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1.
Summary Stability constants of complexes of aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl) methane [ArBPyM] derivatives with thorium(IV) ions were determined by the potentiometric method at 30°C and an ionic strength of 0.1 mol·dm–3 (KNO3) in 75% (v/v) dioxane-water. The evaluation of the titration data indicated that four kinds of complexes ([ThL]2+, [ThLOH]+, [ThL 2], and [ThL(OH)2]2–) were formed. The formation constants for all [ThL]2+ and [ThL 2] complexes have been calculated to compare these values with those previously reported [1, 2] with Ln3+ and UO 2 2+ metal ions [2, 3]. The probable ligand-bonding sites of the complexes are proposed. In addition, the applicability of theHammett equation for the correlation of the stability constants of [Th(IV)-ArBPyM] complexes are discussed.
Stabilitätskonstanten von Thorium(IV)-Komplexen mit Aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl)-methan-Liganden
Zusammenfassung Stabilitätskonstanten von Komplexen von Aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl)-methan — Derivaten [ArBPyM] mit Thorium(IV) — Ionen wurden bei 30°C und einer Ionenstärke von 0.1 mol-dm–3 (KNO3) in 75% (v/v) Dioxan-Wasser potentiometrisch bestimmt. Die Auswertung der Titrationskurven zeigte, daß vier verschiedene Komplexe vorlagen ([ThL]2+, [ThLOH]+, [ThL 2] und [ThL(OH)2]2+). Die Bildungskonstanten aller [ThL]2+- und [ThL 2]-Komplexe wurden berechnet, um sie mit den früher für Ln3+- und UO 2 2+ -Ionen publizierten zu vergleichen. Potentielle Bindungsstellen der Komplexe für Liganden werden vorgeschlagen. Zusätzlich wird die Anwendbarkeit derHammet-Beziehung auf die Korrelation der Stabilitätskonstanten von [Th(IV)-ArBPyM] — Komplexen diskutiert.
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2.
Zusammenfassung Folgende Koordinationsformen entstehen aus [Co(HMPT)4]2+ bei Zusatz von Halogenidionen in Hexamethylphosphorsäuretriamid (HMPT): [Co(HMPT)3Cl]+, [Co(HMPT)2Cl2], [Co(HMPT)Cl3], [CoCl4]2–, [Co(HMPT)3Br]+, [Co(HMPT)2Br2] und [Co(HMPT)3J]+.
Hexamethylphosphoric triamide as a ligand II: Reactions of Co(HMPT)4 2+ with chloride, bromide, and iodide ions
The following coordination species are formed from [Co(HMPT)4]2+, by addition of halide ions in hexamethylphosphoric triamide (HMPT): [Co(HMPT)3Cl]+, [Co(HMPT)2Cl2], [Co(HMPT)Cl3], [CoCl4]2–, [Co(HMPT)3Br]+, [Co(HMPT)2Br2] and [Co(HMPT)3J]+.


Mit 7 Abbildungen

V. Gutmann, A. Weisz undW. Kerber, 1. Mitt., Mh. Chem.100, 2096 (1969).  相似文献   

3.
4.
Zusammenfassung Die Bildung von Chloro-, Bromo- und Jodokomplexen von Co2+ wurde in Äthylensulfit (ES) auf spektrophotometrischem, potentiometrischem und konduktometrischem Wege untersucht. Folgende Komplexformen dürften gebildet werden: [CoCl(ES)5]+, CoCl2(ES)2, [CoCl3 ES], [CoCl4]2–, [CoBr(ES)5]+, CoBr2(ES)2, [CoBr4]2– und [CoJ4]2–. Die Ergebnisse werden hinsichtlich der des Lösungsmittels und des sterischen Baues des Lösungsmittelmoleküles mit denen in anderen Lösungsmitteln verglichen und diskutiert.
Reactions involving the formation of complex species of Co2+ with chloride, bromide and iodide ions have been investigated by spectrophotometric, potentiometric and conductometric methods using ethylene sulphite (ES) as solvent. The following complexes appear to be formed: [CoCl(ES)5]+, CoCl2(ES)2, [CoCl3 ES], [CoCl4]2–, [CoBr(ES)5]+, CoBr2(ES)2, [CoBr4]2– and [CoI4]2–. The influence of the donor number of the solvent and steric contributions by the solvent molecules are discussed.


