Synthesis and Crystal Structure of [CpRu(η5-C5H5)(dppc)Cl][PF6]

The title complex [Ru(η5-C5H5)(dppc)Cl][PF6] has been synthesized by the reaction of [Ru(η5-C5H5)(PPh3)2Cl] with [dppc][PF6] (1,1'-bis(diphenylphosphino)cobaltocenium hexaflurophospate) in CH2Cl2, and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 15.754(8), b =13.704(7), c=19.120(10) (A),β=106.148(9)°, V=3965(4) (A)3, Z=4, C40H35Cl3CoF6P3Ru, Mr=988.94, Dc=1.657 g/cm3, F(000) = 1984 and μ(MoKα) = 1.181 mm-1. The final R = 0.0425 and wR = 0.1001 for 7002 independent reflections. The title complex shows a mononuclear Ru(Ⅱ)capped by an η5-Cp ring, a chelating η2-dppc and a terminal chloride to assume a three-legged piano-stool configuration.     

Synthesis, reactivity and structural studies of (η-methylcyclopentadienyl)(η-tetraphenylcyclobutadiene)cobalt and its derivatives

(η⁵-methylcyclopentadienyl)(η⁴-tetraphenylcyclobutadiene)cobalt (1) and its derivatives, [(1-acetyl-2-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene)cobalt (2) [(1-acetyl-3-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene)cobalt (3) [(1-carbomethoxy-2-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene)cobalt (4) and [(1-carbomethoxy-3-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene) cobalt (5) have been prepared in yields varying from 11% to 28% by introducing the substituents on the cyclopentadienyl ring of methylcyclopentadienyl sodium and then reacting with diphenylacetylene and CoCl(PPh₃)₃. The carboxylic acids [(1-carboxy-2-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene)cobalt (6), [(1-carboxy-3-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene)cobalt (7) have been prepared after ester hydrolysis of compounds 4 and 5 using KOH/ethanol. [(1-dimethylaminomethyl-3-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene) cobalt (8), was prepared selectively by direct substitution on the cyclopentadienyl ring of (η⁵-methylcyclopentadienyl)(η⁴-tetraphenylcyclobutadiene)cobalt in 65% yield. The 1,2-isomer was formed only in traces in this reaction. Reactivity of (η⁵-methylcyclopentadienyl)(η⁴-tetraphenylcyclobutadiene)cobalt and its carbomethoxy derivative have been compared with (η⁵-cyclopentadienyl)(η⁴-tetraphenylcyclobutadiene)cobalt. All new compounds were characterized by ¹H and ¹³C NMR, FT-IR, mass spectra and CHN analysis. Compounds 2, 4, 6 and 8 have also been structurally characterized by single crystal X-ray structural analysis.     

Synthesis and Crystal Structure of [EDA][Ni（dmit）2]3

The crystal structure of the compound [EDA][Ni(dmit)2]3 (EDA=2-diethylamino-1,3-dithioanylium; dmit=1,3-dithiole-2-thione-4,5-dithiolate)C25H14NNi3S32, has been determined by single crystal X-ray diffraction at 300K. The crystal is triclinic with space group P, a=11.252, b=12.192(2), c=20.055(6) , α=108.127(2), β=106.287(8), γ=90.005(9)°; V=2498.3(3) 3, Z=2, Mr=1530.38, Dc=2.03(2) g/cm3. Final R and Rw values were 0.0603 and 0.0704, respectively. The structure consists of thick layers of stacked Ni(dmit)2 entities separated by EDA cations. This salt shows semiconducting behaviour with room temperature conductivity of 0.2 Scm-1 and activation energy of 0.11 eV.     

Synthesis and Crystal Structure of [CpRu（η^5-C5H5）（dppc）Cl][PF6]

1INTRODUCTION The fragment[Ru(η5-C5H5)(PPh3)2Cl]plays an important role in the organo-ruthenium chemistry development,and has been used as a versatile star-ting material for other compounds due to its stability and facile manipulation.Much work has shown that a wide range of ligands with different steric and electronic properties can displace not only the Cl ligand but also the phosphine groups in[Ru(η5-C5H5)(PPh3)2Cl][1].The interest in this fragment and related derivatives concer…     

Synthesis and H NMR spectroscopic properties of substituted (η-tetraarylcyclobutadiene)(η-cyclopentadienyl)cobalt metallocenes

