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1.
Densities of {(1−x)CH3(CH2)n−1OH + xCH3CN} for n=1, 2, 3 or 4 have been determined as a function of composition at 288.15, 293.15, 298.15 and 303.15 K at atmospheric pressure using a vibrating-tube densimeter (Anton Paar DMA 4500, resolution 1×10−5 g cm−3). Excess molar volumes were calculated. The VmE values were negative for acetonitrile–methanol mixtures and sigmoid for acetonitrile–alkanols (C2–C4) mixtures over the complete mole fraction range. VmE values increase in a positive direction with increase in chain length of the alkanols and with the temperature. The Extended Real Associated Solution Model (ERAS-Model) calculations allowing for self-association for the alkanols and complex formation between acetonitrile and alkanols have been used to correlate experimental data. The model is able to reproduce the asymmetrical VmE behavior of the studied systems, although agreement between theoretical and experimental values is less satisfactory for some concentration ranges. 相似文献
2.
Daoli Deng Yongqing Jiang Changtao QianGuang Wu Peiju Zheng 《Journal of organometallic chemistry》1994,470(1-2):99-107
Organolanthanide chloride complexes [(CH3OCH2CH2C5H4)2Ln(μ-Cl)]2 (Ln = La, Pr, Ho and Y) react with excess NaH in THF at 45°C to give the dimeric hydride complexes [(CH3OCH2CH2C5H4)2Ln(μ-H)]2, which have been characterized by IR, 1H NMR, MS and XPS spectroscopy, elemental analyses and X-ray crystallography. [(CH3OCH2CH2C5H4)2Y(μ-H)]2 crystallizes from THF/n-hexane at −30°C, in the triclinic space group P1 with a = 8.795(2) Å, b = 11.040(1) Å, c = 16.602(2) Å, = 93.73(1)°, β = 91.82(1)°, γ = 94.21(1)°, Dc = 1.393 gcm−3 for Z = 2 dimers. However, crystals of [(CH3OCH2CH2C5H4)2Ho(μ-OH)]2 were obtained by recrystallization of holmium hydride in THF/n-hexane at −30°C, in the orthorhombic space group Pbca with a = 11.217(2) Å, b = 15.865(7) Å, c = 17.608(4) Å, Dc = 1.816 gcm−3 for Z = 4 dimers. In the complexes of yttrium and holmium, each Ln atom of the dimers is coordinated by two substituted cyclopentadienyl ligands, one oxygen atom and two hydrogen atoms (for the Y atom) or two hydroxyl groups (for the Ho atom) to form a distorted trigonal bipyramid if the C(η5)-bonded cyclopentadienyl is regarded as occupying a single polyhedral vertex. 相似文献
3.
Montserrat Domínguez-Prez Julieta Jimnez de Llano Luisa Segade Oscar Cabeza Carlos Franjo Eulogio Jimnez 《Thermochimica Acta》2004,420(1-2):45-49
This paper reports excess molar enthalpies, HmE, and excess molar volumes, VmE, of the binary systems {propyl propanoate + o-xylene}, {propyl propanoate + m-xylene} and {propyl propanoate + p-xylene} at the temperature 298.15 K and atmospheric pressure, over the whole composition range. VmE was calculated from the experimental measurement of the corresponding densities, while HmE was measured directly. The excess magnitudes were correlated to a Redlich-Kister type equation. Finally, we will discuss the results of the three mixtures studied here and by comparison with other binary systems containing propyl propanoate and a benzene-based compound previously published. 相似文献
4.
Ekkehard Lindner Ulf Kehrer Manfred Steimann Markus Strbele 《Journal of organometallic chemistry》2001,630(2):3021-274
A series of novel heterobimetallic crown ether-like polyoxadiphosphaplatinaferrocenophanes cis-[1,1′-Fc(CH2O(CH2CH2O)nCH2CH2PPh2)2]PtCl2 (n=1–3) (4a–c) was synthesized in good yield by cyclization of the bis(phosphine) ligands 1,1′-Fc(CH2O(CH2CH2O)nCH2CH2PPh2)2 (n=1–3) (3a–c) and (PhCN)2PtCl2 under high dilution conditions in CH2Cl2. The bisphosphines 3a–c are obtained by reaction of the corresponding diols 1,1′-Fc(CH2O(CH2CH2O)nCH2CH2OH)2 (n=1–3) (1a–c) with: (i) CH3SO2Cl in CH2Cl2 and (ii) LiPPh2 in THF. Although the X-ray crystal structure of 4a shows that the cavity is large enough for the encapsulation of small metal cations, inclusion experiments of 4a–c with Group 1 cations, and Mg2+, or NH4+ in solution applying NMR titration and cyclovoltammetric methods reveal no evidence for the formation of host–guest complexes for 4a,b. In the case of 4c only the addition of Na+ or K+ leads to an insignificant effect. 相似文献
5.
