共查询到20条相似文献,搜索用时 472 毫秒
1.
测定了三核苯甲酸铁配合物[Fe3O(OBz)6(CH3OH)3](NO3)(CH3OH)2(OBz-=苯甲酸根)的电子光谱,应用配体场理论和T-S图求得配体场参数10Dq=12457cm-1.用CNDO/2方法对其简化模型进行了计算。 相似文献
2.
研究了[Ru(phen)2(H2biim)](PF6)2(1)与各种阴离子之间的选择性作用, 发现配合物1与Cl-, Br-, I-, NO3-, HSO4-和H2PO4-阴离子之间存在氢键作用. OAc-阴离子与配合物1作用, 由于强的氢键作用使H2biim上的一个H转移到OAc-上, 使配合物1脱去一个质子, 形成{[Ru(phen)2(H2biim)](OAc)}结合体, 溶液颜色由黄色变为橙棕色. 由于F-能形成非常稳定的HF2-, 配合物1逐步脱去2个质子, 溶液颜色由黄色变为紫色, 因此可作为裸眼检测阴离子的识别剂. 相似文献
3.
研究了三辛基氧化膦(TOPO)和三丁基氧化膦(TBPO)在离子液体(ILs) 1-烷基-3-甲基咪唑双三氟甲基磺酰亚胺盐(CnmimNTf2, n=2, 4, 6, 8)中萃取分离UO2(NO3)2. TOPO-C2mimNTf2和TOPO-C4mimNTf2体系萃取UO2(NO3)2时会出现三相, 而TBPO萃取UO2(NO3)2的萃合物可以很好地溶解在所有离子液体中. 论文也考察了萃取过程中的萃取剂浓度效应、酸效应、盐效应. 水相加入HNO3会降低萃取效率. 盐效应证明了萃取是一种阳离子交换机理. 水相中加入NO3-能够提高U的萃取, 这说明NO3-参与萃取. 选择性研究表明: 除了在高酸度下对Zr 的显著萃取, TBPO-C4mimNTf2萃取体系在低酸度下对U呈现较好的选择性; 去除U后, 在低酸度下该体系对三价Nd 仍保持较好的选择性. 通过定量比较离子液体中NO3-进入量, 电喷雾质谱(ESI-MS)和紫外光谱表征确定了TBPO-CnmimNTf2中萃取机理的差异性. 萃取中存在两种萃合物, 即UO2(TBPO)3(NO3)+和UO2(TBPO)32+, 其中UO2(TBPO)3(NO3)+的比例从C2mimNTf2体系到C8mimNTf2体系逐渐增加. 相似文献
4.
采用水热方法合成了4种Sm3+配合物, 即{[SmZn(2,5-pdc)2(tp)0.5(H2O)]·2H2O}n(1), [Sm2Zn2(C6H5COO)10(Imh)2(H2O)2](2), {[Sm2(NO2C6H4COO)6(H2O)4]·H2O}n(3)和{[SmN(CH2COO)3(H2O)2]·H2O}n(4)[2,5-pdc=2,5-吡啶二羧酸根, tp=对苯二甲酸根, C6H5COO=苯甲酸根, Imh=咪唑, NO2C6H4COO=对硝基苯甲酸根, N(CH2COO)3=氨三乙酸根]. 通过单晶X射线衍射确定了其晶体结构. 在室温下测定了其红外光谱、 紫外-可见-近红外光谱以及在近红外区和可见区的发射光谱. 结果表明, 4种配合物在近红外区或可见区均出现Sm3+离子的特征发射. 这是形成配合物后, Zn-配体部分和配体对Sm3+离子发光的敏化作用所致. 此外, 讨论了不同有机配体或d过渡金属离子对Sm3+离子发光的影响, 并分析了配合物中Sm3+离子的近红外发射带位移、 劈裂和加宽的原因. 相似文献
5.
