Arylkomplexe des typs trans-[Ir(Ar)(CO)(PPh3)2]

The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh₃)₂] (Ar = C₆H₅, C₆F₅, 2-C₆H₄CH₃, 3-C₆H₄CH₃, 4-C₆H₄CH₃, 2-C₆H₄OCH₃, 2,6-C₆H₃-(OCH₃)₂, 4-C₆H₄N(CH₃)₂, 3-C₆H₄Cl, 4-C₆H₄Cl, 4-C₆H₄Cl, 3-C₆H₄CF₃, 4-C₆H₄CF₃) are described, and the most important IR data as well as the ³¹P NMR parameters of these, without exception trans-planar, compounds are given.

Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O₂)(CO)(PPh₃)₂] (Ar = C₆H₅, 3-C₆H₄CH₃, 4-C₆H₄CH₃). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO₂ the similar irreversible addition compound [Ir(4-C₆H₄CH₃)-(SO₂)(CO)(PPh₃)₂] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed.

The first step of the reaction between [Ir(4-C₆H₄CH₃)(CO)(PPh₃)₂] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C₆-H₄CH₃)(CO)(PPh₃)₂]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature.     

硼化合物研究(Ⅲ)——B10H102-、B12H122-以及B3H8-阴离子的二茂铁季铵盐的合成

本文通过B_nH_n^2-(n=10,12)及B₃H₈^-盐分别与C₅H₅FeC₅H₄CH₂N(R)Me₂Cl和Fe(C₅H₄CH₂N(R)Me₂Cl)₂(R=CH₃-,C₂H₅-,n-C₃H₇-,CH₂=CH-CH₂-和CH≡C-CH₂-)在水溶液中进行反应,合成了相应的三十个新的硼烷阴离子衍生物,这些化合物对水稳定性好,B₁₀H₁₀^2-及B₁₂H₁₂^2-衍生物对热、酸、碱和氧化剂均很稳定。研究了反应物之间的用量比例对反应产物的影响。实验结果表明,不论反应物之间的克分子比如何变化,只能得到相应的一种产物(产率90-98％)。     

Synthesis and structural characterization of sulfonates, phosphinates and carboxylates of organometallic Group 4 metal fluorides

Reaction of [Cp^*TiF₃] (Cp^* = (ν⁵-C₅Me₅)) with Me₃SiOSO₂- p-C₆H₄CH₃, Me₃SiOPOPh₂ and 1,2-(Me₃SiOCO)₂C₆H₄ yields the dinuclear complexes [{Cp^*TiF(μ-F)(μ-OSO₂-p-C₆H₄CH₄)}₂] (1), [{Cp^*TiF(μ-F)(μ-OPOPh₂)}₂] (2) and [{Cp^*TiF(μ-F)(μ-OCO-o-C₆H₄CO₂SiMe₃)}₂] (3). The molecular structures of 1 and 2 have been determined by single-crystal X-ray analysis. In complexes 1-3, the two titanium atoms are connected by bridging fluorine atoms as well as bridging sulfonate, phosphinate and carboxylate groups respectively. Each titanium atom is also bonded to a terminal fluorine atom. Reaction of [Cp₂^*ZrF₂] with 1,2-(Me₃SiOCO)₂C₆H₄ leads to the mononuclear pentacoordinate 18-electron species [Cp₂^*ZrF(μ-OCO-o-C₆H₄CO₂SiMe₃)] (4) and its structure was determined by X-ray crystallographic methods.     

Synthese et etude des complexes [C5H4(CH2)3C5H4]Ti(C5H5)2 presentant un pont entre deux ligands cyclopentadienyles

The complex (di-η⁵-C₅H₄CH₂CH₂CH₂C₅H₄)Ti(η¹-C₅H₅)₂ (I) can be obtained unambiguously starting from the corresponding bridged titanocene dichloride. Attempts to synthesize the isomeric compounds (η⁵-C₅H₅)₂ Ti(di-η¹-C₅H₄-CH₂CH₂CH₂C₅H₄) (I′) by the action of a convenient bridged dianion on (C₅H₅)₂ TiCl₂ afford several compounds, one of them is the complex I. The possibility of interconversion of these complexes by a fluctional process is discussed.     