Mit 8 Abbildungen  相似文献   

5.
Summary A spectroscopic study of the association in the Nd3+-SCN system is presented. A characteristic change of the molar absorptivity of the solution with a plateau at 2–4M [SCN] and an increase at 4–8M [SCN] reflects the change from outer- to innersphere complexation.
Untersuchungen zur Komplexierung im Nd3+-SCN-System
Zusammenfassung Es wird eine spektroskopische Studie der Assioziationsverhältnisse im Nd3+-SCN-System präsentiert. Die charakteristische Änderung in der molaren Absorption der Lösung mit einem Plateau bei 2–4M [SCN] und ein Anstieg bei 4–8M [SCN] ist auf einen Wechsel von außensphärischer zu innensphärischer Komplexierung zurückzuführen.
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6.
Several derivatized monosaccharides, the 2-deoxy-D -ribofuranoses, have been studied by liquid-assisted secondary ion mass spectrometry (LSIMS) in order to gain insight into the factors affecting ionization in FAB/LSIMS. Examination of the mass spectra for these compounds obtained in eight liquid matrices (diethanolamine, ethylene glycol, glycerol, 2-hydroxyethyl disulfide, 2-hydroxyphenethyl alcohol, 3-nitrobenzyl alcohol, sulfolane and thioglycerol) reveals that in all cases the anomalous [M – H]+ ion is the predominant species in the molecular ion region and that [M + Na]+ species are observed in the presence of Na+. The analysis of these compounds by chemical ionization with ammonia shows [M + H]+ as the major species while [M – H]+ is essentially absent. This indicates that the ionization processes occurring in the two techniques are not analogous. Thermodynamic considerations based on the gas-phase hydride ion affinities of the protonated matrices do not support a predominant gas-phase mechanism for the formation of [M – H]+ in LSIMS. However, it is possible using solvation energies to rationalize the formation of [M – H]+ in terms of condensed-phase ionization processes which take place either in the liquid matrix or in the dense selvedge region immediately above the surface where extensive solvation is present. Electrospray data obtained for one of the derivatized monosaccharides indicates that the [M – H]+ is not performed in the condensed phase in LSIMS and that it is the product of fast ion beam-induced processes. While the nature of the matrix is seen to have little effect on the intensities of [M – H]+ and [M + H]+ it is observed to be an important factor for the intensity of M+˙ for one of the monosaccharides. This effect can be related to the electron-scavenging properties of the matrices and reinforces the hypothesis that condensed phase processes are significant in ionization.  相似文献   

7.
Summary The title reaction has been followed spectrophotometrically at 325 nm (max of [Mn(CN)6]3–) under pseudo-first order conditions with cyanide in a large excess at pH=10.0, I=0.1M (NaClO4) and 25°C. The reaction follows first-order kinetics in [MnEDTA(OH)]2– and exhibits variable-order dependence in [CN] one at high cyanide concentration, and two at low cyanide concentration. The product of above reaction has been identified as [Mn(CN)6]3–.The kinetics of the reverse reaction,i.e., the reaction of [Mn(CN)6]3- with EDTA4– have also been followed spectrophotometrically. This reactions is first-order with respect to both [Mn(CN) 6 3– ] and [EDTA4–] and exhibits an inverse first-order dependence on [CN]. A six-step mechanism has been proposed in which the penultimate step is rate-determining. The activation parameters have been obtained and support the postulated mechanism.  相似文献   

8.
Zusammenfassung Auf Grund spektrophotometrischer, potentiometrischer und konduktometrischer Befunde entstehen aus [Co(HMPT)4]2+ in Hexamethylphosphorsäuretriamid (HMPT) bei Zusatz von Pseudohalogenidionen folgende Koordinationsformen: [Co(HMPT)3N3]+, [Co(HMPT)2(N3)2], [Co(HMPT)(N3)3], [Co(N3)4]2–, [Co(HMPT)3NCS]+, [Co(HMPT)2(NCS)2], [Co(HMPT)(NCS)3], [Co(NCS)4]2–, [Co(HMPT)2(CN)2], [Co(HMPT)(CN)3], [Co(HMPT)(CN)5]3–.
Hexamethyl phosphoric triamide as a ligand, III: Reactions of [Co(HMPT)4]2+ with rhodanide, cyanide, and azide ions, resp
Spectrophotometric, potentiometric and conductometric results indicate that addition of pseudohalide ions to [Co(HMPT)4]2+ in hexamethylphosphoramide (HMPT) leads to the following coordination forms: [Co(HMPT)3N3]+, [Co(HMPT)2(N3)2], [Co(HMPT)(N3)3], [Co(N3)4]2–, [Co(HMPT)3NCS]+, [Co(HMPT)2(NCS)2], [Co(HMPT)(NCS)3], [Co(NCS)4]2–, [Co(HMPT)2(CN)2], [Co(HMPT)(CN)3], [Co(HMPT)(CN)5]3–.