在溶剂热条件下制备了系列新配合物:[Cr2(tpc)2(HCOO)2(OH)2]·4H2O (1)、[Ba(tpc)2(H2O)2]n (2)、[Zn2(tpc)2(NO3)2]n (3)、[Pb(Htpc)(NO3)2]·2H2O (4)和[Rh(Htpc)Cl3]·CH3OH·H2O (5)(Htpc=2,2′∶6,2″-三联吡啶-4-羧酸)。X射线单晶衍射分析表明,有机配体呈4种不同的配位方式;配合物1~5通过C—H…O/N氢键和π…π相互作用形成了新颖的超分子网络。研究了这些配合物的发光性能。在365 nm紫外辐射下,晶体2~5分别呈现绿色、蓝色... 相似文献
6.
采用CCSD(T)//M06-2X/6-311++G(d,p)方法, 结合传统过渡态理论, 研究了硝酸异丙酯与Cl原子、 OH及NO3自由基的反应机理和动力学. 两个反应物单体首先形成氢键复合物, 随后X(X=Cl原子、 OH和NO3自由基)提取硝酸异丙酯中叔碳的α-H原子或甲基的β-H原子, 室温下, 以X提取α-H原子为主. 反应的主要历程为 Cl原子(OH或NO3自由基)提取(CH3)2CHONO2的α-H原子, 生成HCl(H2O或HNO3)分子和(CH3)2CONO2自由基, 后者分解为丙酮和NO2. 结果表明, 在200~500 K温度范围内, 随着温度的升高, 丙酮和NO2的产率降低; 在室温下, 硝酸异丙酯与Cl原子、 OH和NO3自由基反应的速率常数分别为3.933×10-11, 1.182×10-13和7.134×10-19 cm3·molecule-1·s-1. 计算所得硝酸异丙酯与OH自由基反应的动力学数据与实验结论一致. 相似文献
7.
Qingqing Guo Nanzhu Li Qian Zou Jiage Jia Yifan Wei Songsong Bao Limin Zheng 《中国化学快报》2022,33(6):3259-3262
The thermal decomposition of Ag NO3is known to produce metallic Ag, but single-atomic dispersion is hard to achieve instead of the aggregation state of nanoparticles. Herein, we develop an efficient approach to thermally generate and stabilize single Ag atoms via the coordination effect. Two desired Co-Ag phosphonates [Ag2ⅠCo2Ⅲ(notp H3)2(NO3)]X [X = NO3-(1) or Cl O4- 相似文献
8.
光照法研究超氧化物歧化酶及其模型化合物与超氧离子的反应动力学 总被引:8,自引:0,他引:8
用改进的光照法研究了超氧化物歧化酶及其模型化合物μ-桥基·二(2,6-二乙酰基吡啶)缩二丙二胺合铜(Ⅱ)(桥基为SCN-,N3-,I-,Br-,Cl-,OH-)与超氧离子的反应动力学,测定了反应速率常数kQ,结果表明,超氧化物歧化酶的kQ与脉冲辐解法及黄嘌呤氧化酶法的结果一致。6种配合物中,Cu2L(SCN)(ClO4)3的kQ最大,Cu2L(N3)(ClO4)3的最小,并讨论了真kQ不同的原因。 相似文献
9.
2,6-二甲酚双波长分光光度法同时测定水中NO3-及NO2-的研究 总被引:3,自引:0,他引:3
水中NO3-和NO2-的一般光度法同时测定已见报导,但其操作手续均较麻烦。2,6-二甲酚光度法单独测定NO2-或NO2-虽已有报导,可是它们相互干扰。我们采用双波长光度法,测定NO3-和NO2-在H2SO4介质与2,6-二甲酚的反应产物,既免除了它们的相互干扰,又达到同时测定的目的。 相似文献
10.
