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1.
New Position Isomeric Analoga of Reinecke Salt with m- and p-Tolylenediamine Two position isomeric Reinecke salt analogous complexes, [Cr(NCS)4(m-TolyIenediamine)2]? and [Cr(NCS)4(p-Tolylenediamine)2]?, were obtained by means of substitution reactions of anhydrous K3[Cr(NCS)6] with meta and para tolylenediamine, respectively, without solvent. The formulae of the new complex anions were established by preparation of 18 new derivatives with the hydrochlorides of some alksloides, and cobalt(III) amine bases. From electronic and IR spectral data some structural problems are solved. The thermal stability of some complexes was discussed on the basis of derivatographic analysis.  相似文献   

2.
New Substitution Compounds of K3[Cr(NCS)6] with Tertiary Phosphines . New substitution reactions of K3[Cr(NCS)6] with mixed tertiary phophines in n-butanol were carried out. The formulae of the new anions: [Cr(NCS)4(diethyl-phenylphosphine)2]? and [Cr(NCS)4(diethyl-p-tolyl-phosphine)2]? were established by preparation of 30 new derivatives with the hydrochlorides of some organic N-bases, metals, and metal(III) ammines. Electronic and i.r. spectral data are communicated.  相似文献   

3.
Substitution reactions of K3[Cr(NCS)6] with pyridine and alkyl-pyridine derivatives was studied. The formulas of three complex anions, [Cr(NCS)4(pyridine)2]?, [Cr(NCS)4(β-picoline)2]? and [Cr(NCS)4(γ-picoline)2]?, was established by preparation. 33 new complex compounds of these types have been prepared from the hydrochlorides of aromatic and heterocyclic amines. Their thermal behaviour and the mechanism of pyrolysis of these salts was studied by TGA. From UV and IR spectra some structural problems are resolved and discussed.  相似文献   

4.
New Tetrathiocyanato-diamine-chromiates with Aliphatic Monoamines Two new Reinecke salt like compounds were obtained by a substitution reaction of anhydrous K3[Cr(NCS)6] with aliphatic monoamines (n-propylamine and n-butylamine) in the molten state. The formulae of the [Cr(CNS)4(n-propylamine)2]? and [Cr(NCS)4(n-butylamine)2]? were proved by a series of double decomposition reactions with the hydrochlorides of heterocyclic N-bases and alkaloids and with cobalt(III)-amine bases, respectively. From spectroscopical investigations (u.v. and i.r.) some structural problems are resolved and discussed.  相似文献   

