Photochemistry of the cis- and trans-Dichlorobisethylenediamine Chromium(III) Cations in Acidic Aqueous Solutions. Observation of a Stereochemical Change in Photoaquation

1971 ◽  
Vol 49 (9) ◽  
pp. 1524-1528 ◽  
Author(s):  
A. D. Kirk ◽  
K. C. Moss ◽  
J. G. Valentin
Keyword(s):  
Aqueous Solution ◽  
Quantum Yield ◽  
Aqueous Solutions ◽  
Trans Isomer ◽  
Ligand Field ◽  
Acidic Aqueous Solution ◽  
Ethylenediamine Complex ◽  
Cis And Trans ◽  
Cis Isomer

The photoreactions of cis- and trans-[CrCl2(en)2]+ have been investigated in acidic aqueous solution at pH 3 and 0 °C. On photolysis in the ligand field bands the cis isomer was found to undergo mainly ethylenediamine aquation, apparently to a thermally unstable monodentate protonated ethylenediamine complex, with a quantum yield of 0.13. In addition chloride aquation occurred with[Formula: see text]. In contrast, the trans isomer underwent exclusive chloride aquation with quantum yield 0.32. The results are qualitatively, but not quantitatively, in agreement with predictions of Adamson's empirical rules. It was found that for trans-[CrCl2(en)2]+ photolysis, the reaction product [CrCl(H2O)(en)2]2+ was produced at least 70% in the cis configuration.

The Photolysis in Acidic Aqueous Solutions of the Monooxalato-bisethylenediamine Chromium(III) Cation and the Bisoxalatomonoethylenediamine Chromate(III) Anion: Photolysis Modes and Quantum Yields

1971 ◽  
Vol 49 (3) ◽  
pp. 375-383 ◽  
Author(s):  
A. D. Kirk ◽  
K. C. Moss ◽  
J. G. Valentin
Keyword(s):  
Quantum Yield ◽  
Aqueous Solutions ◽  
Quantum Yields ◽  
Ligand Field ◽  
Intersystem Crossing ◽  
Empirical Correlations ◽  
Complex Ions ◽  
Ethylenediamine Complex ◽  
Ethylenediamine Ligand ◽  
Ph Range

The photolysis reactions of the complex ions [Cr(en)2ox]+ and [Cren(ox)2]− have been studied in the pH range 1 → 3 and at temperatures from 0 to 25 °C. It has been found that both ions photoaquate to a monodentate protonated ethylenediamine complex which then undergoes further aquation thermally with loss of the ethylenediamine ligand. Quantum yields for these aquations were measured for irradiation into the ligand field bands, the values obtained being 0.18 and 0.02, respectively. The results are discussed in terms of known empirical correlations for Cr(III) complexes. Assuming these reactions may occur from the 4T2g state as precursor, arguments are presented that the correlation between quantum yield and ΔE may depend on mixing of the 4T2g and 2Eg states, and its effect on the intersystem crossing rate constant.

scholarly journals Reaction of cis- and trans-Dichlorotetra(Dimethylsulfoxide)Ruthenium(II) With the Antiviral Drug Acyclovir

2000 ◽  
Vol 7 (6) ◽  
pp. 325-334 ◽  
Author(s):  
Aglaia Koutsodimou ◽  
Giovanni Natile
Keyword(s):  
Trans Isomer ◽  
Early Stage ◽  
Antiviral Drug ◽  
Metallic Substrate ◽  
Purine Base ◽  
Coordination Environment ◽  
Molar Ratios ◽  
Discrete Amount ◽  
Cis And Trans ◽  
Cis Isomer

NMR was used to investigate the reaction of cis- and trans-[RuCl2(DMSO)4] with the antiviral drug acyclovir, a guanine derivative containing the acyclic (2-hydroxo) ethoxymethyl pendant linked to N(9). Studies were performed in aqueous solutions at ambient temperature and at 37 °C, and at various molar ratios. Both isomers yielded two compounds, a monoadduct and a bisadduct, the relative yields being dependent upon the metal to ligand concentration ratios. The products derived from the two Ru isomers displayed identical NMR spectra, suggesting that they have the same coordination environment, however the rate of formation of the monoadduct was higher in the case of the trans isomer than in the case of the cis isomer, while the rate of conversion of the monoadduct into the bisadduct appeared to be similar in both cases. As a consequence in the case of the trans isomer there is accumulation of monoadduct in the early stage of the reaction, whose concentration afterwards decreases with the progress of the reaction. As for platinum, also for ruthenium the preferred binding site is N(7) of the purine base, however, in the case of ruthenium a discrete amount of bisadduct is formed even in the presence of an excess of metallic substrate with respect to the acyclovir ligand; under similar conditions a platinum substrate would have given, nearly exclusively, the monoadduct.

