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Application of the oscillator strength of “hypersensitive” transitions to the investigation of complex equilibria of lanthanide ions—I “超敏”跃迁振荡强度在镧系离子复平衡研究中的应用
Pub Date : 1981-01-01 DOI: 10.1016/0022-1902(81)80036-X
K. Bukietyńska, A. Mondry, E. Osmȩda

A method of evaluation of stability constants for the lanthanide complexes from the changes of oscillator strengths of “hypersensitive” f-f transitions as a function of total ligand concentration is proposed. The method is discussed for neodymium acetate and glycolate and holmium lactate complexes. Stability constants calculated for mononuclear species are compared with the potentiometric data of Sonesson. This method is also useful for the calculation of thermodynamic parameters using measurements of the dependence of the oscillator strength on temperature.

The method is limited to lanthanide ions with f2-f6 and f8-f12 electronic configurations.

提出了一种利用“超敏感”f-f跃迁振荡强度随总配体浓度的变化来评价镧系配合物稳定性常数的方法。讨论了醋酸钕与乙醇酸和乳酸钬配合物的合成方法。将计算的单核物质的稳定常数与Sonesson的电位测量数据进行了比较。这种方法也适用于利用测量振荡器强度对温度的依赖性来计算热力学参数。该方法仅限于具有f2-f6和f8-f12电子构型的镧系离子。
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引用次数: 17
Crystal structure of a new insertion compound formed by PdCl2 and tri-methylamine [(CH3)3NH]2PdCl4.(CH3)3NHCl 由PdCl2和三甲胺[(CH3) 3nhh]2PdCl4.(CH3)3NHCl组成的新插入化合物的晶体结构
Pub Date : 1981-01-01 DOI: 10.1016/0022-1902(81)80086-3
Dominique Zveguintzoff, Claudette Bois, Nguyen Quy Dao

The complex 3[(CH3)3NHCl].pdCl2 crystallises in the orthorhombic system, space group Pnma: a = 990(1) pm; b = 1209(1) pm; c = 1721(2) pm; Z = 4; dth = 1.49; dexp = 1.45. The structure is composed of square planar PdCl42− ions (average length PdCl = 230 pm), of two ammonium groups, each one equidistant of two chlorine atoms and in cis position to the plane of PdCl42−. A third (CH3)3NHCl molecule is in insertion in the structure. This is a new type of solvate in which the insertion molecule is an ion pair.

络合物3[(CH3)3NHCl]。pdCl2在正交体系中结晶,空间群Pnma: a = 990(1) pm;B = 1209(1) pm;C = 1721(2) pm;Z = 4;DTH = 1.49;Dexp = 1.45。该结构由两个铵基的方形平面PdCl42−离子(平均长度PdCl = 230 pm)组成,每个铵基与两个氯原子的距离相等,并且与PdCl42−的平面呈顺式位置。第三个(CH3)3NHCl分子插入到结构中。这是一种插入分子为离子对的新型溶剂化物。
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引用次数: 1
Stereoselectivity and exciton cotton effects in mixed complexes of zinc(II) 锌(II)混合配合物的立体选择性和激子棉效应
Pub Date : 1981-01-01 DOI: 10.1016/0022-1902(81)80616-1
S. Bunel ∗, G. Larrazábal, A. Decinti

Mixed complexes of Zn(II) with chiral aminoacids and 1,10-phenanthroline have been prepared and their C.D. and O.R.D. spectra measured. All the C.D. spectra exhibited an exciton splitting at 268 nm and their intensities depended on the chiral ligand. These results were interpreted in terms of steric effects through the exciton theory.