5.
Zusammenfassung Es wurden 34 neue Komplexsalze durch doppelte Umsetzung aus wäßr.-alkohol. Lösungen der folgenden Reineckeat-Analoga: [Cr(NCS)4(m-xylidin)2]–, [Cr(NCS)4(p-xyl)2]– und Hexammin-, Monoacido-pentammin- und Diacido-tetramminkobalt(III)-komplexsalze erhalten. Es wurden in einigen Fällen Unterschiede in physiko-chemischen Eigenschaften, wie Farbtönung, Kristallform, Löslichkeit und papierchromatographischeR f-Werte, bei den stellungsisomeren Salzen vom Typus: Kation · [Cr(NCS)4(xyl)2] und auch bei den Koordinationsisomerpaaren: [Co(DH)2(m-xyl)2] [Cr(NCS)4(p-xyl)2] und [Co(DH)2(p-xyl)2] [Cr(NCS)4(m-xyl)2] usw. beobachtet.
Cobalt(III)ammine derivatives of some reineckate analogues with xylidines
34 new complex salts were prepared by double conversion of the reineckate analogues [Cr(NCS)4(m-xylidine)2]–, [Cr(NCS)4(p-xyl)2]–, with the hexammine-, monoacido-pentammine- and diacidotetrammine-complexes of Co(III). In some of the position and coordination isomeres differences of the standard physico-chemical properties, i.e. color, crystal form, solubility and paper chromatographyR f-values were observed.
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6.
Zusammenfassung Es wurden 39 neue Komplexsalze durch doppelte Umsetzung aus wäßrig-alkohol. Lösungen der folgenden Reineckeat-Analoga: [Cr(NCS)4(o-Toluidin)2]–, [Cr(NCS)4(m-Toluidin)2]– und [Cr(NCS)4(p-Toluidin)2]– und Hexammin-, Monoacido-pentammin-und Diacido-tetrammin-kobalt(III)-komplexsalze erhalten.Es wurden in einigen Fällen Abweichungen in physikochemischen Eigenschaften, wie Farbtönung, Kristallform, Löslichkeit und papierchromatographischeR F-Werte, bei den stellungsisomeren Salzen vom Typus: Kation·[Cr(NCS)4(Toluidin)2] und auch bei den Koordinationsisomerpaaren: [Co(DH)2(o-Toluidin)2][Cr(NCS)4(p-Toluidin)2] und [Co(DH)2(p-Toluidin)2] [Cr(NCS)4(o-Toluidin)2], usw. beobachtet.
Cobalt(III) ammine derivatives of some reineckate analogues with toluidines
39 new complex salts were prepared by double conversion of the reineckate analogues [Cr(SCN)4(o-toluidine)2]–, [Cr(SCN)4(m-toluidine)2]–, and [Cr(SCN)4(p-toluidine)2]– with the hexammine, monoacido-pentammine and diacido-tetrammine complexes of Co(III). In some of the position and coordination isomers deviations from the standard physico-chemical properties, i.e. color, crystal form, solubility and paper chromatographyR f-values were observed.
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7.
A new procedure for measuring time-resolved emission spectra has been implemented. This technique has subnanosecond time resolution combined with the sensitivity and dynamic range needed to cope with extremely weak luminescence. Using this method the emissions of Cr(NH3)2 (NCS)4? and Cr(NCS)63- in aqueous solution at room temperature have each been analyzed into two components. The fast component has a broad spectrum and is assigned to prompt fluorescence with lifetime below 100 ps. The slow component is dominated by phosphorescence but may include some delayed fluorescence. The phosphorescence lifetime is 5.5 ± 0.5 ns in Cr(NH3)2 (NCS)4? and 1.65 ± 0.1 ns in Cr(NCS)63-. Order of magnitude estimates have been derived for other photophysical parameters.  相似文献   

8.
New Tetrathiocyanato Diamin Chromiates with Naphthylamines Substitution reactions of anhydrous K3[Cr(NCS)6] with α- and β-naphthyl- amine without applying of solvents were carried out. The formulae of the new positionisomer complex anions were established with a series of double decomposition reactions with the hydrochlorides of some heterocyclic N-bases and cobalt(III) amines. From spectroscopical investigations -UV and UR) some structural problems are resolved.  相似文献   

9.
Substitution reactions of anhydrous K3[Cr(NCS)6] with tertiary aromatic monoamines such as N,N-dimethylaniline and N,N-diethylaniline were carried out in the absence of solvents. The tertiary amines readily form compounds analogous to Reinecke salts,amine 2H[Cr(NCS)4(N,N-dimethylaniline)2] andamine 2H[Cr(NCS)4(N,N-Diethylaniline)2] respectively. The formula of the new complex anions was established by a series of double decomposition reactions with the hydrochlorides of some heterocyclic N-bases, alcaloids and cobalt(III)-ammine complexes. Some structural problems were resolved by UV and IR spectroscopic studies.  相似文献   

10.
Substitution reactions of K3[Cr(NCS)6] with morpholine were studied. The formula of the complex anion, [Cr(NCS)4(morph)2]–, was established.23 new complex compounds of these types have been prepared from the hydrochlorides of some aliphatic or heterocyclic amines, alkaloids and cobalt(III)ammine bases resp.Their thermal behaviour and the mechanism of pyrolysis of these salts was studied by derivatographic methodes. From UV and IR spectra some structural problems are resolved and discussed.