Jianyong Zhang Jagadese J. Vittal William Henderson Jessica R. Wheaton Iris H. Hall T. S. Andy Hor Yaw Kai Yan 《Journal of organometallic chemistry》2002,650(1-2):123-132
Modified Mannich reactions of amines, amino acids and a model peptide with Ph2PH and CH2O gave bis(diphenylphosphinomethyl)amines (Ph2PCH2)2NR [R=Ph (1), CH2CH2OH (2), CH2COOCH2Ph (3), CH2CONHCH2COOCH2Ph (4), CH2COOH (5)] and (Ph2PCH2)2NCH2CH2N(CH2PPh2)2 (6). Reaction with [ReBr3(CO)3]2− under mild conditions led to [ReBr(CO)3]{(Ph2PCH2)2NR} [R=Ph (7), CH2CH2OH (8), CH2COOCH2Ph (9), CH2CONHCH2COOCH2Ph (10), CH2COOH (11)] and [ReBr(CO)3(Ph2PCH2)2NCH2]2 (12). All new complexes have been characterized by NMR and IR spectroscopy and for 7, 9 and 10, single-crystal X-ray diffraction analyses. Electrospray mass spectrometric studies show that the rhenium–phosphine chelates are very stable, especially in neutral methanolic solution. Hydrolysis of the ester and amide linkages slowly occur in acidic and basic solutions over several weeks; displacement of the bromide ligand also occurs in basic medium. Cytotoxicity testing of 7–10 and 12 showed that all the complexes are active against specific tumor cell lines, especially MCF-7 breast cancer and HeLa-S3 suspended uterine carcinoma. 相似文献
6.
II 《Journal of organometallic chemistry》1993,450(1-2):263-267
Treatment of [Pd{CH2C(CH3)CH2}(Ph2PPy)Cl] (Ph2PPy = 2-(diphenylphosphino)pyridine) with cis-[Pd(tBuNC)2Cl2] in dichloromethane affords the mixed isocyanide-tertiary phosphine complex cis-[Pd(tBuNC)Ph2PPy)Cl2], in which the Ph2PPy is a monodentate P-donor, and [{Pd[CH2C(CH3)CH2]Cl}2]. The steric effects of the Ph2PPy bridging ligand in determining the reaction course is discussed. The complex cis-[Pd(tBuNC)(Ph2PPy)Cl2] was crystallographically characterized: P21/n, a = 15.143(2), b = 9.527(1), c = 17.517(4) Å, β = 113.96(1)°, V= 2309.4(7) Å3, Z = 4. The final R value was 0.044, Rw= 0.046 for the 3078 reflections with I > 3σ(I). 相似文献
7.
Ronan M. Bellabarba Gerald P. Clancy Pedro T. Gomes Ana M. Martins Leigh H. Rees Malcolm L. H. Green 《Journal of organometallic chemistry》2001,640(1-2):93-112
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). 相似文献
8.
Alejandro J. Arce Esther Boyar Antony J. Deeming 《Journal of organometallic chemistry》1987,320(3):385-390
Carbon---hydrogen bond cleavage at the terminal 6-position occurs when hex-5-en-2-one (CH2=CHCH2CH2COMe) oxidatively adds to [Os3(CO)10(MeCN)2] to give [Os3H(μ-CH=CHCH2CH2COMe)(CO)10], which is completely analogous to the simple vinyl complex [Os3H(μ-CH=CH2)(CO)10]. A minor product from the reaction is [Os3(CH3CH=CHCH2COMe)(CO)10], an isomer in which double-bond migration has occurred to give the βγ-unsaturated ketone; stabilisation occurs through chelation and ketone coordination. [Os3H2(CO)10] reacts with CH2=CHCH2CH2COMe in refluxing cyclohexane to give a third isomer, [Os3H(CH3CH2C=CHCOMe)(CO)10], in which further double bond migration has occurred to give the β-unsaturated ketone. Metallation at the β-site gives an Os---C bond as part of a 5-membered chelate ring. Thermolysis of each of the three isomeric decarbonyl species in refluxing cyclohexane or heptane leads to the elimination of an Os(CO)4 group to give the dinuclear compound [Os2H(EtC=CHCOMe)(CO)6] in varying yield. Pathways from γδ to the βγ and finally the β unsaturated ketones may be mapped out. 相似文献
9.