[1H,15N] N.M.R. Kinetic Studies of Reactions of cis- and trans-[PtCl2(15NH3)(c-C6H1115NH2)] with Guanosine 5'-Monophosphate

1999 ◽  
Vol 52 (3) ◽  
pp. 173 ◽  
Author(s):  
Sarah J. Barton ◽  
Kevin J. Barnham ◽  
Abraha Habtemariam ◽  
Urban Frey ◽  
Rodney E. Sue ◽  
...  
Keyword(s):  
Trans Isomer ◽  
Active Metabolite ◽  
Kinetic Studies ◽  
Trans Influence ◽  
Trans Complex ◽  
Kinetics Of Reaction ◽  
Cis And Trans ◽  
Kinetics Of ◽  
Cis Isomer ◽  
Amine Ligand

cis-[PtCl2(15NH3)(c-C6H11NH2)] is an active metabolite of the oral platinum(IV) anticancer drug cis,trans,cis-[PtCl2(CH3CO2)2(NH2)(c-C6H11NH2)]. Since it is likely that guanine bases on DNA are targets for this drug, we have analysed the kinetics of reaction of this platinum(II) metabolite with guanosine 5′-monophosphate (5′-GMP) at 310 K, pH 7, using [1H, 15N] n.m.r. methods. Reactions of the trans isomer are reported for comparison. The reactions proceed via aquated intermediates, and, for the cis isomer, the rates of aquation and substitution of H2O by 5′-GMP are 2-5 times faster trans to the amine ligand (c-C6H11NH2) compared to trans to NH3 for both the first and second steps. For the trans complex, the first aquation step is c. 3 times faster than for the cis complex, as expected from the higher trans influence of Cl¯, whereas the rate of the second aquation step (trans to N7 of 5′-GMP) is comparable to that trans to NH3. These findings have implications for the courses of reactions with DNA.

Sur la réduction de polyméthyldihydro-2,3 phénalènones-1 par l'hydrure de lithium et d'aluminium

1974 ◽  
Vol 52 (17) ◽  
pp. 3106-3112 ◽  
Author(s):  
E. Costakis ◽  
P. Canonne ◽  
R. St-Jean
Keyword(s):  
Trans Isomer ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Considerable Extent ◽  
Lithium Aluminum ◽  
Trans Isomers ◽  
Cis And Trans Isomers ◽  
Cis And Trans ◽  
Cis Isomer ◽  
Steric Constraints

The reduction of some polymethyl-2,3-dihydro phenalen-1-ones by lithium aluminum hydride yields a mixture of cis and trans isomers; the percentage of each isomer depends to a considerable extent on its structure. Indeed, for some, the trans isomer predominates while for others the cis isomer is obtained in up to 88% yields. Moreover, in the particular case in which the trans isomer is formed in low yields, its preferred conformation is trans diaxial.The steric constraints which render certain transition states unfavourable during the attack of the hydride are discussed with the aid of spectroscopic data on the alcohols obtained. [Journal translation]

Electrochemical Reaction Mechanism of Tiron in Acidic Aqueous Solution

2011 ◽  
Vol 396-398 ◽  
pp. 1730-1735 ◽  
Author(s):  
Yan Xu ◽  
Yue Hua Wen ◽  
Jie Cheng ◽  
Gao Ping Cao ◽  
Yu Sheng Yang
Keyword(s):  
Aqueous Solution ◽  
Cyclic Voltammetry ◽  
Aqueous Solutions ◽  
Electrochemical Oxidation ◽  
Electrochemical Reaction ◽  
Mass Spectrometric ◽  
Acidic Aqueous Solution ◽  
Ece Mechanism ◽  
Flow Through ◽  
Electro Oxidation

Electrochemical oxidation of tiron in the presence of H2O as a nucleophile in strongly acidic aqueous solutions was studied by cyclic voltammetry, controlled-voltage coulometry and spectrometric investigations. The mechanism of electrochemical reaction is confirmed by spectrophotometric tracing in various times of controlled-voltage coulometry. The voltammetric and spectrophotometric foundations indicate that a 1,4-Michael addition of H2O from its hydroxy moiety to the position 4 of electrochemically derived o-quinone is occurred. The electrochemical oxidation and reduction of tiron has been successfully accomplished by controlled-voltage coulometry in a redox flow-through type cell and the final electro-reduced product was characterized by spectrophotometric, 1H NMR and mass spectrometric methods. It is demonstrated that the electro-oxidation of tiron follows an ECE mechanism in acidic aqueous solutions, leading to formation of a new compound of para- benzoquinone derivative.

Concertedness in the Thermolysis of Some 1-Pyrazolines

1974 ◽  
Vol 52 (17) ◽  
pp. 3134-3139 ◽  
Author(s):  
Robert J. Crawford ◽  
Masatomi Ohno
Keyword(s):  
Trans Isomer ◽  
Diphenyl Ether ◽  
Rate Determining Step ◽  
Nitrogen Bonds ◽  
Cis And Trans ◽  
Kinetics Of ◽  
Cis Isomer ◽  
Nitrogen Evolution

A mixture of cis- and trans-3,5-divinyl-1-pyrazoline was synthesized and isolated at 0° by the cycloaddition of vinyldiazomethane to butadiene. The kinetics of the thermolysis in diphenyl ether at 35–65° were studied by measuring the rate of nitrogen evolution. The cis isomer gave log (k1/s−1) = (12.28 ± 0.9 ) − (22.8 ± 0.4 )/θ where θ = 2.303RT in kcal mol−1, for the trans isomer log(k2/s−1) = (13.9 ± 0.9 ) − (25.7 ± 0.4 )/θ was obtained. These data when compared with those of 1-pyrazoline and 3-vinyl-1-pyrazoline lead to the conclusion that both carbon–nitrogen bonds are being broken in the rate determining step. Thus the alkyl-1-pyrazolines are concerted whereas the azoalkanes are not.

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