Pub Date : 1981-01-01DOI: 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.
{"title":"Application of the oscillator strength of “hypersensitive” transitions to the investigation of complex equilibria of lanthanide ions—I","authors":"K. Bukietyńska, A. Mondry, E. Osmȩda","doi":"10.1016/0022-1902(81)80036-X","DOIUrl":"10.1016/0022-1902(81)80036-X","url":null,"abstract":"<div><p>A method of evaluation of stability constants for the lanthanide complexes from the changes of oscillator strengths of “hypersensitive” <em>f</em>-<em>f</em> 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.</p><p>The method is limited to lanthanide ions with <em>f</em><sup>2</sup>-<em>f</em><sup>6</sup> and <em>f</em><sup>8</sup>-<em>f</em><sup>12</sup> electronic configurations.</p></div>","PeriodicalId":16275,"journal":{"name":"Journal of Inorganic and Nuclear Chemistry","volume":"43 6","pages":"Pages 1311-1319"},"PeriodicalIF":0.0,"publicationDate":"1981-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0022-1902(81)80036-X","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84845632","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}
Pub Date : 1981-01-01DOI: 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 PdCl = 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.
{"title":"Crystal structure of a new insertion compound formed by PdCl2 and tri-methylamine [(CH3)3NH]2PdCl4.(CH3)3NHCl","authors":"Dominique Zveguintzoff, Claudette Bois, Nguyen Quy Dao","doi":"10.1016/0022-1902(81)80086-3","DOIUrl":"10.1016/0022-1902(81)80086-3","url":null,"abstract":"<div><p>The complex 3[(CH<sub>3</sub>)<sub>3</sub>NHCl].pdCl<sub>2</sub> crystallises in the orthorhombic system, space group <em>Pnma</em>: <em>a</em> = 990(1) pm; <em>b</em> = 1209(1) pm; <em>c</em> = 1721(2) pm; <em>Z</em> = 4; <em>d</em><sub>th</sub> = 1.49; <em>d</em><sub>exp</sub> = 1.45. The structure is composed of square planar PdCl<sub>4</sub><sup>2−</sup> ions (average length PdCl = 230 pm), of two ammonium groups, each one equidistant of two chlorine atoms and in <em>cis</em> position to the plane of PdCl<sub>4</sub><sup>2−</sup>. A third (CH<sub>3</sub>)<sub>3</sub>NHCl molecule is in insertion in the structure. This is a new type of solvate in which the insertion molecule is an ion pair.</p></div>","PeriodicalId":16275,"journal":{"name":"Journal of Inorganic and Nuclear Chemistry","volume":"43 12","pages":"Pages 3183-3185"},"PeriodicalIF":0.0,"publicationDate":"1981-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0022-1902(81)80086-3","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87192427","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}
Pub Date : 1981-01-01DOI: 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.
{"title":"Stereoselectivity and exciton cotton effects in mixed complexes of zinc(II)","authors":"S. Bunel ∗, G. Larrazábal, A. Decinti","doi":"10.1016/0022-1902(81)80616-1","DOIUrl":"10.1016/0022-1902(81)80616-1","url":null,"abstract":"<div><p>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.</p></div>","PeriodicalId":16275,"journal":{"name":"Journal of Inorganic and Nuclear Chemistry","volume":"43 11","pages":"Pages 2781-2783"},"PeriodicalIF":0.0,"publicationDate":"1981-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0022-1902(81)80616-1","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76592177","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}
Pub Date : 1981-01-01DOI: 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.