Mit 7 Abbildungen

2. Mitt.:V. Gutmann undA. Weisz, Mh. Chem.100, 2104 (1969).  相似文献   

9.
Summary The aquation ofcis-[(en)2Co(CO2H)2]+ tocis-[(en)2Co(OH2)(CO2H)]2+ is catalysed by Cu2+ and the rate equation, –d[complex]t/dt=(kCu[Cu2+]+kH [H+]) [complex)T is valid at [Cu2+]T=0.01–0.1, I=0.5 and [HClO4]=0.005 mol dm–3. The rate measurements are reported at 30, 35, 40 and 45°C and the rate and activation parameters for the Cu2+ and H+-catalysed paths are: kH(35°C)=(2.44±0.09)×10–2 dm3 mol–1 s–1, H=83±13 kJ mol–1, S=–8±42 JK–1 mol–1, k Cu (35°C)=(3.30±0.09)×10–3 dm3 mol–1 s–1, H=73.2±6.1 kJ mol–1, S=–55±20 JK–1 mol–1. The formate-bridged innersphere binuclear complex,cis-[(en)2Co{(O2CH)2Cu}]3+ may be involved as the catalytically active intermediate in the copper(II)-catalysed path, just as the corresponding H+-bridged species presumed to be present in the acidcatalysed path.  相似文献   

10.
Zusammenfassung Auf Grund der Löslichkeit des Ce(III)-Malonats in Perchlorsäurelösungen wurden die Dissoziationsgleichgewichte der gebildeten Komplexionen, d. h., von [CeMal 2] und [CeMal]+ untersucht. Gleichzeitig wurden auch die Löslichkeitsprodukte des Ce(III)-Malonats, u. zw.: [Ce3+]2 [Mal 2–]3**, [CeMal +]2 [Mal 2–] und [CeMal +] [CeMal 2–] bestimmt.
Chemistry of the rare earth metals, XXII: Dissociation equilibria of Ce(III)-malonate in weakly acidic solution
The solubility of cerous malonate in perchloric acid solutions was investigated. The dissociation equilibria of the complex ions formed, i.e. [CeMal 2] and [CeMal]+ were studied and the solubility products of the cerous malonates, i.e. [Ce3+]2 [Mal 2–]3, [CeMal +]2 [Mal 2–] and [CeMal +] [CeMal 2–] determined.


21. Mitt.:R. Pastorek, Gleichgewichtskonstanten der Komplex-partikeln im sauren Bereich des SystemsLn 3+–H4 Tart–KOH, Acta Univ. Palack., im Druck.  相似文献   

11.
Summary Mass spectra of seven N-nitrosamines and five alkyl nitrites, the O-nitroso compounds, have been obtained by low pressure negative chemical ionization with CO2 as reagent gas. Intense anions were observed at m/z M–32 for N-nitrosamines and at m/z M–30 for alkyl nitrites. Addition products were found at m/z M+12 and M+43 for N-nitrosamines and at m/z M+14 for alkyl nitrites. By using isotopically labeled CO2, it could be shown that the anions at m/z M+12, M+14 and M+43 correspond to [M - H2NO + CO2 , [M – NO + CO2], and [M – H + CO2], respectively.
Negativionen-CI-Massenspektrometrie einiger Nitrosoverbindungen mit CO2 als Reagensgas
Zusammenfassung Die Massenspektren von sieben N-Nitrosaminen und fünf Alkylnitriten (O-Nitrosoverbindungen) wurden durch negative chemische Ionisation bei niederem Druck mit CO2 als Reagensgas erhalten. Intensive Anionen wurden bei m/z M–32 für N-Nitrosamine und bei m/z M–30 für Alkylnitrite beobachtet. Additionsprodukte fanden sich bei m/z M+12 und M+43 für N-Nitrosamine sowie bei m/z M+14 für Alkylnitrite. Mit Hilfe von Isotopen-markiertem CO2 konnte gezeigt werden, daß die Anionen bei m/z M+12, M+14 und M+43, [M – H2NO + CO2], [M – NO + CO2] bzw. [M – H + CO2] entsprechen.