A tridentate Schiff base ligand [(CH3)2NCH2CH2N=C(CH3)C6H4OH)] (LH) has been synthesized from 2-hydroxyacetophenone and 2-dimethylaminoethylamine. This ligand forms the neutral complexes [Co(L)(N3){o-(CH3C=O)C6H4O}] (1) and [Co(L)(SCN){o-(CH3C=O)C6H4O}]·1/2H2O (2) in presence of equivalent amount of Co(II) acetate, and sodium azide for 1 and sodium thiocyanate for 2. The complexes have been characterized by spectroscopic and crystallographic methods. The coordination geometry around Co(III) in both the complexes is distorted octahedral with one tridentate ligand L, one bidentate 2-hydroxyacetophenone and one monodentate azide for 1 and thiocyanate for 2. The azide and thiocyanate ligands in the two complexes occupy different positions relative to the coordination sites of L. 相似文献
10.
S. Villa N. Riesco I. García de la Fuente J. A. Gonzlez J. C. Cobos 《Fluid Phase Equilibria》2001,190(1-2):113-125
Excess molar volumes, VmE, at 298.15 K and atmospheric pressure over the entire composition range for binary mixtures of methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol and 1-octanol with dipropylamine are reported from densities measured with a vibrating-tube densimeter. All the excess volumes are large and negative over the whole mole fraction range, indicating strong interactions between unlike molecules, which are more important for the system involving methanol, characterized by the most negative VmE. For the remainder mixtures, VmE at equimolar composition, is approximately constant. The VmE curves are nearly symmetrical.
VmE and excess molar enthalpies, HmE, of the mixtures studied are consistently described by the ERAS model. The ERAS parameters confirm that the strongest interactions between unlike molecules are encountered in the methanol+dipropylamine system. 相似文献
11.
New ester salts [R3NH]+[F5SC(SO2F)C(O)OR′]− where RH, CH3CH2 and R′CH3,(CH3)2CH have been prepared from corresponding esters and amines. The sodiumsalt Na[F5SC(SO2F)C(O)OCH(CH3)2] was used to prepare the following -substitutedderivatives: SF5CX(SO2F)C(O)OCH(CH3)2, XBr, Cl. The crystal structure of[(C2H5)3NH]+[F5SC(SO2F)C(O)OCH3]− was determined and is monoclinic: P21/n;a=8.758(2) Å, b=9.645(2) Å and c=19.167(4) Å; β=97.92(3)°; V=1603.6 Å3; Z=4. 相似文献
12.
A spectroscopic study on the reaction-controlled phase transfer catalyst in the epoxidation of cyclohexene 总被引:3,自引:0,他引:3
Jinbo Gao Yangying Chen Bo Han Zhaochi Feng Can Li Ning Zhou Shuang Gao Zuwei Xi 《Journal of molecular catalysis. A, Chemical》2004,210(1-2):197-204
The epoxidation of cyclohexene with hydrogen peroxide in a biphase medium (H2O/CHCl3) was carried out with the reaction-controlled phase transfer catalyst composed of quaternary ammonium heteropolyoxotungstates [π-C5H5N(CH2)15CH3]3[PW4O16]. A conversion of about 90% and a selectivity of over 90% were obtained for epoxidation of cyclohexene on the catalyst. The fresh catalyst, the catalyst under reaction conditions and the used catalysts were characterized by FT-IR, Raman and 31P NMR spectroscopy. It appears that the insoluble catalyst could degrade into smaller species, [(PO4){WO(O2)2}4]3−, [(PO4){WO(O2)2}2{WO(O2)2(H2O)}]3−, and [(PO3(OH)){WO(O2)2}2]2− after the reaction with hydrogen peroxide and becomes soluble in the CHCl3 solvent. The active oxygen in the [W2O2(O2)4] structure unit of these soluble species reacts with olefins to form the epoxides and consequently the corresponding W---Ob---W (corner-sharing) and W---Oc---W (edge-sharing) bonds are formed. The peroxo group [W2O2(O2)4] can be regenerated when the W---Ob---W and W---Oc---W bonds react with hydrogen peroxide again. These soluble species lose active oxygen and then polymerize into larger compounds with the W---Ob---W and W---Oc---W bonds and then precipitate from the reaction solution after the hydrogen peroxide is consumed up. Part of the used catalyst seems to form more stable compounds with Keggin structure under the reaction conditions. 相似文献
13.
