Asymmetrische Hg(II)-Komplexe mit Organothiolato- bzw. Organoselenolato-und Triazenato-Liganden

The mixed mercury complexes (2XC₆H₄)₂N₃HgY (X=CH₃, F, Cl, Br, I;Y=SC₂H₅, SC₆H₅, SeC₆H₅) have been prepared. Both the Hg–S and Hg–Se bonds and, in contrast to other mixed triazenato-mercury compounds, the triazenato-mercury bonds have been shown to be kinetically labile on the NMR time scale by means of⁷⁷Se and¹⁹⁹Hg NMR spectroscopy. Evidence has been obtained for the presence of (2XC₆H₄)₂N₃HgY together with HgY ₂ and [(2XC₆H₄)₂N₃]₂Hg in solution.

     

C-Glucosylflavonoid biosynthesis from 2-hydroxynaringenin by Desmodium uncinatum (Jacq.) (Fabaceae)

[2′,3′,5′,6′-²H₄]-2-Hydroxynaringenin is synthesised and incubated with commercially available UDP-glucose and the crude protein extract from Desmoduim uncinatum leaves. The organic extract produces isotopically labelled [2′,3′,5′,6′-²H₄]-vitexin and [2′,3′,5′,6′-²H₄]-isovitexin. Repeating the experiment with denatured protein or replacing the 2-hydroxynaringenin with [2′,3′,5′,6′-²H₄]-apigenin or [2′,3′,5′,6′-²H₄]-naringenin results in no observable incorporation. 2-Hydroxynaringenin is therefore the substrate for C-glucosylflavonoid biosynthesis in D. uncinatum.     

Synthesis, XRD structure and properties of diaqua(p-toluidine-N,N-di-3-propionato)copper(II) dihydrate [Cu(p-Tdp)(H2O)2]·2H2O

The copper(II) complex [Cu(p-Tdp)(H₂O)₂]·2H₂O, where p-Tdp is the anion of p-toluidine-N,N-di-3-propionic acid (or N,N-di(2-carboxyethyl)-p-toluidine), has been synthesized and characterized by X-ray diffraction. Three crystallographically independent [Cu(p-Tdp)(H₂O)₂] molecules have a similar structure. The Cu atoms have a square pyramidal environment (4+1) with a small trigonal bipyramidal distortion. The ortho-H atom of the benzene ring blocks up the sixth coordination position of the Cu polyhedron. The basal plane is formed by the donor atoms of the tridentate ligand and by the water molecule (average bond length Cu---N 2.03, Cu---O 1.93, Cu---O_w 2.00 Å), the apex is occupied by another water molecule (Cu---O_w 2.27 Å). The Cu atoms are located 0.20–0.30 Å out of the mean planes of the four basal atoms towards the apical O_w atom. The IR and electronic absorption spectra of p-Tdp and the title compound have been described. UV–Vis reflectance spectra shows that the complex has the same square pyramidal geometry in the crystal state and in solution. The protonation constants of the ligand log K₁=6.87(2), log K₂=3.75(2), log K₃=2.57(2) and stability constants log K_CuH(p-Tdp)=2.13(5), log K_Cu(p-Tdp)=6.38(3) were determined by pH-titration at 25.0 °C and I=0.1 M KNO₃.     

Study on structural properties and solution dynamics of zinc complexes with the (N,N-dimethylaminomethyl)ferrocenyl ligand

The reaction of {C,N-[Fe(η⁵-C₅H₅)(η⁵-C₅H₃(CH₂NMe₂)-2)]}Li, (FcN)Li, with zinc chloride affords the diorganozinc complex (FcN)₂Zn (1). In solution, 1 appears as a mixture of rac and meso diastereomers, whereas in the solid state it crystallizes solely as a rac diastereomer. The ratio of rac/meso diastereomers in solution is solvent-, temperature- and concentration-dependent, consistent with an intermolecular exchange between diastereomers. An intramolecular dynamic phenomenon involving dissociation and recoordination of Zn---N bonds was also observed. The reaction of 1 with zinc chloride yields the monoorganozinc compound (FcN)ZnCl (2) as a slightly soluble yellow microcrystalline powder.     

