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1.
The new complex [Ce(CH2=C(CH3)COO)2(NO3)(Phen)]2 was prepared in ethanol-aqueous solution with 8-hydroxyquinoline as the acidity regulator. Its crystal structure was determined by X-ray diffraction analysis. The title complex is triclinic, space group P1, a=1.00832(3)nm, b=1.02858(8)nm, c=1.12350(8)nm, α=113.9250(10)°, β=103.8210(10)°, γ=81.4650(10)°, V=1.03252(14)nm3, Z=1, Dc=1.700g·cm-3, F(000)=522. The coordination number of Ce3+ is nine. CCDC: 211278. 相似文献
2.
K. Wnorowski A. Jowko K. Wojciechowski 《Journal of Radioanalytical and Nuclear Chemistry》2008,278(1):31-37
The kinetics of the peroxy radicals RHFO2 reactions with NO has been studied by using pulse radiolysis and UV absorption spectroscopy. The rate constants of interaction
of oxygen atoms with NO − k
2 = 2.2±0.2·10−12 cm3·s−1 and NO2 − k
3 = 2.1±0.2·10−11 cm3·s−1 were found in agreement with the literature values. The bath gases (SF6 or CO2) have got minor effect on the rate constants of RHFO2+NO→NO2+prod. reactions; RHFO2 = CH3CH2O2, CH3CHFO2, CH3CF2O2, CF3CH2O2, CF3CHFO2. The obtained rate coefficients are in the scope of the literature values, although they are lower than those recommended
in NIST database. The reasons are discussed. 相似文献
3.
T. Yu. Glazunova A. I. Boltalin S. I. Troyanov 《Russian Journal of Coordination Chemistry》2005,31(4):247-252
Novel anhydrous trinuclear 3-oxo complexes of Cr(III), Cr3(3-O)(CF3COO)6(CH3COOH)2(CF3COO) (I) and of Cr(III,III,II), Cr3(3-O)(CF3COO)6(CH3COOH)2(THF) (II) (where THF is (CH2)4O) are synthesized by anodic dissolution of metallic chromium in solutions of trifluoroacetic acid in acetonitrile and in tetrahydrofuran and their structures are studied by X-ray diffraction analysis. Complex I forms orthorhombic crystals with space group Pna21, a = 9.778(1) , b = 16.042(2) , c = 22.851(4) , Z = 4, R
1 = 0.0332; complex II crystallizes in monoclinic system: space group P21/c, a = 9.866(1) , b = 17.895(2) , c = 21.167(4) , = 100.75(2)°, Z = 4, R = 0.0422. The average Cr-(3-O) distances in compounds I and II are almost equal (1.943(3) and 1.927(3) ). An average length of the Cr-O bond in octahedral surrounding of metal atoms is different in complexes I and II (1.985(4) and 2.003(3) , respectively), which is specified by different oxidation states of the metal atom. The CrCr distances lie in an interval of 3.366(1)–3.337(1) .__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 266–272.Original Russian Text Copyright © 2005 by Glazunova, Boltalin, Troyanov. 相似文献
4.
运用量子化学密度泛函理论UB3LYP/6-311+G*和高级电子相关校正的偶合簇(CCSD(T)/6-311+G*)方法,对CH3CH2,CH3CHCl和CH3CCl2自由基与NO2反应的机理和动力学进行了理论研究,得到了体系的势能面信息和可能的反应机理.根据计算得到的各反应热力学参数及反应能垒,采用传统过渡态理论计算了各反应在温度T=298 K和T=700 K时的速率常数.研究结果表明,该类反应均通过1个中间体和1个过渡态生成产物,产物分别为CH3CHO+HNO,CH3CHO+ClNO和CH3CClO+ClNO. 相似文献
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7.