The reaction of diarylacetylenes with CoCl(PPh₃)₃ and sodium cyclopentadienylide or sodium carbomethoxycyclopentadienylide gave (η⁴-tetra-arylcyclobutadiene)(η⁵-cyclopentadienyl)cobalt and (η⁴-tetra-arylcyclobutadiene)(η⁵-carbomethoxycyclopentadienyl)cobalt, respectively, where aryl = para-XC₆H₄ (X = CF₃, F, MeO). The reaction was unsuccessful for the synthesis of (η⁴-tetra(para-methoxyphenyl)cyclobutadiene)(η⁵-cyclopentadienyl)cobalt, which was synthesised instead from dicarbonyl(η⁵-cyclopentadienyl)cobalt. In all of the examples starting with CoCl(PPh₃)₃ an intermediate (η⁵-cyclopentadienyl)- or (η⁵-carbomethoxycyclopentadienyl)(triphenylphosphine)-2,3,4,5-tetraarylcobaltacyclopentadiene complex was isolated, and two examples were characterised by X-ray crystallography. Heating the (η⁵-cyclopentadienyl)- or (η⁵-carbomethoxycyclopentadienyl)(triphenylphosphine)-2,3,4,5-tetraarylcobaltacyclopentadiene complexes resulted in clean conversion to the corresponding metallocenes. The influence of the para-aryl substituents on the ¹H NMR of the cyclopentadienyl moiety is tabulated, together with the influence of a range of R substituents in (η⁴-tetraphenylcyclobutadiene)(η⁵-RC₅H₄)cobalt (R = CO₂Me, CH₂OH, Me, CHO, CCH, CO₂H, CN, CONHR¹, 2-oxazolinyl, NH₂, NHAc, HgCl, Br, I, SiMe₃, SnMe₃, Ph).     

Study of nitrogen- and sulfur-containing heterocycles. 46. New heterocyclic systems — Derivatives of pyrido[3′,2′∶5,6][1,4]thiazino[3,4-c]- and pyrimido-[5′,4′∶5,6][1,4]thiazino[3,4-c][1,2,4]triazines. Synthesis,properties

Representatives of new heterocyclic systems were obtained — pyrido[3,25,6][1,4]thiazino[3,4-c]- and pyrimido[5,45,6][1,4]thiazino[3,4-c][1,2, 4]triazines. Hydrazides of N-(pyrid-3-yl)- and N-(pyrimid-5-yl)oxamic acids were isolated and characterized. Their acylation products were investigated.For communication 45, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 559–562, April, 1993.     

Study on the Ring Eulargment Reaction: Synthesis of 7,8,13, 13a-tetrahydroisoindolo[1,2-b][3]benzazepine and 5,6,8,9,14,14a-hexahydroisoquino[1,2-b][3]benzazepine

In our research on the ring enlargement of certain N-heterocycles, a general procedure for the ring enlargement with the insertion of an extra -CH2- was improved and shown in Scheme I1.Scheme IThe procedure had been carried out with such N-heterocycles as 2-methyl-1,2,3,4-tetrahydroisoquinoline2, tetrahydroberberine and strychnine3 with expected results. Thus, the procedure shown in Scheme I provides a new approach to the synthesis of larger N-heterocycles.Isoindolo[1,2-b][3]benzazepines a…     

New preparation of alkyl- and aryl-mono-η5-cyclopentadienylphosphine compounds or iron,cobalt and nickel

Tertiary phosphine stabilized homoleptic alkyl and aryl compounds of Fe, Co and Ni undergo protonolysis of their MC bonds with cyclopentadiene to produce the corresponding mono-η⁵-cyclopentadienyl complexes. Initial low reaction temperatures and the presence of phosphine ligands prevent the formation of metallocenes. This method allows the easy introduction of various achiral and chiral ligands into complexes of this class.     

Structure of thiocarbamide-containing cobalt(III) dioximates with [BeF4]2− and [BF4]− anions

The crystal structure of the complexes [Co(DH)₂(Tu)₂]₂[BeF₄]·C₂H₅OH (I) and [Co(DfH)₂(Tu)₂][BF₄] 0.5H₂ (II) (where DH^? is the dimethylglyoxime monoanion, DfH^? is the α-benzyldioxime monoanion, and Tu is thiourea) has been determined by X-ray diffraction analysis. The coordination polyhedron of the Co³⁺ atom is an N₄S₂ octahedron formed by four nitrogen atoms of the dioxime molecule and two sulfur atoms of the fragments of thiourea (Tu); the latter have parallel and perpendicular orientations relative to the dioxime residue. The deviation of the cobalt atom from the four-angle plane (formed by the nitrogen atoms of the dimethylglyoxime residues) does not exceed 0.019 Å. The Co-N and Co-S distances vary from 1.877(3) Å to 1.901(3) Å and from 2.280(1) Å to 2.307(1) Å, respectively. The statistically disordered cations [BeF₄]^2? and [BF₄]^? play an important role in crystal formation — they form a complex system of hydrogen bonds.     

