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Osmium complexes olefin

An initial osmium tetraoxide/olefin complex (in Scheme 21) is not generally disputed and is considered a donor/acceptor complex between an alkene as electron donor and 0s04 as an electron acceptor (with a reversible reduction potential E ed = —0.06 V versus SEC),217 e.g.,... [Pg.270]

In our laboratory we have examined the reactivity pattern of [0s3(y-H)2(C0)10], an unsaturated cluster which can be represented as possessing an osmium-osmium double bond in its classical valence bond representation. We find (2,3) that this compound undergoes a number of reactions with metal carbonyls which in some cases can be formulated as proceeding through intermediates analogous to metal olefin complexes ... [Pg.383]

This observation may well explain the considerable difference between metal-olefin and metal-acetylene chemistry observed for the trinuclear metal carbonyl compounds of this group. As with iron, ruthenium and osmium have an extensive and rich chemistry, with acetylenic complexes involving in many instances polymerization reactions, and, as noted above for both ruthenium and osmium trinuclear carbonyl derivatives, olefin addition normally occurs with interaction at one olefin center. The main metal-ligand framework is often the same for both acetylene and olefin adducts, and differs in that, for the olefin complexes, two metal-hydrogen bonds are formed by transfer of hydrogen from the olefin. The steric requirements of these two edgebridging hydrogen atoms appear to be considerable and may reduce the tendency for the addition of the second olefin molecule to the metal cluster unit and hence restrict the equivalent chemistry to that observed for the acetylene derivatives. [Pg.290]

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... [Pg.196]

The [2+2] Mechanism Already in 1977 Sharpless proposed a stepwise [2+2] mechanism for the osmylation of olefins in analogy to related oxidative processes with d°-metals such as alkene oxidations with CrO,Cl2 [23, 24], Metallaoxetanes [25] were suggested to be formed by suprafacial addition of the oxygens to the olefinic double bond. In the case of osmylation the intermediate osmaoxetane would be derived from an olefm-osmium(VIII) complex that subsequently would rearrange to the stable osmium(VI) ester. [Pg.403]

When ligand L is an olefin, reaction of Nal with derivatives 176 and 173 proceeds in two different ways. Complex 176 gives the neutral monoalkyl osmium(II) complex 160 by olefin insertion, whereas complex 173 gives the neutral methyl osmium(II) compound 160 by olefin displacement (47). [Pg.199]

Until recently there has been surprisingly little interest in high oxidation state complexes of terpy. Meyer and co-workers have demonstrated that the ruthenium(IV) complex [Ru(terpyXbipy)0] is an effective active catalyst for the electrocatalytic oxidation of alcohols, aromatic hydrocarbons, or olefins (335,443,445,446). The redox chemistry of the [M(terpy)(bipy)0] (M = Ru or Os) systems has been studied in some detail, and related to the electrocatalytic activity (437,445,446). The complexes are prepared by oxidation of [M(terpy)(bipyXOH2)] . The related osmium(VI) complex [Os(terpyXO)2(OH)] exhibits a three-electron reduction to [Os(terpyXOH2)3] (365,366). The complex [Ru(terpy)(bipyXH2NCHMe2)] undergoes two sequential two-electron... [Pg.86]

Table 6.1 contains a list of known compounds of this type [3-25]. No examples of complexes containing Ti (N)-Pyr ligands are known, in accord with the low basicity of the N-atom in this molecule. On the other hand, metal derivatives containing olefin-like ligands, in either one of the tautomeric forms, ti (C=C)-IH-Pyr or t (C=C)-2H-Pyr, have been characterized for osmium(II) complexes [3-5]. [Pg.154]

Two reaction mechanisms have been proposed for these dihydroxylations (pathway a or b, Figure 7.23), either a concerted [3+2] cycloaddition of the olefins on osmium-diamine complex 7.33 or a stepwise reversible [2+2] cycloaddition followed by a rearrangement [559,1350], An X-ray crystal structure of the resulting osmic ester 2.89A shows its symmetrical structure. Houk s calculations [1351] are in favor of a concerted reaction, and his transition state model is reactant-like, with steric interactions dictating the face selectivity of osmylation. [Pg.400]

Tomioka et al. [61,62] demonstrated a highly enantioselective dihydroxyla-tion of olefins using stoichiometric amoimts of an osmium tetroxide complex with chiral diamine 45 (Fig. 6). [Pg.155]

