Synthesis and explosive decomposition of organometallic dehydro[18]annulenes: an access to carbon nanostructures

The synthesis of eight new cyclobutadiene or ferrocene-fused organometallic dehydroannulenes is reported. Cadiot-type coupling of a 1-bromoethynyl-2-silylethynylbenzene derivative to an organometallic diyne (1,2-diethynyl-3,4-bis(trimethylsilyl)cyclobutadiene(cyclopentadienyl )cobalt or 1,2-diethynylferrocene) is followed by deprotection and Cu(OAc)(2)-promoted ring closure. Five of the organometallic dehydroannulenes were structurally characterized. Three of the novel cycles explode at temperatures from 196 to 293 degrees C and form insoluble carbon materials. The soot produced from 13a shows a high abundance of onion-like carbon nanostructures. The nanostructures were characterized by high-resolution transmission electron microscopy.     

New carbon-rich organometallic architectures based on cyclobutadienecyclopentadienylcobalt and ferrocene modules

This review describes the chemistry of alkynylated cyclobutadiene complexes and alkynylated ferrocenes. These complexes are made by a combination of metalation, formylation and Ohira alkynylation. The transformation of a formyl group into an alkyne is a critical step in these syntheses. The use of a diazophosphonate as the source of a carbon atom is convenient and has allowed for the synthesis of a host of alkynylated π-complexes. Multiply alkynylated ferrocenes and cyclobutadiene(cyclopentadienyl)cobalt complexes are utilized as stepping stone for complex carbon-rich organometallics. Half-wheel, butterfly, and similar structures have been accessed and characterized by single crystal X-ray methods. A ferrocene-fused dehydro[18]annulene decomposes explosively when heated above 200 °C with formation of carbon nanostructures that are bagel- or onion-shaped and that have been characterized by electron microscopy. This account as well describes the synthesis and characterization of organometallic dendrimers and conjugated organometallic polymers.     

Organometallic reactions as tools to build new metal-containing conjugated polymers

By using organometallic reactions like Pd-catalyzed C-C coupling, metal-carbon bond formation and silicon-carbon bond cleavage, novel carbon-rich organometallic monomers HC≡C-C₆H₄-C≡C-[M]-C≡C-C₆H₄-C≡CH ( [M] = -Ru(dppe)₂- and (η⁵-C₅H₄)₂Fe) and organic monomers H-(C≡C-C₆H₄)_X-C≡CH (x = 1 to 3) have been obtained. They have been used for the design of novel homo and hetero metal-containing polymers via organometallic polycondensation reactions based on quantitative metal-carbon bond formation.     

Synthesis,chemical properties,and CO2 electroreduction of π-conjugated polymers bearing imidazolium and imidazolinium rings in the polymer backbone

π-Conjugated polymers (CPs) bearing imidazolium and imidazolinium rings in the polymer backbone were prepared from a previously reported monomer, 1,3-bis(2,3-dimethyl-4-bromophenyl)imidazolium chloride, and a newly synthesized monomer, 1,3-bis(2,3-dimethyl-4-bromophenyl)imidazolinium chloride, via Sonogashira and Suzuki–Miyaura coupling reactions. The corresponding model compounds were also synthesized via the same reactions and monomers. The absorption maxima and onset position of the UV–vis spectra of the polymers were observed at longer wavelengths than those of the model compounds, thus revealing the presence of extended π-conjugation along the polymer backbone chain. Both polymers and model compounds were photoluminescent in solution and exhibited solvatochromism. The cast films of the polymers on the Pt and Ag electrodes were demonstrated to be effective catalysts for CO₂ electroreduction.     

A novel weakly diatropic dehydroannulene containing the cyclobutadiene(cyclopentadienyl)cobalt unit. An organometallic dehydroannulene that obeys Hückel's rule

This contribution describes the synthesis of novel dehydrobenzannulenes containing CpCo-stabilized cyclobutadiene complexes. These dehydrobenzannulenes were made in two different ways. The first access involves a shotgun approach in which 1,2-diethynyl-3,4-bistrimethylsilylcyclobutadiene(cyclopentadienyl)cobalt and 1,2-diiodobenzene are reacted under Heck-type conditions utilizing (PPh₃)₂PdCl₂ as catalyst. The formation of a dimeric dehydrobenzannulene containing two benzene rings, two cyclobutadiene units and four alkyne units — even though in low yield — was observed. The second approach to organometallic dehydroannulenes involves the construction of a precursor by coupling 1,2-diethynyl-3,4-bistrimethylsilylcyclobutadiene(cyclopentadienyl)cobalt to 1-bromo-2-trimethylsilylethynylbenzene under Pd catalysis, deprotection and Vögtle coupling of the formed precursor to furnish the corresponding monomeric cycle in high yield. This cycle has been characterized by X-ray single-crystal analysis.     

