Reaction of azidopentaammineiridium(III) cation with acid. Intermediate formation of coordinated nitrene

Oxidation of pentaamminecarbonylosmium(2+) to .mu.-dinitrogen-bis(cis-tetraamminecarbonylosmium)(4+)

“…The production of the binuclear species was efficient (85%) with up to 2.0 equiv of Ce(IV)/mol of Os(II); above this ratio, there was a continued decrease in yield (66% with 2.5 equiv and 48% with 3.0). In another experiment with Os(II) at 9.1 X 10"3 M, 5 °C, Ce(IV) was added in the molar ratio Ce(IV)/Os(II) = 3.0. The oxidizing agent was observed to be consumed in less than 5 s, but the binuclear product appeared at a slower rate, the slower reaction approximately obeying second-order kinetics.…”

Thermal and light-induced decomposition of azido(bis-2,2'-bipyridine) complexes of ruthenium(III)

“…to a considerable degree recently by the use of flash photolysis techniques2•3 and the results of both product isolation studies and of scavenging experiments for intermediates. [3][4][5][6][7][8][9][10] For the systems which have' been studied, it appears that strong, one-electron oxidants (e.g., Co(III),11 Mn(III)12) react with N3to give azide radicals, N30, and the reduced form of the oxidant. Azide radicals are also produced in the light-induced decomposition of Co(III)2•4 and of other metal azide5 •13 complexes.…”

Failure of the Guidry-Drago reanalysis of spectroscopic data for the reversible oxygenation of amine complexes of cobalt protoporphyrin IX dimethyl ester

“…Basically GD employ a nonlinear, unweighted, least-squares analysis for the simultaneous determination of both K2 and of te -e5, although since e5 is determined before addition of 02 the practical variables in the GD analysis are K2 and ee. Following the solution for the best values (in a least-squares sense) of the variables, where the function minimized is R = X^G^obsd -Scaled)2 (8) the marginal and conditional standard deviations of (17) Since a(log ) = 0AZa(Ki)¡Ki, for log Ki = -2.0 a 10% error in & is reflected in approximately a 2% error in log Ki. It is interesting that nowhere do GD point out this relationship even though it is the log Ki values that are used in the derivation of the thermodynamic quantities.…”

“…itrene intermediates have been reported in the reactions of azide ion,1,2 hydrazoic acid,8 9and of a large number of organic azides.4-6 However, reports of coordinated nitrene intermediates are conspicuously few.7-9 The formation of coordinated nitrenes in the reactions of Ru(NH3)5N32+ and of Ir(NH3)5N32+ with aqueous acid was established in reports from these laboratories. [7][8] The chemistry of these intermediates was described as that of a strong electrophile, and they undergo a number of reactions which have analogs in both nitrene and organic nitrene chemistry.…”