(Dimethylaminoethyl)cyclopentadienyl-liganden in der chemie von gruppe-13-elementen (Al, Ga, In

The synthesis of cyclopentadienyl complexes containing polydentate C₅R₄(CH₂CH₂NMe₂) ligands (R = H, Me) and Group 13 elements (Al, Ga, In) is described. The compounds (C₅Me₄CH₂CH₂NMe₂) AlX₂ (X = Me, Cl, Br, I), (C₅Me₄CH₂CH₂NMe₂)MCl ₂ (M = Ga, In), (C₅H₄CH₂CH₂NMe₂)AlX₂ (X = H, Me, Et, Cl), (C₅H₄CH_2- CH₂NMe₂)GaCl₂,and (C₅H₄CH₂CH₂NMe₂)InMe₂ are obtained by three different procedures. All compounds that have been characterized, so far, by X-ray diffraction studies show an additional intramolecular coordination of the nitrogen atom in the side chain. Monomeric structures and sufficient volatilities make them potential candidates for MOCVD processes.     

Covalently linked ethylmercaptophenyl sulfonic acid and ethylmercaptobenzyl sulfonic acid silica materials—Synthesis and catalytic activity

New covalently linked sulfonic acid modified silicas have been formed and characterised and their catalytic Brönsted activity evaluated. Thus phenylmercaptoethyltrimethoxysilane, (MeO)₃SiCH₂CH₂SC₆H₅ and benzylmercaptoethyltrimethoxysilane, (MeO)₃SiCH₂CH₂SCH₂C₆H₅, were used to prepare the corresponding T-functional silica derivatives silica  CH₂CH₂SC₆H₄-4-SO₃H and silica  CH₂CH₂SCH₂C₆H₄-4-SO₃H by grafting on commercial silica, followed by sulfonation of the aryl group. Solid-state NMR, DTA and surface area characteristics of the materials are reported. The mercaptophenylsulfonic acid materials are thermally robust highly efficient solid catalysts for a range of transformations including, esterification, etherification and carbonyl group protection. An apparent pore size effect on rate of conversion was observed. The mercaptobenzylsulfonic acid materials were comparatively unstable.     

NOFBX新型绿色推进剂燃烧化学反应动力学模型

本文以具有绿色无毒、高性能、低成本等诸多优势的N_2O-C_2烃类燃料单元复合推进剂(即NOFBX)为对象,首先发展了包含52组分、325反应的燃烧化学反应机理模型。该机理不仅能够准确计算N_2O热解过程中重要组分的分布,而且能够在较宽的温度、压力、化学计量比范围内准确预测N_2O-C_2烃类燃料体系的着火延迟时间和层流火焰传播速度。鉴于本文提出的N_2O-C_2烃类燃料反应机理具有机理规模小、实验验证充分的特点,有望在NOFBX发动机的多维燃烧数值模拟中得到广泛应用。     

Protonated ethanol and its neutral counterparts

Collisionally activated dissociation and neutralization-reionization experiments reveal that protonation of ethanol leads to two distinct isomers, the classical ion CH₃CH₂OH⁺₂ and the proton-bound complex C₂H₄…H⁺…OH₂. The neutral counterpart of the latter is unstable, whereas that of the former can be produced in a bound state if the CH₃CH₂OH⁺₂ precursor ion is formed under low ion source pressure conditions and, thus, with higher internal energies. This suggests that there are substantial differences in the geometries of CH₃CH₂OH⁺₂ and the hypervalent CH₃CH₂OH₂ ·. This provides only a partial explanation for unusual isotope effects; C₂H₅OD₂ ·, CH₃CD₂OD₂ ·, and CD₃CH₂OD₂ · are substantially more stable than C₂D₅OD₂ · and C₂H₅OH₂ ·.     

