Investigations of the TeCl(4)-(t)BuNHLi Reaction: Synthesis, X-ray Structures, and Fluxional Behavior of the Tellurium-Nitrogen Compounds [Li(2)Te(N(t)Bu)(3)](2), {[LiTe(N(t)Bu)(2)(NH(t)Bu)](2)LiCl}(2), and {Te(2)(N(t)Bu)(4)[LiTe(N(t)Bu)(2)(NH(t)Bu)]LiCl}(2)

The reaction of (t)BuNHLi with TeCl(4) in toluene at -78 degrees C produces (t)BuNTe(&mgr;-N(t)Bu)(2)TeN(t)Bu (1) (55%) or [((t)BuNH)Te(&mgr;-N(t)Bu)(2)TeN(t)Bu]Cl (2) (65%) for 4:1 or 7:2 molar ratios, respectively. The complex {Te(2)(N(t)Bu)(4)[LiTe(N(t)Bu)(2)(NH(t)Bu)]LiCl}(2) (5) is obtained as a minor product (23%) from the 4:1 reaction. It is a centrosymmetric dimer in which each half consists of the tellurium diimide dimer 1 bonded through an exocyclic nitrogen atom to a molecule of LiTe(N(t)Bu)(2)(NH(t)Bu) which, in turn, is linked to a LiCl molecule. Crystals of 5 are monoclinic, of space group C2/c, with a = 27.680(6) ?, b = 23.662(3) ?, c = 12.989(2) ?, beta = 96.32(2) degrees, V = 8455(2) ?(3), and Z = 4. The final R and R(w) values were 0.046 and 0.047. At 65 degrees C in toluene solution, 5 dissociates into 1, LiCl, and {[LiTe(N(t)Bu)(2)(NH(t)Bu)](2)LiCl}(2) (4), which may also be prepared by treatment of [Li(2)Te(N(t)Bu)(3)](2) (6) with 2 equiv of HCl gas. The centrosymmetric structure of 6 consists of a distorted hexagonal prism involving two pyramidal Te(N(t)Bu)(3)(2)(-) anions linked by four Li atoms to give a Te(2)N(6)Li(4) cluster. Crystals of 6 are monoclinic, of space group P2(1)/c, with a = 10.194(2) ?, b = 17.135(3) ?, c = 10.482(2) ?, beta = 109.21(1) degrees, V = 1729.0(5) ?(3), and Z = 2. The final R and R(w) values were 0.026 and 0.023. VT (1)H and (7)Li NMR studies reveal that, unlike 1, compounds 2, 4, and 6 are fluxional molecules. Possible mechanisms for these fluxional processes are discussed.     

New Thioantimonates(III) with Different Sb:S Ratios: Solvothermal Syntheses and Crystal Structures of [(C3H10NO)(C3H10N)][Sb8S13], [(C2H8NO)(C2H8N)(CH5N)][Sb8S13], [(C6H16N2)(C6H14N2)][Sb6S10], and [C8H22N2][Sb4S7]

