Mechanism of oxidation of L-ascorbic acid by the pentaamminechromatocobalt(III) complex ion in aqueous solution

Author(s):  
Donovan A. Dixon ◽  
Tara P. Dasgupta ◽  
Novelette P. Sadler
2009 ◽  
Vol 87 (1) ◽  
pp. 110-120 ◽  
Author(s):  
Julia R Khusnutdinova ◽  
Peter Y Zavalij ◽  
Andrei N Vedernikov

Oxidation of phenyl PtII complexes K[(dpms)PtIIPh2], 1, (dpms)PtIIPh(MeOH), 2, (dpms)PtIIPh(OH2), 3, and methyl PtII complex (dpms)PtIIMe(NH2Ph), 6, with O2 in aqueous or methanol solutions under ambient conditions leads to corresponding (dpms)PtIVR(X)OH complexes (R = X = Ph, 7; R = Ph, X = OH, 8; R = Ph, X = OMe, 9; R = Me, X = NHPh; 11; dpms = di(2-pyridyl)methanesulfonate). Complexes 7–9 could be isolated in high yield. Complex 11 as well as its phenyl analogue (dpms)PtIVPh(NHPh)OH, 10 can be prepared in high yield by oxidation of corresponding (dpms)PtIIR(NH2Ph) with H2O2 in methanol. Phenyl PtII complexes (dpms)PtIIPh(HX) derived from HX = aniline and DMSO, 4 and 5, respectively, are inert toward O2. The rate of oxidation of 1–5 with O2 decreases in the order 1 > 3 ~ 2 » 4, and 5 is unreactive. Methyl analogues are significantly more reactive compared with their phenyl counterparts. Proposed mechanism of oxidation with O2 includes formation of anionic species (dpms)PtIIR(X)– responsible for reaction with dioxygen. Attempts at C–O and C–N reductive elimination from phenyl PtIV complexes 7–10 do not lead to phenyl derivatives PhX at 80–100 °C, consistent with the results of the DFT estimates of corresponding activation barriers, ΔG0 exceeding 28 kcal/mol.Key words: platinum phenyl complexes, oxidation, dioxygen, aqueous solution, mechanism.


2003 ◽  
Vol 68 (1) ◽  
pp. 65-73 ◽  
Author(s):  
Randjel Mihajlovic ◽  
Natasa Ignjatovic ◽  
Marija Todorovic ◽  
Ivanka Holclajtner-Antunovic ◽  
Vesna Kaljevic

A modified spectrophotometric method using the bismuth phosphomolybdate complex for the determination of phosphorus in coal and coal ash is suggested. Bismuth together with phosphate and molybdate forms a very stable complex in acid medium which turns blue ("molibdenum blue") by reduction with ascorbic acid. The apparent molar absorptivity of PBiMo is 1.66x104 dm3 mol-1cm-1 at 720 nm and 2.10x104 dm3 mol-1cm-1 at 670 nm isobutyl methyl ketone (MIBK). Interference caused by the ions present are within the tolerance limits (?2 %). Beer?s law is obeyed in the for concentration range to 0.6 ?g/mL (aqueous solution) and to 1.2 ?g/mL P (MIBK). The sensitivity of the proposed method is 0.0078 ?g/mL (aqueous solution) and 0.0066 ?g/mL (MIBK).


1963 ◽  
Vol 52 (10) ◽  
pp. 948-954 ◽  
Author(s):  
Per Finholt ◽  
Rolf B. Paulssen ◽  
Takeru Higuchi

2005 ◽  
Vol 53 (6) ◽  
pp. 688-690 ◽  
Author(s):  
Makoto Ichikawa ◽  
Nagatoshi Ide ◽  
Sumihiro Shiraishi ◽  
Kazuhisa Ono

Sign in / Sign up

Export Citation Format

Share Document