Synthesis of methyltrioxorhenium(VII) arylamine complexes and mono- and bis(ortho)-chelated arylaminorhenium(VII) trioxides

From the reaction of MeReO₃ with the neutral arylamine C₆H₅CH₂NMe₂ and the aryldiamine C₆H₄(CH₂NMe₂)₂−1,3, have been isolated in good yields the 1/1 adduct complex [MeReO₃ · C₆H₅CH₂NMe₂], 1, and the 2/1 adduct complex [(MeReO₃)₂ · C₆H₄(CH₂NMe₂)₂− 1,3], 2, respectively. The X-ray molecular structure of 2 shows that both rhenium centres have a trigonal bipyramidal geometry and in the axial positions of each rhenium centre are one of the NMe₂ units of the aryldiamine ligand and a methyl group. The mono(ortho)-chelated arylaminorhenium trioxide complex [ReO₃(C₆H₄CH₂NMe₂−2], 3, can be synthesized by a transmetallation reaction of ClReO₃ with [ZnC₆H₄CH₂NMe₂−2₂] in a 2:1 molar ratio. In a similar way the bis(ortho)-chelated arylaminorhenium trioxide complex [ReO₃C₆H₃(CH₂NMe₂)₂−2,6], 4, can be synthesized by addition of a mixture of [Li₂C₆H₃(CH₂NMe₂)₂−2,6₂] and ZnCl₂ to ClReO₃. Complexes 3 and 4 have been isolated as white solids in 66% and 81% yields respectively. The rhenium centre in complex 4 has a bicapped tetrahedral geometry in which the monoanionic C₆H₃(CH₂NMe₂)₂−2,6⁻ ligand is pseudo-facially bonded with a characteristic N1-Re-N2 angle of 107.7(3)°, a Re-C_ipso bond length of 2.112(11) Å and Re-N1 and Re-N2 bond lengths of 2.518(9) Å and 2.480(8) Å respectively.     

新奇二茂铁甲基氮C60衍生物的合成、结构

尽管目前人们对富勒烯[C₆₀]的过渡金属有机物研究较多^[1],但通过氮卡宾方式连接的C₆₀二茂铁衍生物尚未见报道。鉴于对C₆₀反应的浓厚兴趣及二茂铁的广泛应用价值^[2]我们 利用C₆₀的缺电子性^[3]将其与二茂铁甲基氮卡宾进行[1+2]环加成反应,分离并表征了一种具有齿轮式结构的新奇C₆₀二茂铁衍生物(CpFeC₅H₄CH₂N)5C₆₀(l)。     

INDO Studies on the Electronic Structure of(2,4-C_7H_(11))_2Yb(DME)

ＩＮＤＯＳｔｕｄｉｅｓｏｎｔｈｅＥｌｅｃｔｒｏｎｉｃｓＳｔｒｕｃｔｕｒｅｏｆ（２,４－Ｃ７Ｈ１１）２Ｙｂ（ＤＭＥ）ＦＥＮＧＪｉａｎ－ｎａｎ,ＷＡＮＧＺｈｉ－ｚｈｏｎｇ,ＺＨＡＮＧＳｏ－ｂｏ,ＬＩＵＪｕ－ｚｈｅｎｇ（ＩｎｓｔｉｔｕｔｅｏｆＴｈｅｏｒｅｔ...     

Synthesis and Characterization of Dinuclear Aluminum Complexes Bearing N,N-Dialkylaniline-amido Ligands and Its Catalytic Properties for Lactone Polymerization

Two ligands [ortho-C6H4NR2（CH2NH）]2CH2CH2（3： R=Me; 4： R=EO were prepared by the reduction of preligands [ortho-C6H4NR2（CH=N）]zCH2CH2（1： R=Me; 2： R=Et）. These ligands reacted with AIMe3 to afford the corresponding dinuclear aluminum complexes {A1Me2[ortho-C6H4NR2（CH2N）]}2CHzCH2（5： R=Me; 6： R=Et）. All the compounds were characterized by 1H and UC nuclear magnetic resonance（NMR） spectroscopies and elemental analyses. The catalytic properties of the aluminum complexes towards the ring-opening polymerization of lactones were investi- gated in the presence of benzvl alcohol. All the oolvmerization reactions were proceeded in a controlled manner.     