Diversity-oriented synthesis of 1,2,3,5-tetrahydrobenzo[e][1,2,4]oxadiazepines and 2,3-dihydro-1H-benzo[e][1,2,4]triazepines by base-induced [4 + 3] annulation reactions

The base-induced formal [4 + 3] annulation reactions of N-(ortho-chloromethyl)aryl amides with nitrones or hydrazonoyl chlorides have been reported. When nitrones are used as the 1,3-dipole, the corresponding reaction afforded a series of 1,2,3,5-tetrahydrobenzo[e][1,2,4]oxadiazepine derivatives. Highly functionalized 2,3-dihydro-1H-benzo[e][1,2,4]triazepine derivatives were also synthesized via an unprecedented tandem aza-Michael addition/rearrangement aromatization between N-(ortho-chloromethyl)aryl amides and hydrazonoyl chlorides.     

Synthesis and Crystal Structure of catena-Poly[bis-(benzimidazole)cobalt(II) μ-Phthalato]

1 INTRODUCTION Chemists have recognized that intermolecular inter- actions are the basis of functional properties for most molecular assembles, and detailed understan- ding of non-covalent chemistry is therefore funda- mental to interpreting and predicting the relation- ship between structure and function. Among intermo- lecular interactions, the π-π stacking between aro- matic rings is correlated with the electron transfer process in some biological systems[1], and the nature of π-π s…     

Synthesis of Certain 3-Aminopyrazolo[5,4-b]pyridine and 3,4-Substituted Pyrido[2′,3′：3,4]pyrazolo[5,1-c][1,2,4]triazine Derivatives

2-Thioxo-1,2-dihydropyridine derivatives 2a, 2b were reacted with methyl iodide to give 2-methylthiopyridines 3a, 3b, which were reacted with hydrazine hydrate to produce 3-aminopyrazolo[5,4-b]pyridines 4a, 4b. Compounds 4a, 4b were diazotized to afford the corresponding diazonium salts 5a, 5b, which were reacted with some active methylene compounds 6a-6h to give the corresponding pyrido[2′,3′ ： 3,4]pyrazole[5,1-c][1,2,4]triazines 7-14.     

甘氨酸离子液体[C3mim][Gly]和[C4mim][Gly]水溶液的表面张力

本文用中和法合成了基于烷基咪唑的甘氨酸离子液体[C3mim][Gly]（1-丙基-3-甲基咪唑甘氨酸离子液体）和[c4miml[Gly]（1-丁基-3．甲基咪唑甘氨酸离子液体）,在298．15K下,0．0400-0．5000molkg^-1浓度范围内测定了不同浓度[C4mim][Oly]和[c3mim][Gly]离子液体水溶液的密度和表面张力,得到了溶液等张比容的实验值,提出了预测不同浓度溶液等张比容的经验方程,利用这个经验方程和李以圭等人提出的溶液表面张力模型,分别估算了这两种离子液体水溶液的表面张力,其估算值和实验值在误差范围内很好地吻合．     

分子导体:[NCBzPy][TCNQ]2和[FBzPy][TCNQ]2的合成及光谱研究

合成了两种新的取代苄基吡啶盐[NCBzPy]Cl(1)和[FBzPy]cl(2),1(或2)与LiTCNQ,TCNQ进一步反应生成[NCBzPy][TCNQ]2(3){或[FBzPy][TCNQ]2(4)}。IR研究表明：TCNQ盐中存在TCNQ^o和TCNQ^-,并形成了一维TCNQ分子柱,且TCNQ^o和TCNQ^-之间存在相互作用,有部分电荷发生转移。     

Regioselective, stereoselective, and conformationally controlled synthesis of (η4-tetraarylcyclobutadiene)(η5-carbomethoxycyclopentadienyl)cobalt metallocenes