Reaction of optically active ketone complexes (+)-(R)-[(η5-C5H5)Re(NO)-(PPh3)(η1-O=C(R)(CH3)]+ BF4− (R = CH2CH3, CH(CH3)2m C(CH3)3, C6H5) with K(s-C4H9)3BH gives alkoxide complexes (+)-(RS)-(η5-C5H5)Re(NO)(PPh3)-(OCH(R)CH3) (73–90%) in 80–98% de. The alkoxide ligand is then converted to Mosher esters (93–99%) of 79–98% de. 相似文献
14.
The complexes (O---O)Rh(CH2CH2)2 ((O---OH) = FcC(O)CH2C(O)CH3, PhC(O)CH2C(O)CH3, 1,2-(CH3CO)(OH)C6H4, 3-benzoyl-(+)-camphor) are catalysts for the hydrosilylation of PhMeCO with Ph2SiH2. The optical yield from the reaction catalyzed by the camphor derivative is too low to measure. Only low optical yields (max 8.7% e.e.) are obtained from the same reaction by using similar in situ catalysts with ligands prepared from (+)-PhCH(Me)NH2. Bases such as H− and PhCH(Me)NH− catalyze the hydrosilylation reaction in the absence of rhodium salts, but only low optical yields are obtained. Ph2SiH2 reacts with 2-cyclohexen-1-one under these conditions and the mode of reaction depends on the reaction conditions. 相似文献
15.
The preparation of three Tc(IV) alcoholato complexes: K2[99Tc(OMe)6], K2[99Tc(glyc)3·3C2H5OH (H2glyc = CH2OHCH2OH), and K2[99Tc(butri)2]·CH3OH (H3butri = CH2OHCHOHCH2CH2OH) is described. 相似文献
16.
Treatment of Mn(CO)5SiTolp2H (2) with an excess of LiAlH4, NaBH4, or NaBH3(CN) in THF at room temperature gave hydrosilane H---SiTolp2H in high yield together with Mn2(CO)10. No reduction of CO ligands was observed. On the other hand, treatment of 2 with an excess of Red-Al (=Na[(CH3OCH2CH2O)2AlH2]) in toluene and subsequent addition of aqueous acidic solution afforded alkylsilanols (CH3)SiTolp2(OH) and (C2H5)SiTolp2(OH). Treatment of the reaction mixture of 2 and Red-Al with LiAlH4 in diethyl ether instead of hydrolysis gave alkylhydrosilanes (CH3)SiTolp2H and (C2H5)SiTolp2H. The methyl and ethyl groups on silicon originate from the CO ligands in 2. These products clearly demonstrate that not only the Si---C coupling, but also C---C coupling occurs efficiently in this reaction. 相似文献
17.
Bao-Hua Zhu Wei-Qiang Zhang Quan-Yi Zhao Zhi-Guo Bian Bin Hu Yu-Hua Zhang Yuan-Qi Yin Jie Sun 《Journal of organometallic chemistry》2002,650(1-2):181-187
Six new cluster derivatives [Rh2Co2(CO)6(μ-CO)4(μ4,η2-HCCR)] (R=FeCp2 1, CH2OH 2, (CH3O)C10H6CH(CH3)COOCH2CCH 3) and [RhCo3(CO)6(μ-CO)4(μ4,η2-HCCR)] (R=FeCp2 4, CH2OH 5, (CH3O)C10H6CH(CH3)COOCH2CCH 6) were obtained by the reactions of [Rh2Co2(CO)12] and [RhCo3(CO)12] with substituted 1-alkyne ligands HCCR [R=FeCp2 7, CH2OH 8, (CH3O)C10H6CH(CH3) COOCH2CCH 9] in n-hexane at room temperature, respectively. Alkynes insert into the Co---Co bond of the tetranuclear clusters to give butterfly clusters. [Rh2Co2(CO)6(μ-CO)4(μ4,η2-HCCFeCp2)] (1) was characterized by a single-crystal X-ray diffraction analysis. Reactions of 1, 2 with 7, 8 and ambient pressure of carbon monoxide at 25 °C gave two known cluster complexes [Co2(CO)6(μ2, η2-HCCR)] (R=FeCp2 10, CH2OH 11), respectively. All clusters were characterized by element analysis, IR and 1H-NMR spectroscopy. 相似文献
18.