Ab initio studies on the electronic structures of certain 10π-electron six-membered ring compounds

By using ab initio methods of all-electron or effective core potential calculations, the electronic structures and the possible aromaticity of some 10π-electron systems, C₆H₆⁴⁻ (1), N₆⁴⁻ (2), P₆⁴⁻ (3), S₆²⁻ (4), Te₆²⁻ (5) and S₃N₃⁻ (6), have been studied at the SCF levels using 4-31G//4-31G and 6-31G^*//6-31G^* basis sets. The bonding characteristics of these systems are analysed in terms of the canonical molecular orbital and the Foster-Boys localized molecular orbital results. The application of the second-order Jahn-Teller theorem to the stability of these diamagnetical planar species is presented.     

Splay elasticity in an oligomeric liquid crystal

A magnetically-induced Freedericksz transition was used in conjunction with capacitance techniques to determine the splay elastic constant of the 4,4'-dialkoxyphenylbenzoate monomer '5OO5rsquo; [C₅H₁₁OC₆H₄COOC₆H₄OC₅H₁₁] and its dimer. As a function of reduced temperature in the nematic phase, it was found that K₁₁ of the dimer is only about 20 per cent larger than that of the monomer. Moreover, the values of K₁₁/S² versus reduced temperature, where S is the scalar order parameter, are equal to within experimental noise. These results suggest that for short oligomers Meyer's entropic model for splay elasticity in polymer liquid crystals is not applicable. A lowest order correction to the entropic model is suggested, which partially accounts for excluded volume and dispersive effects.     

Synthesis of metallocenes of zirconium, hafnium, manganese, iron, tin, lead and half-sandwich complexes of rhodium and iridium containing the ligands (η-C5R4CR′2PMe2), where R and R′ may be H or Me

The dimethylphosphino substituted cyclopentadienyl precursor compounds [M(C₅Me₄CH₂PMe₂)], where M=Li⁺ (1), Na⁺ (2), or K⁺ (3), and [Li(C₅H₄CR′₂PMe₂)], where R′₂=Me₂ (4), or (CH₂)₅ (5), [HC₅Me₄CH₂PMe₂H]X, where X⁻=Cl⁻ (6) or PF₆⁻ (7) and [HC₅Me₄CH₂PMe₂] (8), are described. They have been used to prepare new metallocene compounds, of which representative examples are [Fe(η-C₅R₄CR′₂PMe₂)₂], where R=Me, R′=H (9); R=H and R′₂=Me₂ (10), or (CH₂)₅ (11), [Fe(η-C₅H₄CMe₂PMe₃)₂]I₂ (12), [Fe{η-C₅Me₄CH₂P(O)Me₂}₂] (13), [Zr(η-C₅R₄CR′₂PMe₂)₂Cl₂], where R=H, R′=Me (14), or R=Me, R′=H (15), [Hf(η-C₅H₄CMe₂PMe₂)₂]Cl₂] (16), [Zr(η-C₅H₄CMe₂PMe₂)₂Me₂] (17), {[Zr(η-C₅Me₄CH₂PMe₂)₂]Cl}{(C₆F₅)₃BClB(C₆F₅)₃} (18), [Zr{(η-C₅Me₄CH₂PMe₂)₂Cl₂}PtI₂] (19), [Mn(η-C₅Me₄CH₂PMe₂)₂] (20), [Mn{(η-C₅Me₄CH₂PMe₂B(C₆F₅)₃}₂] (21), [Pb(η-C₅H₄CMe₂PMe₂)₂] (23), [Sn(η-C₅H₄CMe₂PMe₂)₂] (24), [Pb{η-C₅H₄CMe₂PMe₂B(C₆F₅)₃}₂] (25), [Pb(η-C₅H₄CMe₂PMe₂)₂PtI₂] (26), [Rh(η-C₅Me₄CH₂PMe₂)(C₂H₄)] 29, [M(η,κP-C₅Me₄CH₂PMe₂)I₂], where M=Rh (30), or Ir, (31).     