[La(CH2ClCOO)2(NO3)(phen)(H2O)]n的合成和晶体结构 总被引:5,自引:0,他引:5
合成了混合阴离子配合物[La(CH2ClCOO)2(NO3)(phen)(H2O)]n。配合物经元素分析、IR、DTA-TG和UV等表征。用X射线单晶结构分析解析了标题配合物的晶体结构,三斜,空间群P1,晶胞参数为a=10.533(2)?,b=13.136(3)?,c=7.776(1)?,α=96.59(1)°,β=95.76(1)°,γ=108.42(2)°,V=1003.3(3)?3,Z=2,Dc=1.940 g/cm3, F(000)=572, μ(Mo Kα)=24.36 cm-1。 相似文献
8.
四元混配配合物[Ce(CH2=C(CH3)-COO)2(NO3)(phen)]2的合成、表征及晶体结构 总被引:5,自引:0,他引:5
A new complex with mixed-quadriligand [Ce(CH2=C(CH3)-COO)2(NO3)(phen)]2 has been synthesized in aqueous solution of slight acidity and characterized by elementary analysis, IR and TGA. The crystal structure determination shows that the complex belongs to triclinic, space group P1, a=9.614?, b=10.047?, c=11.821?, Z=2, α=100.88(3)°, β=106.29(3)°, γ=97.93(2)°, V=1054(5)?3, Dc=1.741g·cm-3, F(000)=546.00, μ(MoKα)=22.06cm-1. And the crystal is consisted of a binuclear molecule. The coordina-tion of Ce3+ is nine. 相似文献
9.
利用量子化学从头算CASSCF方法在6-311+G (d, p)基组水平上对单线态和三线态RN (R=CH3, CH3CH2)异构化反应及RN脱氢反应的微观机理进行了理论研究. 在MP2/6-311+G (d, p)和CCSD/6-311+G (d, p)水平上进行了单点能校正. 单态和三态势能面的交叉点(ISC)的存在清楚地说明了基态反应物3RN异构化为基态产物1R'NH (R'=CH2, CH3CH)的过程. 电子密度拓扑分析显示在整个异构化过程中有两种类型的结构过渡态: 单态反应通道为T型过渡态, 三态反应通道为环状过渡态. 单线态RN脱氢反应通道中“原子-分子键”的存在说明两个H原子是以H2的形式从RN中脱去的. 相似文献
10.
A simple synthesis of [Ru(CF3CO2)(η2-CF3CO2)(CHPh)(PCy3)2] from dimeric [Ru2(CF3CO2)2(μ-CF3CO2)2(CHPh)2(PCy3)2(μ-H2O)] is described. The new complex crystallizes in monoclinic system (P2(1)/c space group) with distorted octahedral coordination. The very low metathesis activity of this new ruthenium benzylidene complex demonstrates that substitution of chlorides with trifluoroacetates in [RuCl2(CHPh)(PCy3)2] results in loss of the catalytic activity. 相似文献
11.
Treatment of Os(κ2-S2CNMe2)H(CO)(PPh3)2 with HSiMeCl2 or HSiCl3 gives in high yield Os(κ2-S2CNMe2)(SiMeCl2)(CO)(PPh3)2 (1) or Os(κ2-S2CNMe2)(SiCl3)(CO)(PPh3)2 (2), respectively. The crystal structures of both compounds have been determined and the Os-Si distances are 2.3672(10) Å for 1 and 2.3449(12) Å for 2. In solution, and under forcing conditions, both compounds are extraordinarily unreactive towards hydroxide ions. 相似文献
12.