制备了锌(II)与手性氨基酸和1,10-菲罗啉的混合配合物,并测定了它们的cd和o.r.d光谱。所有的cd光谱在268 nm处都表现出激子分裂,其强度与手性配体有关。这些结果通过激子理论解释为空间效应。
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引用次数: 5
Synthesis and characterization of some dimeric dialkoxo-bridged Fe(III) complexes with 1, 1, 1, 5, 5, 5-hexafluoropentan-2, 4-dione 与1,1,1,5,5,5 -六氟戊烷- 2,4 -二酮的二聚二氧键接铁(III)配合物的合成与表征
Pub Date : 1981-01-01 DOI: 10.1016/0022-1902(81)80601-X
Neville T. Moxon, Jonathan H. Moffett, Anthony K. Gregson

A series of compounds with the empirical formulae Fe(hfa)2OR (Hfha = 1, 1, 1, 5, 5, 5-hexafluoropentan-2, 4-dione, R = CH3, C2H5, sec-C4H9) and the parent material Fe(hfa)3 have been prepared and characterized using analytical data, IR and optical spectroscopy, magnetic susceptibility measurements and powder X-ray diffraction. The Fe(hfa)2OR adducts are antiferromagnetic dimers with J ∼ 12 cm−1. Unusual products have been isolated when ethylene glycol is used as the alcohol.

本文制备了一系列分子式为Fe(hfa)2OR (Hfha = 1,1,1,5,5,5 -六氟戊烷- 2,4 -二酮,R = CH3, C2H5, sec-C4H9)的化合物和母体材料Fe(hfa)3,并利用分析数据、红外光谱、光学光谱、磁化率测量和粉末x射线衍射对其进行了表征。Fe(hfa)2OR加合物是J ~ 12 cm−1的反铁磁性二聚体。当乙二醇作为醇时,已分离出不同寻常的产物。
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引用次数: 6
Extraction of Zn(II) and Cd(II) with diphenylcarbazone in presence of nitrogen-containing organic bases 含氮有机碱存在下二苯咔唑萃取Zn(II)和Cd(II)
Pub Date : 1981-01-01 DOI: 10.1016/0022-1902(81)80220-5
B. Jain, J. Singh, R. Goyal, S. N. Tandon
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引用次数: 1
Complex formation between silver and halides in fused acetamide 在熔融乙酰胺中银和卤化物之间形成络合物
Pub Date : 1981-01-01 DOI: 10.1016/0022-1902(81)80129-7
Maura Gusteri, Vito Bartocci, Franca Castellani, Giuseppe Scarponi
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引用次数: 0
EPR studies on Cu(3-amino, 5-methyl isoxazole)4 (ClO4)2 and Cu(3-amino, 5-methyl isoxazole)4 (NO3)2 铜(3-氨基,5-甲基异恶唑)4 (ClO4)2和铜(3-氨基,5-甲基异恶唑)4 (NO3)2的EPR研究
Pub Date : 1981-01-01 DOI: 10.1016/0022-1902(81)80329-6
B.A. Sastry, S.Md. Asadullah, G. Ponticelli, M. Massacesi

EPR studies have been carried out on Cu(3-AMI)4(ClO4)2 and Cu(3-AMI)4(NO3)2[3-AMI = 3-amino, 5-methyl isoxazole] in polycrystalline and solution forms both at room (300 K) and liquid nitrogen temperature to obtain stereochemical information and the nature of the metal-ligand bond. Cu(II) hyperfine lines are obtained in these complexes even at room temperature, which is rare for a non-dilute Cu(II) complex. No ligand hyperfine (LHF) structure from bonded nitrogen is obtained in polycrystalline samples of these complexes at the above temperatures to allow the σ-bond strength to be estimated more accurately. The change in the spectral parameters and resolution at liquid nitrogen temperature (LNT) is negligible. The above parameters obtained in MeCN and pyridine solutions of Cu(3-AMI)4(ClO4)2 obtained at LNT are of comparable magnitude with the polycrystalline values indicating less solvation in these solvents. LHF structure from bonded nitrogens observed on the perpendicular component of the above sample in forzen pyridine solution enabled us to calculate the σ-bond strength more accurately than the other cases. The species formed in the DMF (N, N′-dimethylformamide) solution of Cu(3-AMI)4(NO3)2 is characteristic of a CuO6 chromophore indicating stronger solvation in the above solution. The 4s-character in the ground state of Cu(II) in all the above cases was calculated to determine the relative strengths of axial fields.