Four new thioantimonates(III) with compositions [(C₃H₁₀NO)(C₃H₁₀N)][Sb₈S₁₃] ( 1 ) (C₃H₉NO = 1‐amino‐3‐propanol, C₃H₉N = propylamine), [(C₂H₈NO)(C₂H₈N)(CH₅N)][Sb₈S₁₃] ( 2 ) (C₂H₇NO = ethanolamine, C₂H₇N = ethylamine, CH₅N = methylamine), [(C₆H₁₆N₂)(C₆H₁₄N₂)][Sb₆S₁₀] ( 3 ) (C₆H₁₄N₂ = 1,2‐diaminocyclohexane) and [C₈H₂₂N₂][Sb₄S₇] ( 4 ) (C₈H₂₀N₂ = 1,8‐diaminooctane) were synthesized under solvothermal conditions. Compound 1 : triclinic space group P$\bar{1}$ , a = 6.9695(6) Å, b = 13.8095(12) Å, c = 18.0354(17) Å, α = 98.367(11), β = 96.097(11) and γ = 101.281(11)°; compound 2 : monoclinic space group P2₁/m, a = 7.1668(5), b = 25.8986(14), c = 16.0436(11) Å, β = 96.847(8)°; compound 3 : monoclinic space group P2₁/n, a = 11.6194(9), b = 10.2445(5) Å, c = 27.3590(18) Å, β = 91.909(6)°; compound 4 : triclinic space group P$\bar{1}$ , a = 7.0743(6), b = 12.0846(11), c = 13.9933(14) Å, α = 114.723(10), β = 97.595(11), γ = 93.272(11)°. The main structural feature of the two atoms thick layered [Sb₈S₁₃]^2– anion in 1 are large nearly rectangular pores with dimensions 11.2 × 11.7 Å. The layers are stacked perpendicular to [100] to form tunnels being directed along [100]. In contrast to 1 the structure of 2 contains a [Sb₈S₁₃]^2– chain anion with Sb₁₂S₁₂ pores measuring about 8.9 × 11.5 Å. Only if longer Sb–S distances are considered as bonding interactions a layered anion is formed. The chain anion [Sb₆S₁₀]^2– in compound 3 is unique and is constructed by corner‐sharing SbS₃ pyramids. Two symmetry‐related single chains consisting of alternating SbS₃ units and Sb₃S₃ rings are bound to Sb₄S₄ rings in chair conformation. Finally, in the structure of 4 the SbS₃ and SbS₄ moieties are joined corner‐linked to form a chain of alternating SbS₄ units and (SbS₃)₃ blocks. Neighboring chains are connected into sheets that contain relatively large Sb₁₀S₁₀ heterorings. The sheets are further connected by sulfur atoms generating four atoms thick double sheets.     

Syntheses and structures of two chiral zincophosphite compounds: [Zn(C8H8N2)(HPO3)] and (C6H13N2)[Zn3(C6H12N2)(HPO3)3(H2PO3)

Employing achiral organic amines (2-methylbenzimidazole and 1,4-diazabicyclo[2.2.2]octane) as the structure-directing agent and ligand, two chiral zincophosphites, [Zn(C(8)H(8)N(2))(HPO(3))] 1 and (C(6)H(13)N(2))[Zn(3)(C(6)H(12)N(2))(HPO(3))(3)(H(2)PO(3))] 2, have been hydro(solvo)-thermally synthesized, crystallizing in the chiral space group P2(1)2(1)2(1). Single-crystal structural analysis reveals that compound 1 consists of alternating ZnO(3)N and HPO(3) units exhibiting a neutral one-dimensional chiral chain. Interestingly, the organic ligands interact with the inorganic chain via hydrogen-bonds in hydrogen-bonded helix fashion. Compound 2, a three-dimensional chiral open framework with 16-MR channels, is formed by the distorted {Zn(3)P(4)} secondary building unit (SBU). The organic amine molecules play dual roles as both ligands and countercations.     

Synthesis and Crystal Structure of [VO2（C17H11N3O2） ] [VO （C4H13N3）（C6H5N3O） ]（C2H5OH）

The reaction of VO（acac）2 with 2-hydroxyl-1-naphthaldehyde isonicotinyl hydrazone and amines （ethylenediamine or diethylenetriamine） in CH3OH yields crystals of novel vanadium compounds characterized by IR, NMR spectroscopic methods and X-ray single-crystal structure determination. Two different vanadium units exist in the crystal cell of [VO2（C17H11N3O2）][VO- （C4H13N3）（C6H5N3O）]（C2H5OH） which crystallizes in the triclinic system, space group P1 with a = 8.0104（17）, b = 13.898（3）, c = 14.955（3）A, α = 89.103（4）, β = 79.551（4）, γ = 78.352（4）°, V = 1603.3（6）A^3, Mr = 723.54, Dc = 1.499 g/cm^3, Z = 2, λ（MoKα） = 0.71073 ]A,μ= 0.644 mm^-1, F（000） = 748, the final R = 0.0547 and wR = 0.0997 for 8920 observed reflections with I 〉 2σ（I）. According to structure analysis, two different molecules are arranged in the lattice and the two vanadium atoms adopt octahedral and square pyramidal coordination geometries, respectively. The interactions between DNA and vanadium complexes have been investigated by UV-Vis absorption spectro- photometry.     