{"title":"Synthesis and characterization of some dimeric dialkoxo-bridged Fe(III) complexes with 1, 1, 1, 5, 5, 5-hexafluoropentan-2, 4-dione","authors":"Neville T. Moxon, Jonathan H. Moffett, Anthony K. Gregson","doi":"10.1016/0022-1902(81)80601-X","DOIUrl":"10.1016/0022-1902(81)80601-X","url":null,"abstract":"<div><p>A series of compounds with the empirical formulae Fe(hfa)<sub>2</sub>OR (Hfha = 1, 1, 1, 5, 5, 5-hexafluoropentan-2, 4-dione, R = CH<sub>3</sub>, C<sub>2</sub>H<sub>5</sub>, sec-C<sub>4</sub>H<sub>9</sub>) and the parent material Fe(hfa)<sub>3</sub> have been prepared and characterized using analytical data, IR and optical spectroscopy, magnetic susceptibility measurements and powder X-ray diffraction. The Fe(hfa)<sub>2</sub>OR adducts are antiferromagnetic dimers with <em>J</em> ∼ 12 cm<sup>−1</sup>. Unusual products have been isolated when ethylene glycol is used as the alcohol.</p></div>","PeriodicalId":16275,"journal":{"name":"Journal of Inorganic and Nuclear Chemistry","volume":"43 11","pages":"Pages 2695-2702"},"PeriodicalIF":0.0,"publicationDate":"1981-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0022-1902(81)80601-X","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76739208","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}
Pub Date : 1981-01-01DOI: 10.1016/0022-1902(81)80220-5
B. Jain, J. Singh, R. Goyal, S. N. Tandon
{"title":"Extraction of Zn(II) and Cd(II) with diphenylcarbazone in presence of nitrogen-containing organic bases","authors":"B. Jain, J. Singh, R. Goyal, S. N. Tandon","doi":"10.1016/0022-1902(81)80220-5","DOIUrl":"https://doi.org/10.1016/0022-1902(81)80220-5","url":null,"abstract":"","PeriodicalId":16275,"journal":{"name":"Journal of Inorganic and Nuclear Chemistry","volume":"284 1","pages":"773-777"},"PeriodicalIF":0.0,"publicationDate":"1981-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76987064","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}
Pub Date : 1981-01-01DOI: 10.1016/0022-1902(81)80129-7
Maura Gusteri, Vito Bartocci, Franca Castellani, Giuseppe Scarponi
{"title":"Complex formation between silver and halides in fused acetamide","authors":"Maura Gusteri, Vito Bartocci, Franca Castellani, Giuseppe Scarponi","doi":"10.1016/0022-1902(81)80129-7","DOIUrl":"10.1016/0022-1902(81)80129-7","url":null,"abstract":"","PeriodicalId":16275,"journal":{"name":"Journal of Inorganic and Nuclear Chemistry","volume":"43 12","pages":"Pages 3400-3401"},"PeriodicalIF":0.0,"publicationDate":"1981-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0022-1902(81)80129-7","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78125902","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}
Pub Date : 1981-01-01DOI: 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。
{"title":"EPR studies on Cu(3-amino, 5-methyl isoxazole)4 (ClO4)2 and Cu(3-amino, 5-methyl isoxazole)4 (NO3)2","authors":"B.A. Sastry, S.Md. Asadullah, G. Ponticelli, M. Massacesi","doi":"10.1016/0022-1902(81)80329-6","DOIUrl":"10.1016/0022-1902(81)80329-6","url":null,"abstract":"<div><p>EPR studies have been carried out on Cu(3-AMI)<sub>4</sub>(ClO<sub>4</sub>)<sub>2</sub> and Cu(3-AMI)<sub>4</sub>(NO<sub>3</sub>)<sub>2</sub>[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)<sub>4</sub>(ClO<sub>4</sub>)<sub>2</sub> 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)<sub>4</sub>(NO<sub>3</sub>)<sub>2</sub> is characteristic of a CuO<sub>6</sub> chromophore indicating stronger solvation in the above solution. The 4<em>s</em>-character in the ground state of Cu(II) in all the above cases was calculated to determine the relative strengths of axial fields.</p></div>","PeriodicalId":16275,"journal":{"name":"Journal of Inorganic and Nuclear Chemistry","volume":"43 7","pages":"Pages 1521-1524"},"PeriodicalIF":0.0,"publicationDate":"1981-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0022-1902(81)80329-6","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78299209","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}
Pub Date : 1981-01-01DOI: 10.1016/0022-1902(81)80411-3
R.C. Aggarwal, D.S.S. Vara Prasada Rao
{"title":"Preparation and structural studies of addition compounds of Sn(IV) halides, organotin(IV) halides and pseudohalides with acetone picolinoyl, nicotinoyl and isonicotinoyl hydrazones","authors":"R.C. Aggarwal, D.S.S. Vara Prasada Rao","doi":"10.1016/0022-1902(81)80411-3","DOIUrl":"10.1016/0022-1902(81)80411-3","url":null,"abstract":"","PeriodicalId":16275,"journal":{"name":"Journal of Inorganic and Nuclear Chemistry","volume":"43 8","pages":"Pages 1922-1927"},"PeriodicalIF":0.0,"publicationDate":"1981-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0022-1902(81)80411-3","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78426004","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}
Pub Date : 1981-01-01DOI: 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}
Pub Date : 1981-01-01DOI: 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}