以多苯并咪唑配体1,1,4,7,7-五(2-苯并咪唑甲基)-二乙基三胺(DTPB)为主配体, 合成了锰(Ⅱ)配合物[Mn(DTPB)Ac]Ac·8H2O(1)和[Mn2(DTPB)(NO3)2(H2O)2][Mn2(DTPB)(NO3)2(H2O)(CH3OH)]·(NO3)4·5CH3OH·H2O(2), 并对其进行了表征. 利用紫外-可见吸收光谱和黏度实验研究了配合物1和2与DNA的相互作用, 发现这2个配合物均能与DNA结合, 并对配合物与DNA作用的机理进行了探讨. 利用琼脂糖凝胶电泳和直角光散射(RALS)技术研究了配合物1和2促进DNA凝聚的性质. 结果表明, 在近中性条件下2个配合物都能促使DNA凝聚. 利用透射电子显微镜(TEM)观察了不同凝聚体的形态. 相似文献
11.
Víctor Dur-Vil D. Michael P. Mingos Ramn Vilar Andrew J. P. White David J. Williams 《Journal of organometallic chemistry》2000,600(1-2):198-205
Improved syntheses for the dimeric compounds [Pd2(μ-X)2(PBut3)2] (X = Br, I) have been developed and the X-ray crystal structure for the dimer with X = 1 is reported. The reactions of these dimers with CNR (R = 2,6-dimethylphenyl), H2 and a series of terminal and substituted alkynes are also reported. The dimer with X = Br is an initiator for the catalytic polymerisation of phenylacetylene. The product of the dimers with disubstituted alkynes results in the synthesis of trimeric species with formula [Pd3(μ-X){ν2-C4(CO2R)4}2][PBut3)Me]2 (X = Br, I; R = Me, Et). The X-ray crystal structure of one of these compounds (when R = Et and X = I) is presented, demonstrating that the palladium dimers assist the C---C coupling of the alkynes. 相似文献
12.
Günter Urban Karlheinz Sünkel Wolfgang Beck 《Journal of organometallic chemistry》1985,290(3):329-339
The compounds (π-C5H5)(CO)2LM-X (L = CO, PR3; M = Mo, W; X = BF4, PF6, AsF6, SbF6) react with H2S, p-MeC6H4SH, Ph2S and Ph2SO(L′) to give ionic complexes [(π-C5H5)(CO)2LML′]+ X−. Also sulfur-bridged complexes, [(π-C5H5)(CO)3W---SH---W(CO)3(π-C5H5)]+ AsF6− and [(π-C5H5)(CO)3M-μ-S2C=NCH2Ph-M(CO)3(π-C5H5)], have been obtained. Reactions with SO2 and CS2 have been examined. 相似文献
13.
J. Fornis-Cmer A. Aaliti N. Ruiz A.M. Masdeu-Bult C. Claver C.J. Cardin 《Journal of organometallic chemistry》1997,530(1-2):199-209
Addition of 1,4-dithiols to dichloromethane solutions of [PtCl2(P-P)] (P-P = (PPh3)2, Ph2P(CH2)3PPh2, Phd2P(CH2)4PPh2; 1,4-dithiols = HS(CH2)4SH, (−)DIOSH2 (2,3-O-isopropylidene-1,4-dithiol-l-threitol), BINASH2 (1,1′-dinaphthalene-2,2′-dithiol)) in the presence of NEt3 yielded the mononuclear complexes [Pt(1,4-dithiolato)(P-P)]. Related palladium(II) complexes [Pd(dithiolato)(P-P)] (P-P=Ph2P(CH2)3PPh2, Ph2P(CH2)4PPh2; dithiolato = −S(CH2)4S−, (−)-DIOS) were prepared by the same method. The structure of [Pt((−)DIOS)(PPh3)2] and [Pd(S(CH2)4S)(Ph2P(CH2)3PPh2)] complexes was determined by X-ray diffraction methods. Pt—dithiolato—SnC12 systems are active in the hydroformylation of styrene. At 100 atm and 125°C [Pt(dithiolate)(P-P)]/SnCl2 (Pt:Sn = 20) systems provided aldehyde conversion up to 80%. 相似文献
14.