Synthesis and Crystal Structures of New Antimony Polysulfido Complexes: [P(C6H5)4]3Sb3S25 and [P(C6H5)4]2Sb2S15 · 2(C3N2H6)

Reaction of elemental antimony with sulfur under mild hydrothermal conditions yielded different polysulfido-clusters of antimony. These were isolated as tetraphenylphosphonium salts [P(C₆H₅)₄]₃Sb₃S₂₅ and [P(C₆H₅)₄]₂Sb₂S₁₅ · 2(C₃N₂H₆) and their crystal structures were determined. In the first compound two different polysulfide anions are observed, Sb₂S₁₇^2– and Sb₂S₁₆^2–, whereas the second contains the Sb₂S₁₅^2– complex. These dinuclear anions show as a common building principle two ψ-trigonal bipyramidal coordinated Sb centers bridged by two S_x^2– units and an additional S_x^2– chelate ligand bound to each Sb center giving a tricyclic structure.     

Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V) Compounds with the [SbS4]3— Anion Acting as a Monodentate Ligand: [Mn(C6H18N4)(C6H19N4)]SbS4 and [Mn(C6H14N2)3]2[Mn(C6H14N2)2(SbS4)2]·6H2O

The two novel thioantimonate(V) compounds [Mn(C₆H₁₈N₄)(C₆H₁₉N₄)]SbS₄ ( I ) and [Mn(C₆H₁₄N₂)₃][Mn(C₆H₁₄N₂)₂(SbS₄)₂]·6H₂O ( II ) were synthesized under solvothermal conditions by reacting elemental Mn, Sb and S in the stoichiometric ratio in 5 ml tris(2‐aminoethyl)amine (tren) at 140 °C or chxn (trans‐1, 2‐diaminocyclohexane, aqueous solution 50 %) at 130 °C. Compound I crystallises in the triclinic space group P1¯, a = 9.578(2), b = 11.541(2), c = 12.297(2)Å, α = 62.55(1), β = 85.75(1), γ = 89.44(1)°, V = 1202.6(4)ų, Z = 2, and II in the monoclinic space group C2/c, a = 32.611(2), b = 13.680(1), c = 19.997(1)Å, β = 117.237(5)°, V = 7931.7(8)ų, Z = 4. In I the Mn²⁺ cation is surrounded by one tetradentate tren molecule, one protonated tren acting as a monodentate ligand and a monodentate [SbS₄]^3— anion yielding a distorted octahedral environment. In II one unique Mn²⁺ ion is in an octahedral environment of three bidentate chxn molecules and the second independent Mn²⁺ ion is coordinated by two chxn ligands and two monodentate [SbS₄]^3— units leading to a distorted octahedral surrounding. The compounds were investigated and characterized with thermal and spectroscopic methods.     

Crystal structure and luminescence of lanthanide monodentate complexes [Ln(C(4)N(4)H(6)O)(2)(H(2)O)(6)]Cl(3) and [Ln(C(4)N(4)H(6)O)(2)(H(2)O)(3)(NO(3))(3)] (Ln = Tb or Eu)

New eight- and nine-coordinate luminescent europium(III) and terbium(III) complexes 1-4 with carbonyl group coordination have been prepared using the monodentate ligand (L) 2,4-diamino-6-hydroxy pyrimidine and characterized by X-ray and spectroscopic methods.     

Towards a molecular model for bismuth(III) subsalicylate. Synthesis and solid-state structure of [Bi(Hsal)3(bipy)(C7H8]2 and [Bi(Hsal)(sal)(1,10-phenanthroline)(C7H8]2

The synthesis and characterization of the first bismuth salicylate complexes, stabilized by chelating amine ligands, offers the possibility for detailed investigation of molecular precursors of the biologically significant compound bismuth subsalicylate (BSS).     