Fabian Mohr Dana J. Eisler Christopher P. McArdle Khaled Atieh Michael C. Jennings Richard J. Puddephatt 《Journal of organometallic chemistry》2003,670(1-2):27-36
The carbonyl derivatized bis(alkyne) O=C(4-C6H4OCH2CCH)2 was converted into the imine derivatives RN=C(4-C6H4OCH2CCH)2 [R=OH, NHC(O)NH2, NHC6H3-2,4-(NO2)2] and into the 4-bromomethyl-1,3-dioxolane derivative BrCH2C2H3O2C(4-C6H4OCH2CCH)2. The alkyne units in these compounds react with [AuCl(SMe2)] in the presence of base to form the corresponding digold(I) diacetylide complexes, that exist as insoluble oligomers or polymers. They reacted with the diphosphines Ph2PZPPh2 [Z=CC, trans-HC=CH and (CH2)n, n=3–5] to give macrocyclic gold(I) complexes of the type [Au2(μ-LL)(μ-PP)], where LL is the diacetylide and PP the diphosphine ligand. The ability of these macrocyclic complexes to self-assemble to [2]catenanes has been studied. The ketone and imine derivatives do not form [2]catenanes because the orientation of the aryl groups is unfavorable, but the 1,3-dioxolane derivatives may catenate if the ring size is optimum. 相似文献
19.
Fu-Yu Tsai Ray-Hsi Hsu Tsang-Miao Huang Jwu-Ting Chen Gene-Hsiang Lee Yu Wang 《Journal of organometallic chemistry》1996,520(1-2):85-96
Regioselective addition of chalcogenol to an ν3-propargyl complex Pt(PPh3)2(η3-C3H3)](BF4) (2) via the formation of the C---O, C---S, or C---Se bond generates new cationic chalcogenoxyallyl species {Pt(PPh3)2[η3CH2C(ER)CH2]}(BF4) (E = O, R = Me 4(a), Et (4b, iPr (4c), 1Bu (4d), Ph (4e); E=S, E=Et (5b), tBu (5d, Ph (5e); E=Se, R=Ph (6e )) respectively in good yields. Thiol and selenol react with complex 2 much faster than alcohol; and 2 reacts with p-(HO)C6H4(SH) to exclusively yield the thioxyallyl product {Pt(PPh3)2[η3-CH2C(SC6H4OH)CH2]}(BF4) (5f). Among the alcoh and phenol, thereactivity follows the order MeOH > EtOH >, iPrOH >, tBuOH > PhOH. A mechanism comprising a preceding coordination step is postulated. The X-ray structures of 4b, 4e, 5b, 5e and 6e are provided. 相似文献
20.
The title compounds react with unidentate ligands, L, containing either phosphorus or arsenic donor atoms to yield the corresponding compounds of the type Ru(η5---C5Me4Et)(CO)LX; with didentate phosphorus donor ligands the major species formed is the bridged complex {Ru(η5---C5Me4Et)(CO)X}2{Ph2P(CH2)nPPh 2} n = 1, X = Br; n = 2, X = Cl). In contrast, unidentate ligands containing nitrogen donor atoms such as pyridine did not react with Ru(η5---C5Me4Et)(CO)2Cl although reaction with 1,10-phenanthroline or diethylenetriamine yielded the ionic products [Ru(η5---C5Me4Et)(CO)L]+Cl− (L = phen or (NH2CH2CH2)2NH). Reaction of Ru(η5---C5Me4Et)(CO)2Br with AgOAc yielded the corresponding acetato complex Ru(η5---C5Me4Et)(CO)20Ac. Ru(η5--- C5Me4Et)(CO)2X reacts with AgY (Y = BF4 or PF6) in either acetone or dichloromethane to give the useful solvent intermediates [Ru(η5---C5Me4Et)(CO)2(solvent)]+Y−, which readily react with ligands L to yield ionic derivatives of the type [Ru(η5---C5Me4Et)(CO)2L]+Y− (where L = CO, NCMe, py, C2H4 or MeO2CCCCO2Me). 相似文献