A mixed‐valence iron complex of the antitumour drug 6‐mercaptopurine: tris(6‐mercaptopurine)iron(II) tetrachloroferrate(III) chloride

Single crystals of the title complex, tris(1,6‐di­hydro‐9H‐purine‐6‐thione‐N⁷,S)­iron(II) tetra­chloro­ferrate(III) chloride, [Fe(C₅H₄N₄S)₃][FeCl₄]Cl, were grown on the surface of solid 6‐mercaptopurine monohydrate pellets in a solution of iron(III) chloride. The solution of the hexagonal structure required the application of twin refinement techniques. All the component ions lie on threefold rotation axes. The complex contains distorted octahedral [Fe(C₅H₄N₄S)₃]²⁺ cations with three N7/S6‐chelating neutral 6‐mercaptopurine ligands, tetrahedral [FeCl₄]^? anions with a mean Fe—Cl distance of 2.189 (1) Å, and free chloride ions.     

Ansa‐Bridged Bis(benzene) Titanium Complexes

Taking advantage of an improved synthesis of [Ti(η⁶‐C₆H₆)₂], we report here the first examples of ansa‐bridged bis(benzene) titanium complexes. Deprotonation of [Ti(η⁶‐C₆H₆)₂] with nBuLi in the presence of N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (pmdta) leads to the corresponding 1,1′‐dilithio salt [Ti(η⁶‐C₆H₅Li)₂] ? pmdta that enables the preparation of the first one‐ and two‐atom‐bridged complexes by simple salt metathesis. The ansa complexes were fully characterized (NMR spectroscopy, UV/Vis spectroscopy, elemental analysis, and X‐ray crystallography) and further studied electrochemically and computationally. Moreover, [Ti(η⁶‐C₆H₆)₂] is found to react with the Lewis base 1,3‐dimethylimidazole‐2‐ylidene (IMe) to give the bent sandwich complex [Ti(η⁶‐C₆H₆)₂(IMe)].     

Ru(II) complexes imparting N2O2 donor bis chelating ligand N,N-bis(salicylidine)-hydrazine in unusual coordination mode

The synthesis and characterization of binuclear ruthenium complexes [{(η⁶-C₆H₆)Ru}₂(μ-bsh)₂] (1), [{(η⁶-C₁₀H₁₄)Ru}₂(μ-bsh)₂] (2), [{(η⁶-C₆Me₆)Ru}₂(μ-bsh)₂] (3), and rhodium complex [{(η⁵-C₅Me₅)RhCl}₂(μ-bsh)] (4) (bsh=N,N^′-bis(salicylidine)-hydrazine dianion) are reported. The complexes have been fully characterized by analytical and spectral techniques and unusual coordination mode of the ligand H₂bsh has been confirmed by single crystal X-ray analysis of the complex 2. Structural data revealed extensive inter- and intra-molecular C-H?O and C-H?π interactions and involvement of methyl and isopropyl hydrogen from the p-cymene in hydrogen bonding.     

A mixed chloride/trifluoromethanesulfonate ligand species in a ruthenium(II) complex

