Cobalt complexes carbonyl hydride

Methyl acetate probably originates from the reaction of methanol with the intermediate cobalt-acyl complex. The reaction leading to the formation of acetaldehyde is not well understood. In Equation 8, is shown as the reducing agent however, metal carbonyl hydrides are known to react with metal acyl complexes (20-22). For example, Marko et al. has recently reported on the reaction of ri-butyryl- and isobutyrylcobalt tetracarbonyl complexes with HCo(CO) and ( ). They found that at 25 °C rate constants for the reactions with HCo(CO) are about 30 times larger than those with however, they observed that under hydroformylation conditions, reaction with H is the predominant pathway because of the greater concentration of H and the stronger temperature dependence of its rate constant. The same considerations apply in the case of reductive carbonylation. Additionally, we have found that CH C(0)Co(C0) L (L r PBu, ... 

Alkylcobalt carbonyl isomerization via the formation of olefincobalt-carbonyl hydride complexes with retention of the olefin attached to the cobalt atom has been suggested as the mechanism of formation, of the necessary precursors of the products with high stereospecificity. 

Co(OAc)2 in the presence of sodium hydride and a sodium alkoxide has been used to catalyze the carbonylation of aryl bromides, giving mixtures of carboxylic acids and esters, again at normal pressure. When amines were present, amides were formed. Unfortunately, nothing is known about the nature of the cobalt complexes involved. 

Apart from the work on binary metal carbonyls and metal carbonyl hydrides, Flieber and his school also greatly extended the field of carbonyl(ni-trosyl) metal complexes. The first compound of the general composition M(CO)x(NO)- was obtained by Robert L. Mond and Albert Wallis as early as in 1922 [67]. While studying the reactivity of Co2(CO)8 toward various substrates, they observed that slowly at room temperature, but almost instantaneously at 40°C, nitric oxide gas reacts with cobalt tetracarbonyl to form a cherry-red liquid, with the evolution of carbon monoxide . This liquid was... 

The oxidative addition of methyl iodide to an unsaturated cobalt carbonyl according to Equation (27) was proposed by Wender, CO insertion gives an acetyl species (28) which is thought to be hydrogenated by cobalt carbonyl hydride or H to yield acetaldehyde [4]. Numerous examples of the oxidative addition of methyl iodide to transition metal complexes with a electron configuration (e.g. Rh Ir ) ate known from the literature [66, 67]. For the carbonytaiion of methanol, the rate has been found to be the oxidative addition of methyl iodide to rhodium(l) [68]. 

Isomerisation of olefins catalysed 11 by palladium and other transi- (34) tion-metal complexes Hydrogenation reaction with 10 cobalt carbonyl hydride as a (29) hydrogenation agent 7r-Complex adsorption in hydrogen 27 exchange on Group VIII transi- (45) tion metal catalysts... 

Most catalysts that have been mentioned so far are mononuclear. The few binuclear compounds utilized Co2(CO)8 or phosphinesubstituted derivatives) did not give evidence of any unusual type of binuclear catalysis. However, new products could result with catalysts producing two active centers in close vicinity which would not dissociate in the course of the reaction. The expected difference between mononuclear and binuclear catalysis is shown in the accompanying diagram (52). A series of metal salts of cobalt carbonyl hydride of composition M[Co(C0)4]n (M=Zn, Cd, Hg, n = 2 M = In, = 3) were tested as potential binuclear catalysts. The complex salts are relatively easily accessible Zn[Co(CO)4]2, for instance, may be prepared from cobalt carbonyl, metallic zinc, and CO (at 3000 psi initial pressure) using toluene as the solvent and a temperature of 200°. The compound may also be synthesized directly from metallic cobalt, zinc, and CO... 

Huo et al. studied the structure and energies of cobalt-carbonyl radicals as well as the cationic and anionic homoleptic mononuclear cobalt-carbonlys and the cobalt-carbonyl hydrides.35 The B3LYP functional was applied with all-electron triple- quality basis. They found that most of these complexes prefer less symmetrical structures and minor structural deformations may result in large energetic differences. 

The reaction of metal carbonyl dimers with silicon hydrides also probably involves an initial oxidative addition step. Chiral silyl-cobalt and silyl-manganese carbonyl complexes have been obtained through the reaction of optically active organosilicon hydrides with metal carbonyls65 68 (equation 15 and 16). Phosphine-substituted cobalt complexes were similarly obtained by reaction of a chiral hydrosilane with Co2(CO)6L2 [L = PPh3, P(OPh)3, P(c-C6Hn)3]69. 

The transition metal hydrides considered here are those discrete complexes which contain one or more hydrogen atoms bonded directly to a transition metal by an essentially covalent, two-electron bond. For many years, the only known complexes in this class were the unstable and reactive carbonyl hydrides of iron and cobalt and, by virtue of their novelty, the hydride ligand acquired a unique status in the minds of many chemists. Today that status is no longer generally acceptable in view of the number and diversity of presently known hydride complexes, many of which possess... 

The first known complex in this class, frans-bis(triethylphosphine)-platinum chlorohydride, was prepared by Chatt and co-workers (86). In the light of other hydrides known at that time, in particular the carbonyl hydrides of iron and cobalt and bis(7r-cyclopentadienyl)rhenium hydride, the great stability of this complex was quite unique. It rapidly became clear that tertiary phosphine ligands were markedly effective in stabilizing the metal-hydrogen bond, and ligands such as PhjP, EtjP, o-CaH PlVfe, ... 

All the simple carbonyl hydrides (Table IY) may be readily prepared by acidification of alkali metal salts derived from the simple carbonyls. Only the carbonyl hydrides of Mn, Re, Co, and Fe are well characterized. They form highly toxic volatile liquids and are unstable thermally and with respect to oxidation. Pentacarbonylmanganese hydride is stable to light and air for several hours at room temperature (173), while the very unstable cobalt and iron complexes decompose spontaneously at — 20°C (167, 251). It may be noted that solutions of these carbonyl hydrides in inert solvents undergo spontaneous decomposition much more slowly than the pure substances. 

Catalytic Reactions Involving Cobalt Carbonyl Hydride Complexes... 

Alkylcobalts form in stoichiometric reactions of pentacyanocobalt(III) hydride and alkenes. This reaction occurs both for halogenated alkenes such as tetrafluoroethylene and for alkenes that contain other electron-withdrawing groups such as carbonyls, nitriles and arenes as substituents (see Table 6) . The addition is regiospedfic, forming the more substituted alkylcobalt. Prior coordination of alkene to cobalt to form an alkene(hydrido)cobalt complex, an intermediate in hydrometalation reactions, is not important. This reaction is a radical process however, by NMR, additions of [HCo(CN)5 ] " to diastereomeric alkenes such as fumaric and maleic add salts lead to a cr-alkylcobalt by stereospecific cis addition of Co and H to the double bond . The overall reduction is not stereospecific. (r-Alkylcobalt bond formation proceeds by either a concerted addition or a rapid collapse of a radical cage. 

The Bronsted theory states that the acid/base character of a compound depends on its reaction partner and is therefore not an absolute. An indication that transition metal compounds can act as bases is provided by the long-known protonation reactions of transition metal complexes, generally of low oxidation state. An example is cobalt carbonyl hydride, the true catalyst in many carbonylation reactions ... 

In the last reaction, the presence of some carrier such as cysteine or cyanide is essential. Apparently, the carrier forms an intermediate complex containing carbon monoxide and cobalt, which reacts further to yield the salt of the carbonyl hydride and to regenerate the carrier. 

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