共查询到20条相似文献,搜索用时 984 毫秒
1.
Li Xinfang Wang Xueye Liu Wanqiang Wen Xiaohong Long Qingping Tan Yuanqiang Li Jianjun 《化学物理学报(中文版)》2005,18(4):527-532
The molecular geometries optimization and electronic structures of diphenyl disulfide (DPDS) and dibenzyl disulfide (DBDS) compounds were investigated by density functional theory (DFT) and ab initio method at the 6-31G basis set level. The active atoms and bonds of reaction were provided by frontier molecular orbital theory. The molecular orbital parameters of DPDS and DBDS compounds and iron atom cluster were calculated by using density functional theory. The interaction pattern between the organic disulfide compounds and iron atom cluster was discussed based on the approximate rule of orbital energy. Some parameters characterizing the action strength between the organic disulfide compounds and iron atom cluster, including the bonding strength, reactive strength and static action strength, were analyzed by using frontier electron density, super de-localizability, net atomic charge and the interaction energy of chemical adsorption as criteria. The results indicate that S-S chemical bond and C-S chemical bond of the compounds are inclined to be broken when DPDS and DBDS interact with the metal. The anti wear ability order of DPDS and DBDS compounds is DPDS>DBDS, and the extreme pressure ability order of DPDS and DBDS compounds is DBDS>DPDS, and the prediction results based on quantum chemistry calculations are in good accordance with the friction and wear test results. 相似文献
2.
Errede等曾利用氢氧化邻甲基苄基三甲基铵的热解制得螺二邻二亚甲基苯、环二邻二亚甲基苯和聚邻二亚甲基苯。Winberg等人对噻吩的季铵碱的热解有所研究,但未能触及活泼的中间体2,3-二亚甲基-2,3-二氢化噻吩Ⅷ及其二聚体螺环化合物和环状化合物。 相似文献
3.
4.
5.
近年来,随着固氮酶研究的进展,钼铁硫原子簇化学发展很快。迄今国际上已报道了近三十几种钼铁硫簇化合物中,苄基硫醇常作为配体。我们相继合成了含有二苄基二硫的钼铁硫三元包合物。L.Egartner等人在1932年仅测定了二苄基二硫化合物的晶系和晶胞参数。为比较二苄基二硫化合物,当以单体存在 相似文献
6.
对二甲基二烷氧基硅烷的电子轰击质谱进行了研究。断裂方式主要包括以下几种:Si-C键的断裂(脱CH3)、Si-O链的断裂(脱OCH2R、O-O键的断裂(^+CH2R的生成)、C-C键的断裂、氢重排脱烯CnH2n、氢重排脱醛PCHO等。 相似文献
7.
8.
四羰基二(五甲二硅基环戊二烯基)二钼的合成及反应 总被引:3,自引:0,他引:3
本文进一步报道四羰基二(五甲二硅基环戊二烯基)二铜的合成及反应, 五甲二硅基环戊二烯与六羰基钼在甲苯中加热回流9h, 即生成含Mo-Mo键的双核钼配合物1, 1在甲苯中进一步加热回流, 则发生脱羰而生成标题化合物。 相似文献
9.
10.