Mit 3 Abbildungen  相似文献   

11.
A method for the synthesis of stereospecifically, equatorially labelled cis-M(CO)4(13CO)(amine) derivatives where M = Cr, Mo, and W has been developed involves 13CO substitution into the vacant coordination site created by the facile dissociation of an amine ligand from cis-M(CO)4(amine)2 derivatives. The mechanistic implications of this extremely stereoselective reaction are discussed.  相似文献   

12.
A method for the synthesis of stereospecifically, equatorially labelled cis-M(CO)4(13CO)(amine) derivatives where M = Cr, Mo, and W has been developed involves 13CO substitution into the vacant coordination site created by the facile dissociation of an amine ligand from cis-M(CO)4(amine)2 derivatives. The mechanistic implications of this extremely stereoselective reaction are discussed.  相似文献   

13.
30 new binary salts of the heretofore unknown type [Co(NioxH)2(Amin)2]X were obtained by air oxidation of an alcoholic aqueous solution of CoII acetate in the presence of 1,2-cyclohexanedione dioxime (nioxime) and an aromatic amine (aniline, o-and p-ethylaniline and m-xylidine). From the brown solutions of the resulting; Co(NioxH)2(amine)2; acetates the desired salts were separated by means of double decomposition reactions using X ? Br?, NO, ClO, HSO, Pikart, [Cr(NH3)2(NCS)4]?, 1/3[Cr(NCS)6]3? and [Co(NioxH)2(NO2)2]?; NioxH ? C6H9N2O2. From spectroscopical investigations in the UV and IR regions some structural problems are resolved and discussed.  相似文献   

14.
Ligand-field spectra of tetrahedral CoX 4 2– and octahedral Cr(NCS) 6 3– were measured in a number of solvents. Care was taken to ensure complete formation of the anionic species to be investigated. Considerable variations in intensity were found for complexes with highly polarizable ligands. For Co(NCS) 4 2– the oscillator strength of the4T1(P) transition in aqueous solution was only about 1/5 that in a number of organic solvents, with little variation in these solvents. For Cr(NCS) 6 3– the intensities are highest in aqueous solution, and some variation is observed for the nonaqueous solvents. These data for the chromium complex correlate at least qualitatively with variations of the excited state lifetimes in these solvents. Nonlinear changes of intensities in solvent mixtures can be taken as an indication of preferential solvation of the anionic complex by nonaqueous solvent molecules. The reported results are a strong indication of large differences in solvent/solute interactions between water and the nonaqueous solvents.  相似文献   

15.
The compounds [LnL8][Cr(NCS)6] (Ln = La3+, Pr3+, Eu3+, Gd3+, Tb3+, Yb3+, L =?-C6H11NO) were obtained from aqueous solutions containing LnCl3, K3[Cr(NCS)6], and ?-caprolactam at 4–6. All these compounds have thermochromic properties and reversibly changed color from pale violet to dark green when heated in air at 473–483 K. The compounds crystallized as one of the three related structural types with the mutual packing of ions topologically corresponding to the packing in the structure of NaCl. The [EuL8][Cr(NCS)6] single crystal underwent a reversible phase transition at T = 240–250 K, which was accompanied by reversible twinning.  相似文献   

16.
Preparation, Isolation, and Characterization of Mixed Thiocyanato(1.3-diaminopropane) -chromium(III) Complexes The complexes [Cr(NCS)4dap]? and trans-[Cr(NCS)2(dap)2]+ (dap = 1.3-diaminopropane) are prepared for the first time, isolated as salts and characterized by CHN analysis, chromium contents, the electrophoretic behaviour in dimethylformamide, and by UV, VIS, and IR spectra.  相似文献   