The compound [2‐(aminomethyl)pyridine‐κ²N,N′][chlorido/trifluoromethanesulfonato(0.91/0.09)][(10,11‐η)‐5H‐dibenzo[a,d]cyclohepten‐5‐amine‐κN](triphenylphosphane‐κP)ruthenium(II) trifluoromethanesulfonate dichloromethane 0.91‐solvate, [Ru(CF₃SO₃)_0.09Cl_0.91(C₆H₈N₂)(C₁₅H₁₃N)(C₁₈H₁₅P)]CF₃SO₃·0.91CH₂Cl₂, belongs to a series of Ru^II complexes that had been tested for transfer hydrogenation, hydrogenation of polar bonds and catalytic transfer hydrogenation. The crystal structure determination of this complex revealed disorder in the form of two different anionic ligands sharing the same coordination site, which other spectroscopic methods failed to characterize. The reduced catalytic activity of the title compound was not fully understood until the crystallographic data provided evidence for the mixed ligand species. The crystal structure clearly shows that the majority of the synthesized material has a chloride ligand present. Only a small portion of the material is the expected complex [Ru^II(OTf)(ampy)(η²‐tropNH₂)(PPh₃)]OTf, where OTf is triflate or trifluoromethanesulfonate, ampy is 2‐(aminomethyl)pyridine and tropNH₂ is 5H‐dibenzo[a,d]cyclohepten‐5‐amine.     

Synthesis and reactivity of neodymium(III) amido-tethered N-heterocyclic carbene complexes

The reaction of the heteroleptic Nd(III) iodide, [Nd(L′)(N″)(μ-I)] with the potassium salts of primary aryl amides [KN(H)Ar′] or [KN(H)Ar^*] affords heteroleptic, structurally characterised, low-coordinate neodymium amides [Nd(L′)(N″)(N(H)Ar′)] and [Nd(L′)(N″)(N(H)Ar^*)] cleanly (L′ = t-BuNCH₂CH₂[C{NC(SiMe₃)CHNt-Bu}], N″ = N(SiMe₃)₂, Ar′ = 2,6-Dipp₂C₆H₃, Dipp = 2,6-Prⁱ₂C₆H₃, Ar^* = 2,6-(2,4,6-Prⁱ₃C₆H₂)₂C₆H₃). The potassium terphenyl primary amide [KN(H)Ar^*] is readily prepared and isolated, and structurally characterised. Treatment of these primary amide-containing compounds with alkali metal alkyl salts results in ligand exchange to give alkali metal primary amides and intractable heteroleptic Nd(III) alkyl compounds of the form [Nd(L′)(N″)(R)] (R = CH₂SiMe₃, Me). Attempted deprotonation of the Nd-bound primary amide in [Nd(L′)(N″)(N(H)Ar^*)] with the less nucleophilic phosphazene superbase Bu^tNP{NP(NMe₂)₃}₃ resulted in indiscriminate deprotonations of peripheral ligand CH groups.     

不同硅铝比Cu-ZSM-5纳米片上N2O催化分解

以双季铵盐表面活性剂为模板剂,水热条件下合成了硅铝比(nSi/nAl)为18、26和95的ZSM-5沸石纳米片,采用离子交换方法制备了铜改性的ZSM-5纳米片样品,并测试了其催化分解N_2O性能。结合X射线衍射(XRD)、N_2吸附/脱附、X射线荧光光谱(XRF)、扫描电镜(SEM)、透射电镜(TEM)、氢气程序升温还原(H_2-TPR)、氧气程序升温脱附(O_2-TPD)和原位红外漫反射光谱(CODRIFT)等表征结果 ,探讨了沸石硅铝比对于催化剂N_2O分解性能的影响及其原因。结果表明,ZSM-5纳米片硅铝比越低,CuZSM-5纳米片催化剂的活性越高。催化活性的提高归因于低硅铝比催化剂上Cu~+活性物种可还原性的增强和吸附氧脱附能力的提高。     

Synthesis and characterization of a cationic oxorhenium(V) complex containing the pentadentate N3O2-donor ligand bis ( N -methylsalicylideneiminopropyl)amine

The complex salt [ReO(bsa)]PF₆ (H₂bsa?=?bis(N-methylsalicylideneiminopropyl)amine) was prepared from the reaction of cis-[ReO₂I(PPh₃)₂] with H₂bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO³⁺ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis.     