Mercedes Cano Jos A. Campo Margarita Panizo Jesús Tornero Nieves Menndex 《Polyhedron》1994,13(24):3309-3316
Three families of heterobimetallic compounds were obtained by reaction of [Mo(CO)3(CH3CN)2(Cl)(SnRCl2)] (R = Ph, Me) with P(4-XC6H4)3 (X = Cl, F, H, Me, MeO). The type of compound obtained dependent on the solvent and concentration of the starting compound. So, [Mo(CO)2(CH3COCH3)2(PPh3)(Cl)(SnRCl2)]·nCH3COCH3 (R = Ph, n = 0.5; R = Me, n = 1) (type I) and [Mo(CO)3{P(4-XC6H4)3}(μ-Cl)(SnRCl2)]2 (R = Ph, X = Cl, F, H, Me, MeO; R = Me, X = Cl, F) (type II) were isolated from acetone solution in ca 0.05 M and 0.1 M concentrations, respectively. However, [Mo(CO)3(CH3CN) {P(4-XC6H4)3}(Cl)(SnRCl2)] (R = Ph, X = H; R = Me, X = Cl, F, H) (type III) were obtained from dichloromethane solution independently of the concentration used. All new complexes showed a seven-coordinate environment at molybdenum, containing Mo---Cl and Mo---Sn bonds. Mössbauer spectra indicated a four-coordination at tin for type III complexes. 相似文献
15.
Sensuke Ogoshi Takuma Nishida Yoshiaki Fukunishi Ken Tsutsumi Hideo Kurosawa 《Journal of organometallic chemistry》2001,620(1-2):190-193
Isomerization of phenyl-substituted propargylplatinum(II) complex, trans-Pt(CH2CCPh)(Cl)(PPh3)2 (1) to allenyl complex, trans-Pt(CPh=C=CH2)(Cl)(PPh3)2 (2) was found to be catalyzed by zerovalent complex Pd(PPh3)4. The reaction was proposed to proceed through the transfer of the propargyl/allenyl ligand both from Pt(II) to Pd(0) and Pd(II) to Pt(0). The former transfer, which seemingly has a thermodynamic disadvantage, has unambiguously been confirmed to take place; treatment of 1 with Pd(PPh3)4 or a mixture of Pd2(dba)3 and PPh3 resulted in the formation of Pd(I) complex, Pd2(μ-PhCCCH2)(μ-Cl)(PPh3)2 which lies in equilibrium with a mixture of propargyl/allenylpalladium(II) and Pd(0) complexes. 相似文献
16.
Tetsuro Murahashi Hideo Kurosawa Nobuko Kanehisa Yasushi Kai 《Journal of organometallic chemistry》1997,530(1-2):187-189
An η1-butadienyl complex [trans-η1-CH2=C(Me)C=CH2Pd(PPh3)2Cl] (1) reacted with [(μ-η2:η2-1,3-butadiene)Pd2(PPh3)(μCl)Cl] (2) to result in displacement of the diene ligand of 2 accompanied by exchange of PPh3 of 1 with Cl anion of 2 producing a butadienyl tripalladium cluster [(μ-CH2=C(Me)C=CH2)Pd(PPh3)Cl2 · Pd2(PPh3)2(μ-Cl)] (3) stabilized by the zwitterionic structure in moderate yield. The X-ray structure analysis of 3 revealed rigid binding of [Pd2(PPh3)2(μ-Cl)]+ and [CH2 =C(Me)C=CH2Pd(PPh3)Cl2]− through the π-bond coordination of the butadienyl group to the dipalladium cation. 相似文献
17.
W. Ryba-Romanowski S. Go
b G. Dominiak-Dzik W. A. Pisarski D. Podsiada Z. Czapla 《Journal of Molecular Structure》1998,450(1-3):219-222
Chromium doped (CH3)2NH2Al(SO4)2·6H2O (DMAAlS) and (CH3)2NH2Ga(SO4)2·6H2O (DMAGaS) single crystals were grown and investigated using the methods of optical spectroscopy. It was found that the Cr3+ ions in the two crystals are situated in a strong crystal field in which the 2E state is the lowest. The single narrow R-line associated with the 2E–4A2 phosphorescence of Cr3+ in DMAAlS in a ferroelectric phase indicates an undistorted octahedral site, whereas important distortion of Oh symmetry and structural disorder was inferred from spectral data obtained with DMAGaS:Cr3+ in a low temperature phase. Results of optical investigation are discussed taking into account the structural data. 相似文献
18.
