Chromium complexes, absorption solutions

In summary, spectroscopic studies show that at low temperatures higher excited states of chromium(III) complexes undergo rapid internal conversion to the metastable T2g or 2Eg levels. Intersystem crossing from the 4T2g to the aEg level occurs with near unit efficiency in many chromium(III) complexes. Phosphorescence competes, usually unfavorably, with radiationless decay from the 2Eg state. Studies of the excited states of Mo(III), (4d)3, based on absorption spectra of its complexes in solution, have recently been reported.134-137... 

Metal carbonyl halides can also undergo photoredox reactions if an MLCT chromophoreofsuitableenergyispresentinthecomplex.ThecomplexCrI(CO)5, for example, has a characteristic long-wavelength absorption at 638 nm that is due to an I - Cr (LMCT) absorption. Irradiation into this chromophore for a solution of CrI(CO)5 in acetonitrile leads to the formation of iodine and the zerovalent chromium complex Cr(CO)5MeCN with a quantum yield of 0.01 (Ref. 65) ... 

Moffett [179] determined chromium in seawater by Zeeman corrected graphite tube atomisation atomic absorption spectrometry. The chromium is first complexed with a pentan-2,4 dione solution of ammonium 1 pyrrolidine carbodithioc acid, then this complex extracted from the water with a ketonic solvent such as methyl isobutyl ketone, 4-methylpentan-2-one or diisobutyl ketone. 

The collection behaviour of chromium species was examined as follows. Seawater (400 ml) spiked with 10-8 M Crm, CrVI, and Crm organic complexes labelled with 51Cr was adjusted to the desired pH by hydrochloric acid or sodium hydroxide. An appropriate amount of hydrated iron (III) or bismuth oxide was added the oxide precipitates were prepared separately and washed thoroughly with distilled water before use [200]. After about 24 h, the samples were filtered on 0.4 pm nucleopore filters. The separated precipitates were dissolved with hydrochloric acid, and the solutions thus obtained were used for /-activity measurements. In the examination of solvent extraction, chromium was measured by using 51Cr, while iron and bismuth were measured by electrothermal atomic absorption spectrometry. The decomposition of organic complexes and other procedures were also examined by electrothermal atomic absorption spectrometry. 

The intermediate cyclooctene complex appears to be more reactive with respect to CS coordination and more sensitive to oxidation when the arene ring bears electron-withdrawing groups (e.g., C02CH3). Dicarbonyl(methyl rj6-benzoate)-thiocarbonyl)chromium is air stable in the solid state and reasonably stable in solution.9 The infrared spectrum exhibits metal carbonyl absorptions at 1980 and 1935 cm"1 and a metal thiocarbonyl stretch at 1215 cm"1 (Nujol) (these occur at 1978, 1932, and 1912 cm"1 in CH2C12 solution).10 Irradiation of the compound in the presence of phosphite or phosphine leads to slow substitution of CO by these ligands, whereas the CS ligand remains inert to substitution. The crystal structure has been published."... 

Both absorption and emission spectra have been recorded for a variety of octahedral chromium(III) complexes. For the systems of interest here, A/B 2. Inspection of Figure 2 leads to the expectation of three spin-allowed, parity-forbidden transitions between the iA2g and the other quartet states and two spin- and parity-forbidden transitions between the iA2g and the 2Eg and 2T2g states. Aqueous solutions of Cr(H20)s3+ display three bands with e 15 at 17,400, 24,500, and 38,000 cm-1, assigned respectively to the transitions iA2g- iT2g,... 

Electronic Circular Dichroism In contrast to most organic compounds in which CD measurements are limited to the ultraviolet region, most metal complexes possess d-d absorption bands in the more accessible visible and near-infrared regions, allowing for relatively easier application of electronic circular dichroism (ECD) measurements. In fact, the first observation by Cotton of optical rotation measurements through an absorption band and interpretation in terms of differential absorption of the circularly polarized beam was performed on solutions of L-tartrate chromium(III) and copper(II) complexes.100... 

Tables 1 and 2 gives the numerical data for a series of vanadium (II), chromium (III), manganese (IV), molybdenum (III), rhenium (IV), iridium (VI), cobalt (II), and nickel (II) complexes. The first spin-allowed absorption band, caused by an internal transition in the partly filled shell, has the wavenumber equal to A. If spin-forbidden transitions are superposed on this band, a certain distortion from the usual shape of Gaussian error curve can be observed, and one takes the centre of gravity of intensity as the corrected wavenumber ai. One has to be careful not to confuse electron transfer or other strong bands with the internal transitions discussed here. Obviously, one has also to watch for absorption due to other coloured species, produced e. g. by oxidation or hydrolysis of the solutions. In the case of certain octahedral nickel (II), and nearly all tetrahedral cobalt (II) complexes, the first band has not actually been...

Ganescu et al. used a thiocyanto-Cr(III)-complex for the spectro-photometric determination of dipyridamole (1-15 mg) in 25 mL of solution [16]. The solution was acidified with 1-2 mL of 1 M hydrochloric acid, and treated with a slight excess of ammonium diimidazoletetrakis (thiocyanato) chromium (III). The precipitate was collected and washed, dissolved in acetone, and diluted to 25 mL with the same solvent. The absorbance was measured at 540 nm (molar absorptivity equal to 846). 

Ti, P) furthermore, none of these states cross each other as the strength of the interaction changes. As an example, we take the case of [Cr(H,0),] +. The aqueous solutions of salts of trivalent chromium are green in colour as a result of absorption bands at 17 000, 24 000, and 37 000 cm (there are also two very weak spin forbidden bands at 16 000 and 22 000 cm ). If the complex is specified by fitting the transitions TtjF) At,(F) and to 17 000 and... 

Transient absorption measurements have recently been recorded from the organometallic species chromium hexacarbonyl in ethanol solution [94], Absorption of a 65-fs, 310-nm excitation pulse was followed by measurement of excited-state absorption of a 65-fs, 480-nm probe pulse. The data shown in Figure 14 indicate a rapid nonexponential decay at short times followed by a gradual exponential rise. The slower feature was observed previously [95] and is known to correspond to the solvent complexation of Cr(CO)5 to yield Cr(CO)j(MeOH). The initial feature, which is observed at other probe wavelengths as well, is believed to correspond to the initial ligand loss reaction. Note that this case is different from ICN in that the initially excited wavepacket is not on the side of the Sj potential but rather (as is clear from the molecular symmetry) on a local potential maximum. The wavepacket must then spread that is, dissociation along either direction is equally likely. The rapid nonexponential decay was analyzed in terms of classical kinematics along a dissociative potential. 

With chromium(III), EDTA forms a violet complex in slightly acidic medium. The complex is formed slowly in the cold, but more rapidly if the solution is heated [28,29]. The sensitivity of the method is not high. The molar absorptivity is 1.4-10 at 540 nm (a = 0.003). The colour intensity diminishes as the pH is reduced. In a hot solution EDTA reduces Cr(VI) to Cr(III). This reaction is catalyzed by traces of Mn(II). 

The color and solubilities of these chromium(III) ammines are very similar to those of the corresponding cobalt(III) complexes.5 The chlorides, bromides, nitrates, and perchlorates in the acidopentamminechromium(III) series are not very soluble in water, whereas the analogous aquopentamminechromium(III) salts are soluble. In aqueous solutions, these chromium(III) ammines are much more readily decomposed than the corresponding cobalt(III) ammines. Decomposition may be perceptible within a few minutes. The absorption spectra of aqueous solutions of some acidopentamminechromium(III) salts have been studied.6,7... 

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