A novel group of alkaline earth metal amides: syntheses and characterization of M[N(2,6-(i)Pr(2)C(6)H(3))(SiMe(3))](2)(THF)(2) (M = Mg,Ca, Sr,Ba) and the linear,two-coordinate Mg[N(2,6-(i)Pr(2)C(6)H(3))(SiMe(3))](2)

Novel alkaline earth metal aryl-substituted silylamides were prepared using alkane (Mg) and salt elimination reactions (Mg, Ca, Sr, and Ba). The salt elimination regime involved the treatment of the alkaline earth metal iodides with 2 equiv of the respective potassium amide KNDiip(SiMe(3)), (Diip = 2,6-i-Pr(2)C(6)H(3)). The organomagnesium source for the alkane elimination was ((n)()Bu/(s)()Bu)(2)Mg. All compounds were characterized using (1)H, (13)C NMR, and IR spectroscopy, in addition to X-ray crystallography (except Mg[NDiip(SiMe(3))](2)THF(2)). Crystal data with Mo Kalpha (lambda = 0.710 73 A) are as follows: Mg[NDiip(SiMe(3))](2), 1, a = 9.4687(6) A, b = 9.6818(6) A, c = 17.9296(1) A, alpha = 96.487(1) degrees, beta = 94.537(1) degrees, gamma = 89.222(1) degrees, V = 1608.8(2) A(3), Z = 2 (two independent molecules), triclinic, space group P(-)1, R1 (all data) = 0.0508; (n)()BuMg[NDiip(SiMe(3))]THF(2), 2, a = 9.5413(1) A, b = 16.493(2) A, c = 9.8218(1) A, beta = 108.149(2) degrees, V = 1468.7(4) A(3), Z = 2, monoclinic, space group P2(1), R1(all data) = 0.1232; Ca[NDiip(SiMe(3))](2)THF(2), 4, a = 9.7074(1) A, b = 20.9466(4) A, c = 21.6242(3) A, alpha = 73.573(1) degrees, beta = 78.632(1) degrees, gamma = 89.621(1) degrees, V = 4129.1(1) A(3), Z = 4 (two independent molecules), triclinic, space group P(-)1, R1 (all data) = 0.0902; Sr[NDiip(SiMe(3))](2)THF(2), 5, a = 20.5874(5) A, b = 9.8785(2) A, c = 20.8522(5) A, beta = 102.035(2) degrees, V = 4147.6(2) A(3), Z = 4 (two independent molecules), monoclinic, space group P2/n, R1 (all data) = 0.0756; Ba[NDiip(SiMe(3))](2)THF(2), 6, a = 20.5476(2) A, b = 10.0353(2) A, c = 20.9020(4) A, beta = 101.657(1) degrees, V = 4221.0(1) A(3), Z = 4 (two independent molecules), monoclinic, space group P2/n, R1 (all data) = 0.0573.     

Synthesis and X-ray structures of dilithium complexes of the phosphonate anions [PhP(E)(N(t)Bu)(2)](2-) (E = O,S, Se,Te) and dimethylaluminum derivatives of [PhP(E)(N(t)Bu)(NH(t)Bu)](-) (E = S,Se)

The dilithium salts of the phosphonate dianions [PhP(E)(N(t)Bu)(2)](2-) (E = O, S, Se) are generated by the lithiation of [PhP(E)(NH(t)Bu)(2)] with n-butyllithium. The formation of the corresponding telluride (E = Te) is achieved by oxidation of [Li(2)[PhP(N(t)Bu)(2)]] with tellurium. X-ray structural determinations revealed dimeric structures [Li(THF)(2)[PhP(E)(N(t)Bu)(2)]](2) in which the monomeric units are linked by Li-E bonds. In the case of E = Se or Te, but not for E = S, transannular Li-E interactions are also observed, resulting in a six-rung ladder. By contrast, for E = O, this synthetic approach yields the Li(2)O-templated tetramer [(THF)Li(2)[PhP(O)(N(t)Bu)(2)]](4).Li(2)O in THF or the tetramer [(Et(2)O)(0.5)Li(2)[PhP(O)(N(t)Bu)(2)]](4) in diethyl ether. The reaction of trimethylaluminum with PhP(E)(NH(t)Bu)(2) produces the complexes Me(2)Al[PhP(E)(N(t)Bu)(NH(t)Bu)] (E = S, Se), which were shown by X-ray crystallography to be N,E-chelated monomers.     

