tetrahedron are bridged by CuCl units. The bridging of Mo and Cu centres by all four S atoms hardly affects the tetrahedral coordination of Mo and leads to a distorted trigonal planar coordination geometry for Cu, with both chloro ligands terminal.