Taku Katayama Kiyotaka Onitsuka Shigetoshi Takahashi 《Journal of organometallic chemistry》2000,610(1-2):31-37
Treatment of ruthenium complexes [CpRu(AN)3][PF6] (1a) (AN=acetonitrile) with iron complexes CpFe(CO)2X (2a–2c) (X=Cl, Br, I) and CpFe(CO)L′X (6a–6g) (L′=PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X=Cl, Br, I) in refluxing CH2Cl2 for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO)2X (3a–3c) (X=Cl, Br, I) and CpRu(CO)L′X (7a–7g) (L′=PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X=Br, I), respectively. Similar reaction of [CpRu(L)(AN)2][PF6] (1b: L=CO, 1c: P(OMe)3) causes double ligand transfer to yield complexes 3a–3c and 7a–7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(μ-I)]2 was isolated from the reaction of 1a with 6a at 0°C. Complex 11a slowly decomposes in CH2Cl2 at room temperature to give 3a, and transforms into 7a by the reaction with PMe3. 相似文献
19.
《Journal of Molecular Structure》2003,650(1-3):49-56
Two novel hydrogen maleato (HL) bridged Cu(II) complexes ∞1[Cu(phen)Cl(HL)2/2] 1 and ∞1[Cu(phen)(NO3)(HL)2/2] 2 were obtained from reactions of 1,10-phenanthroline, maleic acid with CuCl2·2H2O and Cu(NO3)2·3H2O, respectively, in CH3OH/H2O (1:1 v/v) at pH=2.0 and the crystal structures were determined by single crystal X-ray diffraction methods. Both complexes crystallize isostructurally in the monoclinic space group P21/n with cell dimensions: 1 a=8.639(2) Å, b=15.614(3) Å, c=11.326(2) Å, β=94.67(3)°, Z=4, Dcalc=1.720 g/cm3 and 2 a=8.544(1) Å, b=15.517(2) Å, c=12.160(1) Å, β=90.84(8)°, Z=4, Dcalc=1.734 g/cm3. In both complexes, the square pyramidally coordinated Cu atoms are bridged by hydrogen maleato ligands into 1D chains with the coordinating phen ligands parallel on one side. Interdigitation of the chelating phen ligands of two neighbouring chains via π–π stacking interactions forms supramolecular double chains, which are then arranged in the crystal structures according to pseudo 1D close packing patterns. Both complexes exhibit similar paramagnetic behavior obeying Curie–Weiss laws χm(T−θ)=0.414 cm3 mol−1 K with the Weiss constants θ=−1.45, −1.0 K for 1 and 2, respectively. 相似文献
20.
The attempted preparation of bis(trifluoromethylsulphanyl)thioketene is described. Mono-and di-(trifluoromethylsulphanyl)-substituted orthothioesters may be prepared fromCH3C(SC2H5)3 and CF3SCl in the presence of anhydrous ZnCl2. The unstable compoundshave been isolated and characterized. The corresponding CF3Se and CF3SO2 derivativesare only formed as intermediates which decompose to ketene diethylmercaptal. Suchmono- and di-substituted products are obtained in good yield from H2C=C(SC2H5)2 andCF3ECl (E=S, Se). The reaction of H2C=C(SC2H5)2 with CF3SO2F gave only poor yieldsof (CF3SO2)nCH2−n=C(SC2H5)2 (n=1, 2) which were only capable of characterizationin etheral solution by spectral means. Attempts to prepare (CF3S)2C=C=S by refluxing(CF3S)2CHC(O)Cl, (CF3S)2CHC(O)OH or (CF3S)2C=C=O with P4S10 in toluene yieldedonly the cyclic dimer and the corresponding 1,3,4-trithiolan. 相似文献