本文报告烯酮(Ⅲ)的合成,与(Ⅲ)相当的烯醇体即1,2-二羟二环辛四烯(Ⅱ)。合成的关键中間物,二酮(Ⅳ),由一新合成步驟制备,总产率19—36%:低温加氯化氫于环戊二烯得3-氯环戊烯(85—92%),再用鎂使之双合而成二烯(Ⅴ)(80—92%)。(Ⅴ)的臭氧化合物經过氧乙酸分解而形成四元酸(Ⅵ),酯化后得其四甲酯(Ⅶ)(由(Ⅴ)至(Ⅶ)总产率66—75%);后者可环化为二甲氧羰基二酮(Ⅷ)(52—67%),(Ⅷ)經水解脫羧即生成二酮(Ⅳ)(79—84%)。二酮(Ⅳ)可还元为二醇(Ⅸ)(65%)。由二酮(Ⅳ)再經四步反应后即得烯酮(Ⅲ):氯化二酮(Ⅳ)得二氯二酮(Ⅹ)(64—74%);將(Ⅹ)与乙二醇一同脫水縮合得縮二酮(Ⅺ)(52—66%);自(Ⅺ)脫氯化氫后得二烯縮二酮(Ⅻ)(69%),后者与丙酮經交換反应即变为烯酮(Ⅲ)(76%)。上述各化合物的分子結構,均經証明。烯酮(Ⅲ)不含其相当的烯醇体(Ⅱ);在鹼性溶液中亦不能形成稳定的二环幸四烯二醇-陰离子。因此可以相信,二环辛四烯体系具有芳族性的可能性極微。 相似文献
11.
Gaël Zucchi Dr. Olivier Maury Dr. Pierre Thuéry Dr. Frédéric Gumy Jean‐Claude G. Bünzli Prof. Dr. Michel Ephritikhine Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(38):9686-9696
Treatment of Ln(NO3)3?nH2O with 1 or 2 equiv 2,2′‐bipyrimidine (BPM) in dry THF readily afforded the monometallic complexes [Ln(NO3)3(bpm)2] (Ln=Eu, Gd, Dy, Tm) or [Ln(NO3)3(bpm)2]?THF (Ln=Eu, Tb, Er, Yb) after recrystallization from MeOH or THF, respectively. Reactions with nitrate salts of the larger lanthanide ions (Ln=Ce, Nd, Sm) yielded one of two distinct monometallic complexes, depending on the recrystallization solvent: [Ln(NO3)3(bpm)2]?THF (Ln=Nd, Sm) from THF, or [Ln(NO3)3(bpm)(MeOH)2]?MeOH (Ln=Ce, Nd, Sm) from MeOH. Treatment of UO2(NO3)2?6H2O with 1 equiv BPM in THF afforded the monoadduct [UO2(NO3)2(bpm)] after recrystallization from MeOH. The complexes were characterized by their crystal structure. Solid‐state luminescence measurements on these monometallic complexes showed that BPM is an efficient sensitizer of the luminescence of both the lanthanide and the uranyl ions emitting visible light, as well as of the YbIII ion emitting in the near‐IR. For Tb, Dy, Eu, and Yb complexes, energy transfer was quite efficient, resulting in quantum yields of 80.0, 5.1, 70.0, and 0.8 %, respectively. All these complexes in the solid state were stable in air. 相似文献
12.
Rare examples of amido‐iodo complexes of selected divalent lanthanides can be synthesized by using deprotonated Ap*H {Ap*H = 2,6‐diisopropylphenyl)‐[6‐(2,4,6‐triisopropylphenyl)‐pyridin‐2‐yl]‐amine} as a stabilizing ligand. Reaction of [Ap*K]n with [LnI2(thf)n] (Ln = Eu, Yb, n = 4,5) in THF leads to [Ln(Ap*)I(thf)2]2 (Ln = Eu, Yb). An attempted reduction of these divalent heteroleptic complexes with KC8 to synthesize complexes containing an unsupported Ln–Ln bond resulted in the formation of [Ln(Ap*)2(thf)2]. These lanthanide complexes were characterized by X‐ray structure analysis. 相似文献
13.
《Polyhedron》1986,5(4):995-998
Lanthanide perchlorate complexes with 4-N-(2′-hydroxy-1′-naphthylidene) aminoantipyrine [HNAAP(HL)] of types [Ln(L)2ClO4] (where Ln = La, Pr, Nd or Sm) and [Ln(HL)4](ClO4)3 (where Ln = Gd, Tb, Dy, Ho or Y) have been synthesized and characterized. HNAAP acts as a monovalent terdentate ligand in the complexes of the lighter lanthanides and as a neutral bidentate ligand in the complexes of the heavier lanthanides. The perchlorate group is coordinated only in the complexes of the lighter lanthanides. 相似文献
14.