First planar chiral bidentate ligand based on a (eta5-cyclopentadienyl)(eta4-cyclobutadiene) cobalt backbone: high efficiency in enantioselective palladium-catalyzed allylic substitutions

The synthesis of the planar chiral (R)-[eta5-(1-diphenylphosphino-2-tert-butylsulfenyl)cyclopentadienyl](eta4-tetraphenylcyclobutadiene) cobalt and its high efficiency as P,S-bidentate ligand in Pd-catalyzed allylic substitutions is described.     

Chelate polymers. VI. New copolymers of the some siloxane containing bis(2,4-dihydroxybenzaldehyd-imine)Me with bis(p-carboxyphenyl)diphenylsilane

New high complex polymeric structures containing metal chelate sequences alternating, through esteric bridges, with silane units were obtained. The azomethine of 2,4-dihydroxybenzaldehyde with 1,3-bis(aminopropyl)tetramethyldisiloxane has been synthesized and in situ complexed with copper (II), nickel (II), cobalt (II) and cadmium (II). The obtained bis-phenolic chelates were covalently inserted in polymeric linear structures by their polycondensation with bis(p-carboxyphenyl)diphenylsilane as a diacid chloride. The structures of the obtained polymers were confirmed by IR, UV, ¹H NMR and elemental analysis. The characterization was made by TGA, DSC, solubility tests and GPC. The electrical conductivity of both chelate monomers and their polymers was investigated, all compounds showing typical semiconducting behaviors.     

Diamidophosphites with remote P1-stereocentres and their performance in Pd-catalyzed enantioselective reactions

Diamidophosphite ligands based on 1,1′-bis(hydroxymethyl)ferrocene or N¹,N²-bis((S)-1-hydroxy-3,3-dimethylbutan-2-yl)oxalamide and bearing 1,3,2-diazaphospholidine rings with stereogenic phosphorus atoms were obtained. The use of these ligands provides up to 96% ee in Pd-catalyzed asymmetric allylations of (E)-1,3-diphenylallyl acetate, up to 70% ee in Pd-catalyzed desymmetrizations of N,N′-ditosyl-meso-cyclopent-4-ene-1,3-diol bis-carbamate and up to 80% ee in Pd-catalyzed allylic alkylations of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate. Results obtained with a diamidophosphite containing an oxalamide framework show the considerable potential of such ligands in enantioselective catalysis.     

有机钛化学——Ⅳ.某些新型双和单(烯基环戊二烯基)钛衍生物的合成与催化烯烃异构化

用几种不同路线设计和合成了16个新型的烯基取代环戊二烯及其钛衍生物。取代环戊二烯基钛催化剂在烯烃异构化反应中具有较高的活性和选择性。对反应机理进行了初步的研究。     

New approach to the synthesis of tetrazole-containing buta-1,3-diynes: The total synthesis of 1,4-bis(2-(tert-butyl)-2H-tetrazol-5-yl)buta-1,3-diyne

An approach for the total synthesis of 1,4-bis(2-(tert-butyl)-2H-tetrazol-5-yl)buta-1,3-diyne was reported. Developed approach to the synthesis of 1,4-bis(2-(tert-butyl)-2H-tetrazol-5-yl)buta-1,3-diyne can be used for obtaining different 2,5-bis(tetrazol-5-yl)-disubstituted five-membered heterocycles (e.g. thiophenes, pyrroles, furans etc.), as well as tetrazole-containing monomers for the synthesis of new types of electroconductive and high energetic polymers.     

新型结构规整的三联苯桥基四官能度化合物的合成与表征

以对-溴甲苯、对苯二酚、1-溴己烷、1,4-对苯二异氰酸酯等为原料, 通过Williamson反应、溴化反应、格氏反应、氧化反应、Suzuki反应等一系列反应合成了用于合成梯形聚合物的两种重要单体: 2,5-二[4′-N-(1,1-二羟甲基)丙胺基甲酰苯基]-1,4二己氧基苯和2,5-二｛4′-N-[1,1-二(对异氰酸酯基苯胺甲酸酯基)丙胺基甲酰苯基]｝-1,4二己氧基苯, 并利用元素分析、红外光谱(IR)、核磁共振氢谱(¹H NMR)和质谱(MS)等手段对其进行了结构表征.     