相转移催化下4-氯苯磺酰基乙酸异丙酯的烷基化反应

在有机合成中可用芳磺酰基作暂时性活化基团。芳磺酰基乙酸酯是具有活性亚甲基的弱酸性化合物。通常要在氢化钠、醇钠存在下才能起烷基化反应。Ono等曾报道4-甲苯磺酰基乙酸甲酯在DBu存在下进行烷基化反应,但反应时间长。近年来,相转移催化在有机反应中的应用受到重视,然而用固液相转移催化法使芳磺酰基乙酸酯起烷基化反应还未见报道。我们在K₂CO₃/DMF体系中,用TEBA作催化剂,研究了4-氯苯磺酰基乙酸异丙酯与不同类型卤代烃所起的烷基化反应。合成了尚未见报道的一或二烷基化产物。     

富勒烯C36及其衍生物C36H2n的量子化学研究

应用密度泛函B₃LYP方法和从头算(abinitio)HF方法,在3-21G理论水平上,对具有C_2v,D_2d,D_3h和D_6h对称性的四种C₃₆异构体以及在保持D_2d,D_3h和D_6h对称性条件下形成的不同氢化物进行了量子化学计算,研究了它们在不同量子态时的分子几何构型和电子结构.结果表明,电子相关效应在C₃₆簇化合物的电子结构中起着重要作用.它们最稳定的结构是C₃₆的³A_2u量子态D_6h异构体,而C₃₆的氢化物是在D_3h异构体的C₂位置等同碳原子上形成的¹A_1'量子态氢化物C₃₆H₁₂.     

Observation of alkali-metal-carboxylate radical anions in fast-atom bombardment

The existence of a series of 32 molecular radical anions from carboxylic acids salts RCOO-Cat^−., where R = CH₃, CH₃CH₂, CH₃CH₂CH₂, (CH₃)₂CH, C₆H₅, o-CH₃-C₆H₄, m-CH₃-C₆H₄, and p-CH₃-C₆H₄ and Cat = Li, Na, K, Rb, has been proven by the observation of their fragmentation in negative-ion fast-atom bombardment tandem mass spectrometry. These species occur at very low abundance and are not detected in the fast-atom bombardment spectra because they are hidden in the background. However, the collision-induced dissociation fragmentation of ions selected at the mass-to-charge ratio values that correspond to these species display characteristic signals that are completely different from the signals observed from pure matrix or after addition of corresponding metal hydroxide to the matrix. The main fragmentation observed is the loss of the neutral metal atom from RCOOCat^−., followed by a loss of CO₂ for the aromatic compounds. Neutral loss experiments also confirm the existence of these radical anions. Scans for the loss of a selected metal after addition of one of the carboxylic acid salts to the matrix display abundant peaks at mass-to-charge ratio values that correspond to the salt radical anions. Some weaker peaks appear at other mass-to-charge ratio values independent of the salt that is used and also are observed from the matrix when the corresponding metal hydroxide is added. When alkali metal salts from some deuterated acids are analyzed, the predicted shifts are observed. The loss of the neutral metal is more pronounced from RCOONa^−., RCOOK^−., and RCOORb^−. than from RCOOLi^−..     

N,N'-diphenyldithiomalonamide as a gravimetric reagent for nickel and cobalt

N,N'-Diphenyldithiomalonamide, (C₆H₆. NH. CS)₂CH₂, is found to be a very suitable gravimetric reagent for nickel(II) and cobalt(II). The complexes, of composition Ni(C₁₅H₁₃N₂S₂)₂ and Co(C₁₅H₁₃N₂S₂)₃, are stable and can be weighed after drying at 110°. Separation from base metals has been studied, and the structural interpretation is supported by DTA, TG, infrared and NMR data.     

N-苯基硫代膦酰基氨基酸及氨基乙酸乙酯衍生物的研究

本文报告了42个新的N-苯基硫代膦酰基氨基酸及氨基乙酸乙酯衍生物的制备;改进了N-膦酰基氨基酸酯衍生物的制备方法;对衍生物的生物活性以及某些衍生物在酸碱水溶液中的稳定性进行了初步探讨。