The Friedel-Crafts reaction of (η(4)-tetraphenylcyclobutadiene)(η(5)-carbomethoxycyclopentadienyl)cobalt with acid chlorides/aluminum chloride resulted exclusively in para-phenyl acylation. Both monoacylated (1.1 equiv of RCOCl/AlCl(3)) and tetraacylated products (>4 equiv of RCOCl/AlCl(3)) were synthesized. Reaction of PhCC(o-RC(6)H(4)) (R = Me, i-Pr) with Na(C(5)H(4)CO(2)Me) and CoCl(PPh(3))(3) gave predominantly (η(4)-1,3-diaryl-2,4-diphenylcyclobutadiene)(η(5)-carbomethoxycyclopentadienyl)cobalt metallocenes (1,3-[trans] vs 1,2-[cis] selectivity up to 6:1). Conformational control of Friedel-Crafts reactions on the major isomers gave exclusively para-acylation of the unsubstituted phenyl groups.     

Ionic liquid [bmim][BF4] acts as solvent and promoter for synthesis of halo-containing N-arylphthalimides

A new synthetic process of N-arylphthalimide and halo-containing N-arylphthalimides through the reaction between phthalic anhydride and aromatic amines bearing halo groups in[bmim][BF_4]was described,ionic liquid[bmim][BF_4]acted as the dual role of solvent and promoter.     

Synthesis and Structure of Some 6,7-Dihydro-thiazolo[4,5- d ][1,3,2]diaza-λ 5 -phosphorines

1,2,4-Thiadiazol-5(2 H )-imines 1 react with malononitrile under ring cleavage cycloaddition and subsequent ring rearrangement. The products 2 incorporate the enaminonitrile fragment. Treatment of compounds 2 with phosphorus pentachloride results in thiazolo[4,5- d ][1,3,2]diaza- u 5 -phosphorine derivatives 3 with a reactive chloro substituent in position 2 and 4 which can be substituted by various nucleophiles. The structure of the trimethoxy derivative 7c was determined by an X-ray structure analysis.     

Nucleophilic substitution reactions of acetylides on substituted tricarbonyl(η6-fluoroarene)chromium and reactions of tricarbonyl[η6-(2-trimethylsilylethynyl)toluene]chromium and tricarbonyl[η6-(p-ethynyl-phenylethynyl)benzene]chromium with dicobalt octacarbonyl

Nucleophilic substitution reactions of various acetylides on substituted tricarbonyl(η⁶-fluoroarene)chromiums were pursued. The reaction presumably underwent a more complicated mechanism rather than the direct substitution on the fluorine-bearing carbon. The organometallic compounds (η⁶-C₆H₃R¹R²R³)Cr(CO)₃ (R¹: CC–C₆H₄CH₃, R²: o-Me, R³: H (5a), R¹: CC–C₆H₄CH₃, R²: o-OMe, R³: H (6a), R¹: CC–C₆H₄CH₃, R²: m-OMe, R³: H (6b), R¹: CCPh, R²: o-Me, R³: o-OMe (8b), R¹: CCPh, R²: m-Me, R³: m-OMe (8c), R¹: CCSiMe₃, R²: o-Me, R³: H (9a), R¹: CC–C₆H₄CCH, R²: H, R³: H (12), R¹: CC–C₆H₄CCH, R²: o-Me, R³: H (13)) as well as the organometallic dimmer [{(η⁶-o-Me-C₆H₄)Cr(CO)₃(di-ethynyl)] (di-ethynyl: CC–C₆H₄CC (14)) have been synthesized from nucleophilic substitution reactions of tricarbonyl(η⁶-fluoroarene)(chromium) compounds with suitable acetylides. The products have been characterized by spectroscopic means. In addition, (8b) and (8c) were characterized by X-ray diffraction studies. Further reactions of (9a) and (12) with appropriate amount of Co₂(CO)₈ yielded μ-alkyne bridged bimetallic complexes, Co₂(CO)₆{μ-Me₃SiCC–(o-tolueneCr(CO)₃} (10) and (Co₂(CO)₆)₂{μ-HCC–C₆H₄–CC–(benzene)Cr(CO)₃)}(15), respectively. Both (10) and (15) were characterized by spectroscopic means as well as single crystal X-ray crystallography. The core of these molecules is quasi-tetrahedron containing a Co₂C₂ unit. A two-dicobalt-fragments coordinated di-enyls complex, (Co₂(CO)₆)₂{μ-HCC–C₆H₄–CC–H} (17), was synthesized from the reaction of 1,3-diethynylbenzene with Co₂(CO)₈. Crystallographic studies of (17) also show that it exhibits a distorted Co₂C₂ quasi-tetrahedral geometry.