Synthesis and characterization of polybinaphthalene incorporating chiral (R) or (S)-1,1′-binaphthalene and oxadiazole units by Heck reaction

Chiral conjugated polymers P-1 and P-2 were synthesized by the polymerization of (R)-3,3′-diiodo-2,2′-bisbutoxy-1,1′-binaphthalene ((R)-M-1) and (S)-3,3′-diiodo-2,2′-bisbutoxy-1,1′-binaphthalene ((S)-M-1) with 2,5-bis(4-vinylphenyl)-1,3,4-oxadiazole (M-2) under Pd-catalyzed Heck coupling reaction, respectively. Both monomers and polymers were analysed by NMR, MS, FT-IR, UV, DSC-TG, fluorescent spectroscopy, GPC and CD spectra. The chiral conjugated polymers exhibit strong Cotton effect in their circular dichroism (CD) spectra indicating a high rigidity of polymer backbone. CD spectra of polymers P-1 and P-2 are almost identical and have opposite signs for their position. These polymers have strong blue fluorescence.     

γ-核酸碱基取代丙基甲基二乙氧基硅烷的合成及其聚合反应研究

本文以Υ-溴丙基甲基二乙氧基硅烷分别与尿嘧啶、胸腺嘧啶、腺嘌呤和5-氟尿嘧啶进行烷基化反应,制得了四种含有核酸碱基或5-氟尿嘧啶的新型有机硅单体。通过它们的缩聚反应,合成了六种侧基含核酸碱基或5-氟尿嘧啶的聚硅氧烷。     

Polyimides with main-chain photosensitive groups: Synthesis, characterization and their properties as liquid crystal alignment layers

In this work, a series of polyimides containing main-chain chalcone groups and side-chain cinnamate or acetate groups were synthesized. In the synthetic route, three dianhydride monomers were prepared by the reactions of 1,3-dihydro-1,3-dioxoisobenzofuran-5-carbonyl chloride with 1,3-bis(4-hydroxylphenyl)prop-2-en-1-one, 1,3-bis(4-(2-hydroxyethyl)phenyl)prop-2-en-1-one, and 1,3-bis(4-hydroxyphenyl)-pent-1-en-3-one-4-en, respectively. The precursor polyimides were obtained by the polycondensation of the dianhydride monomers with 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and the in situ imidization. After the polymerization, the final products were obtained by introducing the side groups through the reactions of the polyimide precursors with cinnamoyl chloride or acetic anhydride. The chemical structures and properties of the polyimides were characterized by elemental analysis, ¹H NMR, ¹³C NMR, FTIR, GPC, and thermal analysis. The polyimides show high thermal stability and good solubility in aprotic polar organic solvents. The polyimides can undergo sensitive [2+2] photocycloaddition reaction upon the UV light irradiation. After irradiation with linearly polarized UV light, the polyimide thin films can induce 5CB liquid crystal molecules to homogeneously align in the liquid crystal cells. Both the alignment ability and pretilt angles of the molecular orientation depend on the chemical structures of the polyimides.     

Arylidene Polymers. IX. Synthesis,Characterization, and Morphology of New Polyesters of Diarylidenecycloalkanones Containing Thianthrene Units

New polyesters containing thianthrene tetraoxide were synthesized by the interaction of 2,7-dichloroformylthianthrene-5,5′,10, 10′-tetraoxide with 2,5-bis(p-hydroxybenzylidene)cyclopentanone, 2,5-divanillylidenecyclopentanone, 2,6-bis(p-hydroxybenzyiidene)-cyclohexanone, 2,6-divanillylidenecyclohexanone, and 2,7-bis(p-hydroxybenzylidene)cycloheptanone by using the interfacial polycondensation technique. The resulting polyesters were characterized by elemental and spectral analyses. All the synthesized polymers readily dissolved at room temperature in dimethylsulfoxide. The thermal properties of the polymers were evaluated and correlated to their structural units by TGA and DSC measurements. X-ray analysis of polymers showed that all the polyesters are amorphous. Moreover, the morphology of a new high performance polyester, poly[oxycarbonyl-2,7-thianthrene-5,5′,10,10′-tetraox-idecarbonzeoxyl(2-methoxy-p-phenylene)methylidyne(2-oxo-1,3-cyclohexanediylidenemethylidyne)methylidene(3-methoxy-p-phenylene)], has been investigated by scanning electron microscopy.     