Abstract The oxidative functionalization of olefins is an important reaction for organic synthesis as well as for the industrial production of bulk chemicals. Various processes have been explored, among them also metal-catalyzed methods using strong oxidants like osmium tetroxide. Especially, the asymmetric dihydroxylation of olefins by osmium(Vlll) complexes has proven to be a valuable reaction for the synthetic chemist. A large number of experimental studies had been conducted, but the mechanisms of the various osmium-catalyzed reactions remained a controversial issue. This changed when density functional theory calculations became available and computational studies helped to unravel the open mechanistic questions. This mini review will focus on recent mechanistic studies on osmium-mediated oxidation reactions of alkenes. [Pg.143]

The oxidative functionalization of olefins mediated by transition metal oxides leads to a variety of products including epoxides, 1,2-diols, 1,2-aminoalcohols, and 1,2-diamines [1]. Also the formation of tetrahydrofurans (THF) from 1,5-dienes has been observed, and enantioselective versions of the different reactions have been developed. Although a lot of experimental data has been available, the reaction mechanisms have been a subject of controversial discussion. Especially, osmium (VIII) complexes play an important role there, as the proposal of a stepwise mechanism [2] for the dihydroxylation (DH) of olefins by osmium tetroxide (OSO4) had started an intense discussion about the mechanism [2—11],... [Pg.144]

Castro-Rodrigo R, Esteruelas MA, Fuertes S, Lopez AM, Mozo S, Onate E. Olefin-alkylidene equilibrium of 2-vinylpyridine in osmimn- and ruthenium-hydrido-tris (pyrazolybborate and osmium-cyclopentadienyl complexes. Organometallics. 2009 28 594-5951. [Pg.253]

The only reported unconjugated olefin complexes of osmium are t clo-octa-1,5-diene complexes OsCl2PPh2Et [97] and [Os(C8Hi2)Cl2]x [98]. For rhenium a few olefin cottq>lexes are known such as the cyclopenta-diene derivative 7r-CsHsRe(CO)2CsH6 (p. 23) which may be compared to the 7r-CsHsMn(CX))2 olefiua analogues (p. 125). [Pg.34]

Diols are applied on a multimilhon ton scale as antifreezing agents and polyester monomers (ethylene and propylene glycol) [58]. In addition, they are starting materials for various fine chemicals. Intimately coimected with the epoxidation-hydrolysis process, dihydroxylation of C=C double bonds constitutes a shorter and more atom-efficient route to 1,2-diols. Although considerable advancements in the field of biomimetic nonheme complexes have been achieved in recent years, still osmium complexes remain the most efficient and reliable catalysts for dihydroxylation of olefins (reviews [59]). [Pg.90]

The formation of these compounds has been rationalized according to Scheme 6. The reaction of Os (E )-CH=C 11 Ph C1 (C())( P Pr3)2 with n-BuLi involves replacement of the chloride anion by a butyl group to afford the intermediate Os (/i> CH=CHPh ( -Bu)(CO)(P Pr3)2, which by subsequent hydrogen (3 elimination gives OsH ( >CI I=CHPh (CO)( P Pr3)2. The intramolecular reductive elimination of styrene from this compound followed by the C—H activation of the o-aryl proton leads to the hydride-aryl species via the styrene-osmium(O) intermediate Os r 2-CH2=CHPh (CO)(P Pr3)2. In spite of the fact that the hydride-aryl complex is the only species detected in solution, the formation of OsH ( )-CH=CHPh L(CO)(P Pr3)2 and 0s ( )-CH=CHPh (K2-02CH)(C0)(P,Pr3)2 suggests that in solution the hydride-aryl complex is in equilibrium with undetectable concentrations of OsH ( )-CH=CHPh (CO)(P,Pr3)2. This implies that the olehn-osmium(O) intermediate is easily accessible and can give rise to activation reactions at both the olefinic and the ortho phenyl C—H bonds of the... [Pg.9]


See other pages where Osmium complexes olefin is mentioned: [Pg.687]    [Pg.247]    [Pg.204]    [Pg.388]    [Pg.1153]    [Pg.207]    [Pg.19]    [Pg.492]    [Pg.401]    [Pg.122]    [Pg.102]    [Pg.153]    [Pg.274]    [Pg.168]    [Pg.85]    [Pg.335]    [Pg.186]    [Pg.604]    [Pg.33]    [Pg.179]    [Pg.676]    [Pg.229]    [Pg.6]    [Pg.22]    [Pg.125]    [Pg.237]   
See also in sourсe #XX -- [ Pg.93 ]




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