N-(2-吡咯甲基)-1-苯基乙亚胺·二甲基铝的合成、结构及其催化丙交酯的活性

通过席夫碱配体N-（2-吡咯甲基）-1-苯基乙亚胺与三乙基铝按物质的量之比为1：1在无氧无水的条件下反应,合成了席夫碱铝的有机金属化合物N-（2-吡咯甲基）-1-苯基乙亚胺·二甲基铝。其结构分别用核磁氢谱、碳谱,元素分析和X射线单晶衍射技术进行了表征。铝化合物在催化外消旋丙交酯开环聚合反应中表现出了中等的活性并得到了以等规聚合为主的高聚物。     

Influence of chloride anions on the electrodeposition and electroactivity of the polymer matrix in polypyrrole,poly(<Emphasis Type="Italic">N</Emphasis>-methylpyrrole) and polypyrrole derivatives functionalized by titanocene centers,in dry non-aqueous solutions

We report electrochemical studies on the influence of a small concentration of chloride ions on the electroactivity of the polymer matrix of polypyrrole (PPy), poly(N-methylpyrrole) [p(N-MePy)] and a poly(titanocene-propyl-pyrrole) derivative, p(Tc3Py) [Tc(CH₂)₃NC₄H₄; Tc=CpCpTiCl₂; Cp=C₅H₅; Cp=C₅H₄] in acetonitrile (AN), tetrahydrofuran (THF) and N,N-dimethylformamide (DMF). The polymer films were obtained on Pt disc electrodes from AN solutions of the monomers containing 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF₆) as the supporting electrolyte and then transferred to the corresponding monomer-free solution. Studies in Cl^–-containing solutions have shown that the p(Tc3Py) matrix is very sensitive to the presence of Cl^– ions in all the above solvents, namely that it was subjected to electrochemical degradation at potentials above 0.1 V vs. a Ag/0.01 M Ag⁺ in AN reference electrode. Degradation of the p(Tc3Py) matrix was also observed in chloride-free DMF+TBAPF₆ solutions. Addition of chloride ions to the AN solution containing pyrrole, N-methylpyrrole or Tc3Py inhibits the deposition of the polymer films. On the other hand, we have found that PPy and p(N-MePy) matrices after their deposition in chloride-free AN solutions show much more stable redox responses in contact with chloride and/or DMF solutions. Possible mechanisms of these effects are discussed.Abbreviations AN acetonitrile - Cp cyclopentadienyl - DMF N,N-dimethylformamide - N-MePy N-methylpyrrole - p(N-MePy) poly(N-methylpyrrole) - PPy polypyrrole - p(Tc3Py) poly[Tc(CH₂)₃NC₄H₄] - Py pyrrole - Tc titanocene=bis(cyclopentadienyl)titanium dichloride, Cp₂TiCl₂, or its radical CpCpTiCl₂ (Cp=C₅H₄) - Tc3Py titanocene-propyl-pyrrole, Tc(CH₂)₃NC₄H₄ - THF tetrahydrofuran Contribution to the 3rd Baltic Conference on Electrochemistry, Gdansk-Sobieszewo, Poland, 23–26 April 2003Dedicated to the memory of Harry B. Mark, Jr. (28 February 1934–3 March 2003)     

An ion pair uniting a gadolinium(III)–Schiff base complex and uranyl tetrachloride

The Schiff base N‐(tert‐butyl)‐3‐methoxy­salicyl­ald­imine (LH) forms a complex with gadolinium(III) chloride, [GdCl₂(LH)₂(C₅H₅N)₂]⁺, in which the two O atoms of each ligand are coordinated (the phenolic O atom being deprotonated) and the imine N atom is protonated and involved in a hydrogen bond with the phenoxide group. This complex crystallizes as an ion pair with uranyl tetrachloride, i.e. bis{bis­[2‐(tert‐butyl­iminio­methyl)‐6‐methoxy­phenolato‐O,O′]­dichlorobis­(pyridine‐N)­gadolinium(III)} tetra­chlorodi­oxo­uran­ium(VI) tetra­pyri­dine solvate [GdCl₂(C₁₂H₁₇NO₂)₂(C₅H₅N)₂]₂[UCl₄O₂]·4C₅H₅N. The U atom of the UCl₄O₂ anion lies on an inversion centre.     