Merlín Rosales Beatriz Alvarado Federico Arrieta Carlos De La Cruz Ángel González Karely Molina Otto Soto Yslamar Salazar 《Polyhedron》2008
The synthesis and solid-state IR, 1H and 31P{1H} NMR spectroscopic characterization of complexes of the type MH(CO)(κ3-OCOR)(PPh3)2 [M = Ru, Os; R = CH3, CH2Cl, C6H5 and CH(CH3)2] are reported in this paper. These compounds were obtained by reaction of the respective cationic complex [MH(CO)(NCMe)2(PPh3)2]BF4 with the sodium salt of the corresponding carboxylic acid in a 1:1 v/v dichloromethane/methanol solution at room temperature. The spectroscopic data of these complexes and some DFT calculations reveal an octahedral geometry with a bidentated carboxylate, two equivalent triphenylphosphines in a mutually trans positions, a linear hydride and a linear carbonyl both in the cis-positions of the coordination sphere. The catalytic results indicate that these complexes are efficient and regioselective precatalysts for the quinoline hydrogenation and for the hydroformylation of 1-hexene, under mild reaction conditions (130 °C and 4 atm H2 and 120 °C and 15 atm H2/CO, respectively). For benzothiophene hydrogenation, the osmium complexes showed low activities whereas the analogous ruthenium complexes were catalytically inactive under somewhat more drastic reaction conditions to those of the quinoline hydrogenation (140 °C and 10 atm H2). 相似文献
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Todd W. Graham 《Journal of organometallic chemistry》2007,692(21):4481-4485
The reaction of CpTi(μ2-Me)(μ2-NPi-Pr3)(μ4-C)(AlMe2)3 with ClSnMe3 and MeO3SCF3 affords the species CpTi(μ2-Cl)(μ2-NPi-Pr3)(μ4-C)(μ2-Cl)(AlMe)(AlMe2)21 and CpTi(μ2-Me)(μ2-NPi-Pr3)(μ4-C)(μ2-O3SCF3)(AlMe)(AlMe2)22, respectively. Both 1 and 2 have been structurally characterized. 相似文献
15.
Donna S. Amenta John W. Gilje Frank T. Edelmann Steffen Blaurock 《Journal of organometallic chemistry》2006,691(23):5065-5068
The reaction of with p-CH3C6H4S(O)2O(CH2)3C6H5 produces (η5-C5H5)(OC)3Mo(CH2)3C6H5. This is only the second structurally characterized organometallic species in which an aromatic moiety is separated by three or more methylene groups. The alkyl chain adopts a staggered conformation, the Mo-C(1)-C(2)-C(3)-C(4) unit is nearly coplanar, and the alkyl chain eclipses the trans-carbonyl group on Mo. NMR evidence indicates that this conformation is preserved in solution. 相似文献
16.
A. A. Pasynskii I. V. Skabitskii Yu. V. Torubaev I. M. Krylov G. G. Aleksandrov 《Russian Journal of Coordination Chemistry》2011,37(8):613-618
A reaction of the dimer [Mn(CO)4(SPh)]2 with (PPh3)2Pt(C2Ph2) gave the heterometallic complex (CO)4Mn(μ-SPh)Pt(PPh3)2 (I) and its isomer (CO)3(PPh3)Mn(μ-SPh)Pt(PPh3)(CO) (II). A reaction of complex I with a diphosphine ligand (Dppm) yielded the heterometallic complex (CO)3Mn(μ-SPh)Pt(PPh3)(Dppm) (III). Complexes I–III were characterized by X-ray diffraction. In complex I, the single Mn-Pt bond (2.6946(3) ?) is supplemented with a thiolate bridge with the shortened Pt-S and Mn-S bonds (2.3129(5)
and 2.2900(6) ?, respectively). Unlike complex I, in complex II, one phosphine group at the Pt atom is exchanged for one CO group at the Mn atom. The Mn-Pt bond (2.633(1) ?) and the thiolate
bridge (Pt-S, 2.332(2) ?; Mn-S, 2.291(2) ?) are retained. In complex III, the Mn-Pt bond (2.623(1) ?) is supplemented with thiolate (Pt-S, 2.341(2) ?; Mn-S, 2.292(2) 0?) and Dppm bridges (Pt-P,
2.240(1)?; Mn-P, 2.245(2) ?). Apparently, the Pt atom in complexes I–III is attached to the formally double bond , as in Pt complexes with olefins. 相似文献
17.