A full account of this work including the negative chemical ionization mass spectra obtained with other reagent gases will be submitted to the Journal of Mass Spectrometry.  相似文献   

12.
Summary The bromate ion reduction by 12-tungstocobaltate(II) anion has been investigated. The reaction obeys the empirical rate law:-d[reductant]/dt=5(a+b[H+]2)[BrO 3 ][reductant]: where a=(2.49±0.18)×10–4M–1 s–1, b=(4.65±0.20)×10–5M–3s–1 at 24.5±0.1°C [H+]=0.05–1.50M and I=2.0M (NaClO4). This rate law is interpreted in terms of parallel reactions of BrO 3 and H2BrO 3 + . On the basis of the observed anion catalysis, substitution intertness of the reductant and Marcus type linear free energy relations, the outer sphere mechanism is proposed for both pathways.  相似文献   

13.
Summary Solid complexes of 3-acetyl-1,5-diaryl and 3-cyano-1,5-diaryl formazans were prepared and characterized by elemental analysis, IR, NMR, TGA and DTA analyses. Based on these studies, the suggested general formula for the complexes is [M(HL) m (OH) n or (NO 3 or Cl) x ·(H2O) y or (C2H5OH orDMSO) z , where HL=formazanM=Ce3+, Th4+, and UO 2 2+ ,m=1–2,n=0–3,x=0–3,y=0–4 andz=0–3. The metal ions are expected to have coordination numbers 6–8.
Strukturuntersuchungen an 3-Acetyl-1,5-diaryl- und 3-Cyan-1,5-diaryl-formazan-Chelaten mit Cer(III), Thorium(IV) und Uran(VI)
Zusammenfassung Die hergestellten Chelate wurden mittels Elementaranalyse, IR, NMR, TGA und DTA charakterisiert. Darauf basierend wird die generelle Formel [M(HL) m (OH) n bzw. (NO 3 oder Cl) x ·(H2O) y oder (C2H5OH bzw.DMSO) z ] vorgeschlagen, wobei HL=Formazan,M=Ce3+, Th4+ oder UO 2 2+ ,m=1–2,n=0–3,x=0–3,y=0–4 undz=0–3. Die Metallionen haben Koordinationszahlen von 6–8.
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14.
Summary Volumetric measurements of ethylene and simple EDTA titration of copper(I) and copper(II) ions confirm that [CuL]+ and [CuL2]+ are formed when an aqueous solution of copper(II) is reduced by copper metal in the presence of ethylene, (L). The formation constants,K 1=[CuL+]2[Cu2+]–1[L]–2 andK 2=[CuL 2 + ]–1[L]–1, have been estimated. The formation of [CuL]+ is accompanied by an enthalpy change, H, of –25 kJ mol–1, and a positive entropy change, S, of 13 J mol–1 K–1.  相似文献   

15.
Under Ammonia chemical Ionization conditions the source decompositions of [M + NH4]+ ions formed from epimeric tertiary steroid alchols 14 OHβ, 17OHα or 17 OHβ substituted at position 17 have been studied. They give rise to formation of [M + NH4? H2O]+ dentoed as [MHsH]+, [MsH? H2O]+, [MsH? NH3]+ and [MsH? NH3? H2O]+ ions. Stereochemical effects are observed in the ratios [MsH? H2O]+/[MsH? NH3]+. These effects are significant among metastable ions. In particular, only the [MsH]+ ions produced from trans-diol isomers lose a water molecule. The favoured loss of water can be accounted for by an SN2 mechanism in which the insertion of NH3 gives [MsH]+ with Walden inversion occurring during the ion-molecule reaction between [M + NH4]+ + NH3. The SN1 and SNi pathways have been rejected.  相似文献   