2,6‐Bis(azaindole)pyridine: reactivity with iron(III) and copper(II) salts

1‐[6‐(1H‐Pyrrolo[2,3‐b]pyridin‐1‐yl)pyridin‐2‐yl]‐1H‐pyrrolo[2,3‐b]pyridin‐7‐ium tetrachloridoferrate(III), (C₁₉H₁₄N₅)[FeCl₄], (II), and [2,6‐bis(1H‐pyrrolo[2,3‐b]pyridin‐1‐yl‐κN⁷)pyridine‐κN]bis(nitrato‐κO)copper(II), [Cu(NO₃)₂(C₁₉H₁₃N₅)], (III), were prepared by self‐assembly from FeCl₃·6H₂O or Cu(NO₃)₂·3H₂O and 2,6‐bis(1H‐pyrrolo[2,3‐b]pyridin‐1‐yl)pyridine [commonly called 2,6‐bis(azaindole)pyridine, bap], C₁₉H₁₃N₅, (I). Compound (I) crystallizes with Z′ = 2 in the P space group, with both independent molecules adopting a trans–trans conformation. Compound (II) is a salt complex with weak C—H...Cl interactions giving rise to a zigzag network with π‐stacking down the a axis. Complex (III) lies across a twofold rotation axis in the C2/c space group. The Cu^II center in (III) has an N₃O₂ trigonal–bipyramidal environment. The nitrate ligand coordinates in a monodentate fashion, while the bap ligand adopts a twisted tridentate binding mode. C—H...O interactions give rise to a ribbon motif.     

Positional and compositional disorder in a ruthenium(II) piano‐stool complex

In (η⁶‐p‐cymene)(difluorophosphinato‐κO){2‐[(1H‐pyrazol‐1‐yl)methyl‐κN²]pyridine‐κN}ruthenium(II) 0.85‐hexafluorophosphate 0.15‐tetrafluoroborate, [Ru(PO₂F₂)(C₁₀H₁₄)(C₉H₉N₃)](PF₆)_0.85(BF₄)_0.15, (I), the [PO₂F₂]⁻ ligand exhibits positional disorder due to one F atom and one O atom sharing the same two positions related by a mirror reflection across the O—P—F plane. The correct composition of this coordinated anion was successfully determined to be [PO₂F₂]⁻ by refining the complex with various tetrahedral anions in which terminal atoms have similar atomic form factors. The noncoordinated counter‐ion is compositionally disordered between [PF₆]⁻ and [BF₄]⁻. The difficulty in determining the correct composition of this anion illustrates the importance of a crystallographer remaining impartial and open to encountering unexpected moieties in the process of elucidating a structure.     

New bifunctional N-thiophosphorylated thiourea and 2,5-dithiobiurea derivatives. Crystal structures of R[C(S)NHP(S)(OiPr)2]2 (R = –N(Ph)CH2CH2N(Ph)– and –NHNH–)

A new bifunctional N-thiophosphorylated thiourea and 2,5-dithiobiurea of the common formula R[C(S)NHP(S)(OiPr)₂]₂ [R = –N(Ph)CH₂CH₂N(Ph)– (H₂L^a); –NHNH– (H₂L^b)] have been synthesized and characterized by IR, ¹H, ³¹P spectroscopy and the single crystal X-ray diffraction method. The structure of the latter compound in CDCl₃ and acetone-d₆ solutions has been discussed in comparison with the monofunctional thiosemicarbazide PhNHNHC(S)NHP(S)(OiPr)₂ (HL^c).     