17.
The [Cr(NCS)(edtrp)]−, [Cr(NCS)(R-pdtrp)]− and [Cr(NCS)(S-pdtra)]− complexes, that are derivatives of the trans-equatorial isomers of [Cr(edtrp)(H2O)]° and [Cr(R-pdtrp)(H2O)]° and the cis-equatorial isomer of [Cr(S-pdtra)-(H2O)]° (edtrp = ethylenediamine-N,N,N′-tripropionate, R-pdtrp = R-propane-1,2-diamine-N,N,N′-tripropionate, S-pdtra = S-propane-1,2-diamine-N,N,N′-triacetate) undergo aquation in alkaline media with a strong dependence of the rate on [OH−] for the trans-equatorial isomers and a very weak dependence for the cis-equatorial isomer. The thiocyanate ligand release follows a stereoretentive course for all reactants. Based on kinetic data the reaction mechanism has been discussed. Rate differences between the isomers are interpreted in terms of an interchange via a conjugate base (I c.b.) mechanism, assuming an equilibrium between the cis-equatorial-CrIII-S-pdtra complexes with penta- and tetradentate coordination of the edta-like ligand. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

18.
Zusammenfassung Neue gravimetrische, oxydimetrische und spektrophotometrische Methoden für die Bestimmung kleiner Wismutmengen (1–15 mg/ 25 ml) als [Bi(Thio)4] [Cr(NCS)4(Amin)2]3 (Thio=Thioharnstoff; Amin=Anilin bzw. Morpholin) wurden beschrieben und die Resultate statistisch verarbeitet.
Thiocyanato-chromium(III) complexes in chemical analysis
Summary New gravimetric, oxidimetric and spectrophotometric methods for determining small amounts of bismuth (1–15 mg Bi/25 ml test solution) as [Bi(thio)4][Cr(NCS)4(amine)2]3 (thio=thiourea; amine=aniline, morpholine) are described and the results analysed statistically.
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19.
Three new complex ions, [Cr(NCS)(R-pdtrp)]-, [Cr(R-pdtrp)(NCSHg)]+ and [Cr(edtrp)(NCSHg)]+, that are derivatives of the trans-equatorial isomers of [Cr(R-pdtrp)(H2O)]0 and [Cr(edtrp)(H2O)]0 (edtrp= ethylenediamine-N,N,N-tripropionate, R-pdtrp= R-propane-1,2-diamine-N,N,N-tripropionate) have been obtained and characterized in solution. Rate constants and activation parameters, including, in two cases, volumes of activation, have been determined. Rate retardation for NCS- ligand release has been observed with increasing acidity within the pH 0–2 range. The mechanism of the reactions has been discussed.  相似文献   

20.
A novel supramolecular assembly [{Cu(enac)}2Cr(NCS)4(NH3)2][Cr(NCS)4(NH3)2]3 · 4(CH3)2CO (enac = 4,6,6-trimethyl-3,7-diazanon-3-ene-1,9-diamine), the first example of a Cu/Cr heterometallic compound containing a Schiff-base ligand such as enac, and an anion of Reineckes salt, Cr(NCS)4(NH3)2−, as a building block, was obtained by the self-assembly reaction of copper powder and Reineckes salt in an acetone/methanol (1:4) solution of ethylenediamine in the open air. An X-ray study shows that the complex includes a trinuclear Cu2Cr cation, constructed from two Cu(enac)2+ moieties and a trans-[Cr(NCS)4(NH3)2]− block as a two-linking bridging ligand. The metal–metal separations within the cation are Cu?Cr = 6.393(31) Å and Cu?Cu = 12.786(63) Å. The supramolecular architecture of the complex involves two types of H-bonded chains, the first chain is generated by trinuclear cations [{Cu(enac)}2Cr(NCS)4(NH3)2]2+, [Cr(NCS)4(NH3)2]− anions and (CH3)2CO molecules, while the second by crystallographically different anions of Reineckes salt and (CH3)2CO. Variable-temperature (1.8–300 K) magnetic susceptibilities show a slight change of the μB value at low temperature, indicative of weak antiferromagnetic interactions (JCuCr = −0.9 cm−1) between the paramagnetic centers.  相似文献   

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