用量子化学密度泛函方法,在B3LYP/6-31G*水平下研究了叔丁基自由基(CH3)3C和NO2气体的反应机理.研究表明,该反应是在单、三态势能面上的多通道反应.不同反应通道的产物不同,单态下反应更容易发生.常温下对于一个敞开体系(例如在大气当中),(CH3)3C自由基和NO2作用主要生成比较稳定的化合物(CH3)3CONO和(CH3)3CNO2.这对于消除大气污染起到一定的作用. 相似文献
18.
用Co2(CO)8分别与两个杂环配体C(S)NHP(S)(C6H4OCH3)OC(Ph)CH (L1)和C(S)NHC(CH3)2P(S)(Cl)N(Ph) (L2)反应,合成两个新的三核钴羰基硫簇合物Co3(CO)7(μ3-S)[μ,η2-CNP(S)(C6H4OCH3)OC(Ph)CH](Ⅰ)和Co3(CO)7(μ3-S)[μ,η2-SCNC(CH3)2P(S)(Cl)N(Ph)](Ⅱ)。用元素分析,IR, 1H NMR, 31P NMR及MS谱表征了它们的结构,同时用X射线衍射法测定了它们的晶体分子结构,二者属于三斜晶系,空间群P1,Ⅰ的晶胞参数为:a=0.84768(1)nm,b=1.19049(3)nm,c=1.43639(1)nm,α=86.926(1)°,β=81.601(3)°,γ=88.535(2)°,V=1.4318(5)nm3,Z=2,Dc=1.641g·cm-3,F(000)=716,μ=1.893mm-1,R=0.0602,Rw=0.1515。Ⅱ的晶胞参数为:a=1.2050(2)nm,b=1.2448(2)nm,c=0.8951(2)nm,α=97.49(1)°,β=93.552(4)°,γ=108.432(3)°,V=1.2554(3)nm3,Z=2,Dc=1.841g·cm-3,F(000)=690,μ=2.419mm-1,R=0.0423,Rw=0.1075。Ⅰ和Ⅱ的分子骨架Co3S为三角锥构型,S作为面桥基配体,所有CO作为端基配体与三个Co原子成键。Ⅰ中含有CoCoCN四元环组件,Ⅱ中含有CoCoSCN五元环组件。 相似文献
19.
Svetlana I. Pomogailo Victoria A. Ershova Vladimir M. Pogrebnyak Anatoly V. Golovin Anatolii D. Pomogailo 《Journal of organometallic chemistry》2005,690(19):4258-4264
The complex [(μ-H)Os3(μ-OCNMe2)(CO)9{P(CH2CHCH2)Ph2}] derived from the replacement of a lightly-stabilizing NMe3 ligand in [(μ-H)Os3(μ-OCNMe2)(CO)9(NMe3)] by allyldiphenylphosphine molecule was physico-chemically and X-ray structurally characterized and served further as a metal cluster monomer to be immobilized on a polymer surface. The copolymerization of this cluster monomer with styrene was studied. It was found that the cluster molecule, when copolymerized, maintains its integrity and the overall structure. The cluster copolymers obtained have been tested as catalysts for oxidative dehydrogenation and cyclohexenol hydroxylation reactions. 相似文献
20.
多组态二级微扰理论计算CH3O2激发光谱以及CH3O2→CH3+O2解离反应 总被引:1,自引:0,他引:1
在Cs对称性和aug-cc-pVTZ基组水平下, 采用全活化空间自洽场方法(CASSCF)研究了CH3O2自由基基态及其阴阳离子的12个低激发态. 为了进一步考虑动态电子相关效应, 采用二级多组态微扰理论(CASPT2)获得更加精确的能量值. 所有计算得到的电子态都是价电子态, 而且所得绝热激发能和电子亲和势与实验值非常接近.在CASPT2//CASSCF理论水平下计算了CH3O2从2A"和2A'电子态的CH3O2→CH3+O2的解离反应的势能曲线(PECs). 优化得到的裂解产物的几何结构和能量与分别优化CH3和O2得到的结果进行比较, 从而确定裂解产物的电子态. 结果表明, 从2A"和2A'电子态的解离反应分别对应产物CH3(2A")+O2(3A")和CH3(2A")+O2(1A"). 相似文献