Dr. Dmitry M. Lyubov Tatyana V. Mahrova Anton V. Cherkasov Prof. Georgy K. Fukin Prof. Yury V. Fedorov Prof. Alexander A. Trifonov 《欧洲无机化学杂志》2023,26(25):e202300292
We report the synthesis of Ln3+ nitrate [Ln(Tpm)(NO3)3] ⋅ MeCN (Ln=Yb ( 1Yb ), Eu ( 1Eu )) and chloride [Yb(Tpm)Cl3] ⋅ 2MeCN ( 2Yb ), [Eu(Tpm)Cl2(μ-Cl)]2 ( 2Eu ) complexes coordinated by neutral tripodal tris(3,5-dimethylpyrazolyl)methane (Tpm). The crystal structures of 1Ln and 2Ln were established by single crystal X-ray diffraction, while for 1Yb high resolution experiment was performed. Nitrate complexes 1Ln are isomorphous and both adopt mononuclear structure. Chloride 2Yb is monomeric, while Eu3+ analogue 2Eu adopts a binuclear structure due to two μ2-bridging chloride ligands. The typical lanthanide luminescence was observed for europium complexes ( 1Eu and 2Eu ) as well as for terbium and dysprosium analogues ([Ln(Tpm)(NO3)3] ⋅ MeCN, Ln=Tb ( 1Tb ), Dy ( 1Dy ); [Ln(Tpm)Cl3] ⋅ 2MeCN, Ln=Tb ( 2Tb ), Dy ( 2Dy )). 相似文献
15.
T. V. Balashova A. P. Pushkarev V. A. Il’ichev I. D. Grishin D. V. Govorova M. N. Bochkarev 《Russian Chemical Bulletin》2016,65(7):1739-1742
Heterometallic complexes Ln(L1)5Zn (Ln = Sc, Sm, Gd) were obtained by the reactions of silylamides Ln[N(SiMe)2]3 with 2-(benzoxazol-2-yl)phenol (HL1) in the presence of diethylzinc. Similar reactions with 3-(benzothiazol-2-yl)-2-naphthol (HL2) led to the formation of complexes Ln(L2)5Zn (Ln = Nd, Er, Gd, Yb). The introduction of the zinc-containing fragments provided a considerable increase of photo- and electroluminescence intensity of the scandium complex. 相似文献
16.
《Journal of Coordination Chemistry》2012,65(4):583-592
Two complexes [Ln2(hfga)2(phen)4(H2O)6] · hfga · 2H2O (H2hfga = hexafluoroglutaric acid, phen = 1, 10-phenanthroline, Ln=Tb, 1; Eu, 2) were synthesized under hydrothermal conditions and their structures determined by X-ray crystallography. The complexes consist of dinuclear units with an inversion center. Each Ln(III) is nine-coordinate with two carboxylate oxygens from two hfga ligands, three oxygens from water and four nitrogens from two phen molecules. Two carboxylate groups of one hfga adopt monodentate coordination to Ln(III) as a long bidentate bridge linking two Ln(III) ions to form a dimer. Ln(III) ··· Ln(III) distances of 9.027(3) Å for 1 and 9.043(3) Å for 2 were observed. Both complexes emit strong fluorescence and show characteristic emission of Tb(III) and Eu(III) ions, respectively. 相似文献
17.