Synthesis,molecular and electronic structure of [ReCl2(N2COPh)(C4N2H4)(PPh3)2]

A new organodiazenido rhenium complex, [ReCl₂(N₂COPh)(C₄N₂H₄)(PPh₃)₂] has been obtained from the direct reaction of [ReCl₂(η²–N₂COPh–N′,O)(PPh₃)₂] with pyrazine in acetone. The complex has been characterized by spectroscopic methods and its structure determined using single-crystal X-ray diffraction techniques.     

C3N6H6(H3BO3)2的合成及晶体结构

以三聚氰胺和硼酸为原料在水溶液中反应合成出了一种新的BCN化合物先驱体C3N6H6(H3BO3)2。XRD表征结果表明三聚氰胺和硼酸的最佳配比为1∶3(物质的量比)。用单晶X-射线衍射分析法测定了该化合物的晶体结构。该化合物属单斜晶系,空间群为P21/C,晶胞参数为a=0.3597(7)nm,b=2.0105(4)nm,c=1.4112(3)nm,α=90,°β=92.07(3),°γ=90,°V=1.0199(3)nm3,Z=4,D c=1.627g.cm-3,μ(MoKα)=0.144mm-1,F(000)=520。晶体结构经全矩阵最小二乘法修正,最终可靠因子R1=0.0519,wR2=0.1361。该化合物是由C3N6H6分子和H3BO3分子通过氢键加合组装形成的三维超分子结构化合物。     

A comparison of the influences of alkoxide and thiolate ligands on the electronic structure and reactivity of molybdenum(3+) and tungsten(3+) complexes. preparation and structures of M(2)(O(T)Bu)(2)(S(t)Bu)(4), [Mo(S(t)Bu)(3)(NO)](2), and W(S(t)Bu)(3)(NO)(py)

M(2)(O(t)Bu)(6) compounds (M = Mo, W) react in hydrocarbon solvents with an excess of (t)BuSH to give M(2)(O(t)Bu)(2)(S(t)Bu)(4), red, air- and temperature-sensitive compounds. (1)H NMR studies reveal the equilibrium M(2)(O(t)Bu)(6) + 4(t)BuSH <==> M(2)(O(t)Bu)(2)(S(t)Bu)(4) + 4(t)BuOH proceeds to the right slowly at 22 degrees C. The intermediates M(2)(O(t)Bu)(4)(S(t)Bu)(2), M(2)(O(t)Bu)(3)(S(t)Bu)(3), and M(2)(O(t)Bu)(5)(S(t)Bu) have been detected. The equilibrium constants show the M-O(t)Bu bonds to be enthalpically favored over the M-S(t)Bu bonds. In contrast to the M(2)(O(t)Bu)(6) compounds, M(2)(O(t)Bu)(2)(S(t)Bu)(4) compounds are inert with respect to the addition of CO, CO(2), ethyne, (t)BuC triple bond CH, MeC triple bond N, and PhC triple bond N. Addition of an excess of (t)BuSH to a hydrocarbon solution of W(2)(O(t)Bu)(6)(mu-CO) leads to the rapid expulsion of CO and subsequent formation of W(2)(O(t)Bu)(2)(S(t)Bu)(4). Addition of an excess of (t)BuSH to hydrocarbon solutions of [Mo(O(t)Bu)(3)(NO)](2) and W(O(t)Bu)(3)(NO)(py) gives the structurally related compounds [Mo(S(t)Bu)(3)(NO)](2) and W(S(t)Bu)(3)(NO)(py), with linear M-N-O moieties and five-coordinate metal atoms. The values of nu(NO) are higher in the related thiolate compounds than in their alkoxide counterparts. The bonding in the model compounds M(2)(EH)(6), M(2)(OH)(2)(EH)(4), (HE)(3)M triple bond CMe, and W(EH)(3)(NO)(NH(3)) and the fragments M(EH)(3), where M = Mo or W and E = O or S, has been examined by DFT B3LYP calculations employing various basis sets including polarization functions for O and S and two different core potentials, LANL2 and relativistic CEP. BLYP calculations were done with ZORA relativistic terms using ADF 2000. The calculations, irrespective of the method used, indicate that the M-O bonds are more ionic than the M-S bonds and that E ppi to M dpi bonding is more important for E = O. The latter raises the M-M pi orbital energies by ca. 1 eV for M(2)(OH)(6) relative to M(2)(SH)(6). For M(EH)(3) fragments, the metal d(xz)(),d(yz)() orbitals are destabilized by OH ppi bonding, and in W(EH)(3)(NO)(NH(3)) the O ppi to M dpi donation enhances W dpi to NO pi* back-bonding. Estimates of the bond strengths for the M triple bond M in M(2)(EH)(6) compounds and M triple bond C in (EH)(3)M triple bond CMe have been obtained. The stronger pi donation of the alkoxide ligands is proposed to enhance back-bonding to the pi* orbitals of alkynes and nitriles and facilitate their reductive cleavage, a reaction that is not observed for their thiolate counterpart.     

