Osmium oxo compounds

Osmium tetraoxide and permanganate are the textbook example reactants for the direct addition of the hydroxyl function to double bonds as shown in Figure 1. Several reagents such as hydrogen peroxide, periodate, hexacyanoferrate(III) or recently also molecular oxygen [2-6] have been used to reoxidize the different metal-oxo compounds. 

The reaction mechanisms of these transition metal mediated oxidations have been the subject of several computational studies, especially in the case of osmium tetraoxide [7-10], where the controversy about the mechanism of the oxidation reaction with olefins could not be solved experimentally [11-20]. Based on the early proposal of Sharpless [12], that metallaoxetanes should be involved in alkene oxidation reactions of metal-oxo compounds like Cr02Cl2, 0s04 and Mn04" the question arose whether the reaction proceeds via a concerted [3+2] route as originally proposed by Criegee [11] or via a stepwise [2+2] process with a metallaoxetane intermediate [12] (Figure 2). 

The resolution of the hot debate on the mechanism of metal-oxo mediated oxidations is one of the success stories of DFT calculations. An early publication by Sharpless on chromylchloride oxidations of alkenes10 started a long ongoing discussion11-25 on the mechanism of metal-oxo mediated oxidations. Sharpless proposed an interaction between the chromium metal and the alkene and generalized his proposal to include all metal-oxo compounds, especially osmium tetroxide and permanganate. Especially the mechanism of the reaction of osmium tetroxide with alkenes was the subject of an intense debate within the community of experimental organic chemists (Scheme 2). 

It was later found that this transformation can be also carried out using other transition metal-oxo compounds like ruthenium-oxo species [51] and osmium tetroxide [23, 24], which has been reviewed by Piccialli in 2007 [52]. 

Organometallic compounds asymmetric catalysis, 11, 255 chiral auxiliaries, 266 enantioselectivity, 255 see also specific compounds Organozinc chemistry, 260 amino alcohols, 261, 355 chirality amplification, 273 efficiency origins, 273 ligand acceleration, 260 molecular structures, 276 reaction mechanism, 269 transition state models, 264 turnover-limiting step, 271 Orthohydroxylation, naphthol, 230 Osmium, olefin dihydroxylation, 150 Oxametallacycle intermediates, 150, 152 Oxazaborolidines, 134 Oxazoline, 356 Oxidation amines, 155 olefins, 137, 150 reduction, 5 sulfides, 155 Oxidative addition, 5 amine isomerization, 111 hydrogen molecule, 16 Oxidative dimerization, chiral phenols, 287 Oximes, borane reduction, 135 Oxindole alkylation, 338 Oxiranes, enantioselective synthesis, 137, 289, 326, 333, 349, 361 Oxonium polymerization, 332 Oxo process, 162 Oxovanadium complexes, 220 Oxygenation, C—H bonds, 149... 

Reactions between salts of [ z<7o-7-CB10I b3] and [Fe3(CO)12] afford the mononuclear anionic iron compound [2,2,2-(CO)3-c/oxo-2,l-FeCB10Hn], typically isolated as its [N(PPh3)2]+ salt (11) (Chart 4).14 No anionic triiron complex analogous to 5 and 7 is formed in this reaction. The anionic mononuclear iron, ruthenium and osmium complexes and the previously mentioned neutral mononuclear ruthenium dicarbollide complex 4, obtained from [Ru3(CO)12] and /zfo-7,8-C2B9H13, are iso-lobal with the cyclopentadienide species [Mn(CO)3(ti-C5H5)] and [Fe(CO)3 (tl-C5H5)] +. ... 

The oxo complexes of osmium dominate the chemistry of the element, the duster carbonyls notwithstanding, and the tetroxide is the single most important compound of the element. 

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