Regioselective synthesis of functionalized ferrocenylphenols based on cyclocondensation reactions of free and masked 1,3-dicarbonyl dianions

Highly functionalized ferrocenyl-substituted phenols were prepared by cyclization of masked or free dianions with 1,3-dielectrophilic 1-η5-ferrocenyl-3,3-bis(methylthio)prop-2-en-1-ones. While the cyclizations of 1,3-bis(silyloxy)-1,3-butadienes (masked dianions) proceed by initial 1,2-addition, the reactions of free 1,3-dicarbonyl dianions proceed by initial 1,4-addition. Therefore, both regioisomeric ferrocenylphenols are available from one and the same electrophile dependent on the type of nucleophile and reaction conditions employed. The reactions reported represent the first examples of the application of formal [3 + 3] cyclizations to the synthesis of organometallic compounds.     

Electron impact and chemical ionisation mass spectrometry in the characterisation of organometallic silicon, germanium, tin and lead compounds

The electron impact and chemical ionisation mass spectra of a number of organometallic derivatives of silicon, germanium, tin and lead, incorporating inter alia 2-bis(trimethylsilyl)methylpyridyl or cyclopentadienyl ligands have been recorded. Representative spectra are presented and illustrate the utility of these mass spectrometric techniques in the characterisation of such compounds, particularly so in light of the highly informative nature arising from their fragmentation patterns and the numerous isotopes of the nuclei involved. Copyright 2000 John Wiley & Sons, Ltd.     

Metal-Mediated Oligomerization Reactions of the Cyaphide Anion

The cyaphide anion, CP⁻, is shown to undergo three distinct oligomerization reactions in the coordination sphere of metals. Reductive coupling of Au(IDipp)(CP) (IDipp=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) by Sm(Cp*)₂(OEt₂) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl), was found to afford a tetra-metallic complex containing a 2,3-diphosphabutadiene-1,1,4,4-tetraide fragment. By contrast, non-reductive dimerization of Ni(SIDipp)(Cp)(CP) (SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolidin-2-ylidene; Cp=cyclopentadienyl), gives rise to an asymmetric bimetallic complex containing a 1,3-diphosphacyclobutadiene-2,4-diide moiety. Spontaneous trimerization of Sc(Cp*)₂(CP) results in the formation of a trimetallic complex containing a 1,3,5-triphosphabenzene-2,4,6-triide fragment. These transformations show that while cyaphido transition metal complexes can be readily accessed using metathesis reactions, many such species are unstable to further oligomerization processes.     

Dissociation of 2,4-bis(2,4,6-tri-tert-butylphenyl)-cyclo-1,3-dipnicta-2,4-diazanes (pnict = P, As, Sb) imposed by substituent steric strain: a cyclobutane/olefin analogy

Three 2,4-bis(Mes)-cyclo-1,3-dipnicta-2,4-diazanes, 2PnX, have been synthesized as 1,3-dichloro- (Pn = As; X = Cl) or 1,3-bis(triflato)- (Pn = P, Sb; X = OTf) derivatives (Mes = 2,4,6-tri-tert-butylphenyl; OTf = triflato = trifluoromethanesulfonoxy). The compounds have been structurally characterized as cyclodimers, but spectroscopic characterization of melts and solutions indicates facile dissociation of the diphosphadiazane 2POTf derivative to give the corresponding iminophosphine 1POTf and of the diarsadiazane 2AsCl derivative to give the corresponding iminoarsine 1AsCl. 1,3-Bis(triflato)-2,4-bis(Mes)-cyclo-1,3-distiba-2,4-diazane (2SbOTf) does not dissociate in the melt or in solution. The presence of the sterically bulky Mes substituent does not preclude association of N-Pn olefin analogues to give single bonded cyclobutane analogues. The facile dissociation of 2POTf and isolation of 1POTf implicates a relatively high degree of substituent steric strain in the dimer. In comparison, dissociation of 2AsCl is only apparent in the melt and in solution, likely the result of the lower substituent strain in the larger N(2)As(2) framework. The largest N(2)Pn(2) framework in 2SbOTf provides sufficient space for the Mes substituents, and the monomer is not observed under the conditions examined.     

含噁二唑单元共轭聚合物合成与性质研究

单体 2 ,5 双 (4 溴苯 ) 1,3,4 二唑 (M Ⅰ )与 1,4 二乙烯基 2 ,5 二正丁氧基苯 (M Ⅱ ) ,在钯催化下通过Heck偶合反应合成得到共轭聚合物 ;单体和聚合物进行了1 H NMR ,1 3C NMR、质谱、FT IR、UV、荧光光谱、GPC、元素分析、热分析等测试 ;二唑 (OXD)基团是一种很好的生色团 ,对氧和热特别稳定 ,二唑环的亲电子性能使其特别适合于作为电子传输层 ,聚合物能发射很强的绿色荧光 ,它将是一类潜在的光电高分子材料