N-(1-亚氨基乙基)乙脒铂配合物合成、结构和性质

四氯合铂酸钾分别与邻、间、对磺基苯甲酸在乙腈和水中利用水热合成获得了3个铂的N-(1-亚氨基乙基)乙脒配合物:[Pt(NIA)_2]·(2-sb)·2H_2O(1),[Pt(NIA)_2]·(3-sb)·3H_2O(2)和[Pt(NIA)_2]·(1,4-dsb)·2H_2O(3)(NIA=N-(1-亚氨基乙基)乙脒,2-sb~2-=2-磺基苯甲酸二价阴离子、3-sb~2-=3-磺基苯甲酸二价阴离子、1,4-dsb~2-=1,4-二磺基苯二价阴离子)。合成过程中发生了乙氰三聚以及4-sb~2-转变为1,4-dsb~2-的反应。对配合物进行了元素分析、红外、紫外、荧光、热重和粉末X射线衍射表征,并利用单晶X射线衍射测定了配合物的晶体结构。3个配合物为阳离子-阴离子物种,阳离子为[Pt(NIA)_2]~(2+),中心金属离子四配位平面构型;阴离子与阳离子、水形成氢键,组成一个三维网络结构,但3个配合物的氢键模式不同。配合物在热稳定性、荧光性质上有一定差异。     

N-(2-吡咯甲基)-1-苯基乙亚胺·二甲基铝的合成、结构及其催化丙交酯的活性

通过席夫碱配体N-（2-吡咯甲基）-1-苯基乙亚胺与三乙基铝按物质的量之比为1：1在无氧无水的条件下反应,合成了席夫碱铝的有机金属化合物N-（2-吡咯甲基）-1-苯基乙亚胺·二甲基铝。其结构分别用核磁氢谱、碳谱,元素分析和X射线单晶衍射技术进行了表征。铝化合物在催化外消旋丙交酯开环聚合反应中表现出了中等的活性并得到了以等规聚合为主的高聚物。     

Seven-coordinate complexes of molybdenum(II) and tungsten(II) containing pyrazole as a ligand

Summary Equimolar quantities of [MI₂(CO)₃(NCMe)₂] (M = Mo or W) and C₃H₄N² (pyrazole) react in CH₂C1₂ at room temperature to give the iodo-bridged dimers [M(μ-I) (CO)₃(C₃H₄N²)]₂ (1) and (2). Two equivalents of C₃H₄N² react with [MI₂(CO)₃(NCMe)₂] (M = Mo or W) to give the bis(pyrazole) complexes [MI₂(CO)₃(C₃H₄N²)₂] (3) and (4) in good yield. Three and four equivalents of pyrazole react with [MoI₂(CO)₃(NCMe)₂] to give the cationic complexes [MoI(CO)₃(C₃H₄N²)₃]I (5) and [MoI(CO)₂(C₃H₄N²)₄]I (6), respectively. The mixed ligand complexes [MI₂(CO)₃(C₃H₄N²)L] (M = Mo or W; L = PPh₃, AsPh₃ or SbPh₃) (7)-(12) are prepared by reacting equimolar amounts of [MI₂(CO)₃(NCMe)₂] and L in CH₂C1₂ at room temperature, followed by an in situ reaction with one equivalent of C₃H₄N². The MoSnCl₃ complex [MoCl(SnCl₃)(CO)₃(C₃H₄N²)₂] (13) is prepared in an analogous manner using acetone as the solvent, whilst the mixed ligand compound [MoCl(SnQ₃)(CO) ₃(C₃H₄N²)(PPh₃)] (14) was prepared by treating the dimeric complex [Mo(μ-Cl)(SnCl₃)(CO)₃(PPh₃)]₂ with two equivalents of C₃H₄N². All the new complexes were characterised by elemental analysis (carbon, hydrogen and nitrogen), i.r. and ¹H n.m.r. spectroscopy.