Syntheses, luminescence behavior, and assembly reaction of tetraalkynylplatinate(II) complexes: crystal structures of [Pt((t)Bu(3)trpy)(Ctbd1;CC(5)H(4)N)Pt((t)Bu(3)trpy)](PF(6))(3) and [Pt(2)Ag(4)(Ctbd1;CCtbd1;CC(6)H(4)CH(3)-4)(8)(THF)(4)

A series of tetraalkynylplatinate(II) complexes, (NBu(4))(2)[Pt(Ctbd1;CR)(4)] (R = C(6)H(4)N-4, C(6)H(4)N-3, and C(6)H(3)N(2)-5), and the diynyl analogues, (NBu(4))(2)[Pt(Ctbd1;CCtbd1;CR)(4)] (R = C(6)H(5) and C(6)H(4)CH(3)-4), have been synthesized. These complexes displayed intense photoluminescence, which was assigned as metal-to-ligand charge transfer (MLCT) transitions. Reaction of (Bu(4)N)(2)[Pt(Ctbd1;CC(5)H(4)N-4)(4)] with 4 equiv of [Pt((t)Bu(3)trpy)(MeCN)](OTf)(2) in methanol did not yield the expected pentanuclear platinum product, [Pt(Ctbd1;CC(5)H(4)N)(4)[Pt((t)Bu(3)trpy)](4)](OTf)(6), but instead afforded a strongly luminescent 4-ethynylpyridine-bridged dinuclear complex, [Pt((t)Bu(3)trpy)(Ctbd1;CC(5)H(4)N)Pt((t)Bu(3)trpy)](PF(6))(3,) which has been structurally characterized. The emission origin is assigned as derived from states of predominantly (3)MLCT [d(pi)(Pt) --> pi((t)Bu(3)trpy)] character, probably mixed with some intraligand (3)IL [pi --> pi(Ctbd1;C)], and ligand-to-ligand charge transfer (3)LLCT [pi(Ctbd1;C) --> pi((t)()Bu(3)trpy)] character. On the other hand, reaction of (Bu(4)N)(2)[Pt(Ctbd1;CCtbd1;CC(6)H(4)CH(3)-4)(4)] with [Ag(MeCN)(4)][BF(4)] gave a mixed-metal aggregate, [Pt(2)Ag(4)(Ctbd1;CCtbd1;CC(6)H(4)CH(3)-4)(8)(THF)(4)]. The crystal structure of [Pt(2)Ag(4)(Ctbd1;CCtbd1;CC(6)H(4)CH(3)-4)(8)(THF)(4)] has also been determined. A comparison study of the spectroscopic properties of the hexanuclear platinum-silver complex with its precursor complex has been made and their spectroscopic origins were suggested.