Complexes of lanthanide perchlorates with 4-cyano pyridine-1-oxide, 4-chloro 2-picoline-1-oxide and 4-dimethyl-amino 2-picoline-1-oxide
have been isolated for the first time and characterized by analysis, conductance, infrared, NMR and electronic spectra. The
complexes of 4-cyano pyridine-1-oxides have the composition Ln(CyPO)6(ClO4)3. 2H2O (Ln=La, Sm, Dy and Ho); Ln(CyPO)7 (ClO4)3. 2H2O (Ln=Pr, Nd, Er and Yb); and Ln(CyPO)5 (ClO4)3. 2H2O (Ln=Gd and Tb). The complexes of 4-chloro 2-picoline-1-oxide analyse for the formulae Ln(CpicO)6 (ClO4)3 (Ln=La, Pr, Nd and Ho); and Ln (CpicO)5 (ClO4)3 (Ln=Er and Yb), and those of 4-dimethylamino 2-picoline-1-oxide for Ln(DMPicO)6 (ClO4)3 (Ln=La and Nd); Ln(DMPicO)7 (ClO4)3 (Ln=Gd, Er and Yb); and Ln(DMPicO)8 (ClO4)3 (Ln=Dy and Ho). 相似文献
18.
19.
Dr. Paul Benndorf Dipl.‐Chem. Jochen Kratsch Larissa Hartenstein Dipl.‐Chem. Corinna M. Preuss Prof. Dr. Peter W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(45):14454-14463
The treatment of the recently reported potassium salt (S)‐N,N′‐bis‐(1‐phenylethyl)benzamidinate ((S)‐KPEBA) and its racemic isomer (rac‐KPEBA) with anhydrous lanthanide trichlorides (Ln=Sm, Er, Yb, Lu) afforded mostly chiral complexes. The tris(amidinate) complex [{(S)‐PEBA}3Sm], bis(amidinate) complexes [{Ln(PEBA)2(μ‐Cl)}2] (Ln=Sm, Er, Yb, Lu), and mono(amidinate) compounds [Ln(PEBA)(Cl)2(thf)n] (Ln=Sm, Yb, Lu) were isolated and structurally characterized. As a result of steric effects, the homoleptic 3:1 complexes of the smaller lanthanide atoms Yb and Lu were not accessible. Furthermore, chiral bis(amidinate)–amido complexes [{(S)‐PEBA}2Ln{N(SiMe3)2}] (Ln=Y, Lu) were synthesized by an amine‐elimination reaction and salt metathesis. All of these chiral bis‐ and tris(amidinate) complexes had additional axial chirality and they all crystallized as diastereomerically pure compounds. By using rac‐PEBA as a ligand, an achiral meso arrangement of the ligands was observed. The catalytic activities and enantioselectivities of [{(S)‐PEBA}2Ln{N(SiMe3)2}] (Ln=Y, Lu) were investigated in hydroamination/cyclization reactions. A clear dependence of the rate of reaction and enantioselectivity on the ionic radius was observed, which showed higher reaction rates but poorer enantioselectivities for the yttrium compound. 相似文献
20.
A. G. Martynov E. A. Safonova Yu. G. Gorbunova A. Yu. Tsivadze 《Russian Journal of Inorganic Chemistry》2010,55(3):347-354
Two series of heteroleptic crown-substituted tris(phthalocyaninate) complexes (Pc)Ln[(15C5)4Pc]Ln(Pc) and [(15C5)4Pc]Ln[(15C5)4Pc]Ln(Pc), where 15C5 is 15-crown-5, (Pc2−) is the phthalocyaninate dianion, Ln = Nd, Eu, Ho, Er, and Yb, were prepared by the reaction of tetra-15-crown-5-phthalocyanine
H2[(15C5)4Pc] with the corresponding lanthanide acetylacetonates and lanthanum bis(phthalocyaninate) La(Pc)2, which was used as a phthalocyaninate dianion donor. The composition and structure of the synthesized complexes were confirmed
by MALDI TOF mass spectrometry, UV-Vis absorption spectroscopy, and 1H NMR. Complete assignment of the proton resonance signals of the paramagnetic lanthanide complexes was based on analysis
of lanthanide-induced shifts. 相似文献