16.
The electron-impact mass spectra of coordination compounds of nickel(II) with the general formula NiL2, in which the radical anions [C6H5N -N-C(SR)=NR1], where R=CH3 and R=H(I), R=CD3 and R=H(II), R=C2H5 and R=H(III), and R=CH3 and R=C6H5(IV), serve as the ligands, have been studied. In the mass spectra of compounds I–IV the peaks of the molecular ions have the highest intensity among the organometallic fragments. The initial stage of the fragmentation of [M]+. is associated with the formation of the rearrangement ions [NiL + H]+, [NiL + C6H5]+, and [NiL + SR]+, ions, whose appearance becomes understood, if it is taken into account that the removal of one ligand is accompanied by the impairing of spins and the mass spectra of compounds I–IV is the presence of lines for the [NiL]+ ion in them. The dissociative ionization of compounds I–IV is strongly reminiscent of the behavior of ordinary complexes of metals with ligands of the nonradical type. The fragmentation scheme of the molecular ions under the effects of electron impact has been presented and discussed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 3, pp. 368–371, May–June, 1990.  相似文献   

17.
Summary The reaction of [CrCl3(DMF)3] with C-meso-5, 12-dimethyl-1, 4, 8, 11-tetra-azacyclotetradecane(LM) in DMF gives a mixture ofcis-[CrLMCl2]Cl (ca. 90%) andtrans-[CrLMCl2]Cl (ca. 10%). These complexes are readily separated, as thecis-isomer is insoluble in warm methanol while thetrans-isomer is soluble. Using the dichlorocomplexes as precursors it has been possible to prepare a range ofcis-[CrLMX2]+ complexes (X=Br, NO 3 , N 3 , NCS and X2=bidentate oxalate) and alsotrans-[CrLMX2]+ complexes (X=Br, H2O or NCS). The spectroscopic properties and detailed stereochemistry of the complexes are discussed.The aquation and base hydrolysis kinetics ofcis- andtrans-[CrLMCl2]+ have been studied at 25° C. Base hydrolysis of thecis-complex is extremely rapid with KOH =1.46×105 dm3 mol–1 at 25° C. This unusual reactivity appears to be associated with thetrans II stereochemistry of thesec-NH centres of the macrocycle. Base hydrolysis of thetrans complex with thetrans III chiral nitrogen stereochemistry is quite normal with kOH =1.1 dm3 mol–1 s–1 at 25° C.  相似文献   

18.
Spatial structures of complexes [DyAc]2+, [DyBz]2+, [DyAc2]+ and [DyBz2]+ in aqueous solutions (Ac and Bz, acetate and benzoate anions, respectively) are studied using the paramagnetic double refraction method. The polyhedra of [DyAc(H2O)6]2+ and [DyBz(H2O)6]2+ are dodecahedra with ligands coordinated at one of the edges. In the complexes [DyAc2(H2O)4]+ and [DyBz2(H2O)4]+ the ligands are coordinated at the edges of a square antiprism at an angle of 50 (55)° to the local symmetry axis of higher symmetry.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1038–1040, June, 1993.  相似文献   

19.
Nonempirical calculations of the electronic structure of the [PF5]2– ion and of the clusters [M5PF5]3+ and [M4PF5]2+ (M=H+, Li+, Na+) have been carried out. The character of the dependence of the geometric parameters of the [PF5]2– ion on the properties and structure of the second coordination sphere has been discussed.Institute of Chemistry, Academy of Sciences of the USSR, Far-Eastern Branch. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 2, pp. 17–22, March–April, 1991.  相似文献   

20.
Zusammenfassung Die Dissoziation von Ce2 Suc 3·3 H2O** in Perchlorsäure-Lösungen wurde verfolgt und die Dissoziationskonstanten der Succinationen: (CeSuc)+ und (CeSuc 2) unter Benützung einer Löslichkeitsmethode in 1m-NH4ClO4-Lösung bei 25°C bestimmt. Die Löslichkeitsprodukte von Ce2 Suc 3: [Ce3+]2[Suc 2–]3, [CeSuc +]2[Suc 2–], [CeSuc +][CeSuc 2 ] wurden bestimmt.
The dissociation of Ce2 Suc 3·3H2O in perchloric acid solutions was investigated. The dissociation constants of the succinate ions (CeSuc)+ and (CeSuc 2) were determined inM-NH4ClO4 at 25° using a solubility method and the solubility products of Ce2 Suc 3, i. e. [Ce3+]2[Suc 2–]3, [CeSuc +]2[Suc 2–], [CeSuc +][CeSuc 2 ] measured.


18. Mitt.:R. Pastorek, Lanthantartrate im neutralen und alkal. Bereich. Mh. Chem.99, 676 (1968).  相似文献   

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