在室温(300 K)和液氮温度下,对Cu(3-AMI)4(ClO4)2和Cu(3-AMI)4(NO3)2[3-AMI = 3-氨基,5-甲基异恶唑]在多晶和溶液形态下进行了EPR研究,以获得立体化学信息和金属-配体键的性质。这些配合物在室温下也能得到Cu(II)的超细线,这在非稀Cu(II)配合物中是罕见的。在上述温度下,这些配合物的多晶样品中没有得到由键合氮形成的配体超细(LHF)结构,从而可以更准确地估计出σ-键强度。在液氮温度下,光谱参数和分辨率的变化可以忽略不计。在LNT得到的Cu(3-AMI)4(ClO4)2的MeCN和吡啶溶液中得到的上述参数与多晶值相当,表明在这些溶剂中溶剂化程度较低。从上述样品在刚性吡啶溶液中的垂直分量上观察到的键合氮的LHF结构,使我们能够比其他情况更准确地计算出σ-键强度。在Cu(3-AMI)4(NO3)2的DMF (N, N ' -二甲基甲酰胺)溶液中形成的物质具有CuO6发色团的特征,表明在上述溶液中溶剂化作用较强。通过计算上述所有情况下Cu(II)基态的4s- s特征来确定轴向场的相对强度。
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引用次数: 3
Preparation and structural studies of addition compounds of Sn(IV) halides, organotin(IV) halides and pseudohalides with acetone picolinoyl, nicotinoyl and isonicotinoyl hydrazones 锡(IV)卤化物、有机锡(IV)卤化物和假卤化物与丙酮吡啶酰、烟碱酰和异烟碱酰腙加成化合物的制备和结构研究
Pub Date : 1981-01-01 DOI: 10.1016/0022-1902(81)80411-3
R.C. Aggarwal, D.S.S. Vara Prasada Rao
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引用次数: 3
The preparation of some complexes of Th(IV) and U(IV) with tetradentate Schiff bases The crystal structure of bis[N,N′-ethylenebis (3-methoxysalicylaldiminato)] thorium(IV) monopyridine Th(IV)和U(IV)与四齿席夫碱配合物的制备[N,N ' -乙烯双(3-甲氧基水杨酸钠)]钍(IV)单吡啶的晶体结构
Pub Date : 1981-01-01 DOI: 10.1016/0022-1902(81)80210-2
R. J. Hill, C. Rickard, H. White
{"title":"The preparation of some complexes of Th(IV) and U(IV) with tetradentate Schiff bases The crystal structure of bis[N,N′-ethylenebis (3-methoxysalicylaldiminato)] thorium(IV) monopyridine","authors":"R. J. Hill, C. Rickard, H. White","doi":"10.1016/0022-1902(81)80210-2","DOIUrl":"https://doi.org/10.1016/0022-1902(81)80210-2","url":null,"abstract":"","PeriodicalId":16275,"journal":{"name":"Journal of Inorganic and Nuclear Chemistry","volume":"12 1","pages":"721-726"},"PeriodicalIF":0.0,"publicationDate":"1981-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78433342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 9
Cu(II) complexes of a tetradentate twelve membered macrocyclic ligand 四齿十二元大环配体的Cu(II)配合物
Pub Date : 1981-01-01 DOI: 10.1016/0022-1902(81)80363-6
Y. K. Bhoon, R. Singh
{"title":"Cu(II) complexes of a tetradentate twelve membered macrocyclic ligand","authors":"Y. K. Bhoon, R. Singh","doi":"10.1016/0022-1902(81)80363-6","DOIUrl":"https://doi.org/10.1016/0022-1902(81)80363-6","url":null,"abstract":"","PeriodicalId":16275,"journal":{"name":"Journal of Inorganic and Nuclear Chemistry","volume":"86 1","pages":"1685-1686"},"PeriodicalIF":0.0,"publicationDate":"1981-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76052526","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 4
期刊
Journal of Inorganic and Nuclear Chemistry
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