Metal carbonyls alkene hydrogenation

However, the pathways for these reactions, particularly in the gas phase, have been only -.rtially characterized. In a wide variety of these reactions, coordinatively unsaturated, highly reactive metal carbonyls are produced [1-18]. The products of many of these photochemical reactions act as efficient catalysts. For example, Fe(C0)5 can be used to generate an efficient photocatalyst for alkene isomerization, hydrogenation, and hydrosilation reactions [19-23]. Turnover numbers as high as 3000 have been observed for Fe(C0)5 induced photocatalysis [22]. However, in many catalytically active systems, the active intermediate has not been definitively determined. Indeed, it is only recently that significant progress has been made in this area [20-23]. 

A variety of metal carbonyls upon sonication will catalyze the isomerization of 1-alkenes to the internal alkenes (J 8),(27). Initial turnover rates are as high as 100 mol alkene isonierized/mol of precatalyst/h, and represent rate enhancements of 1(P over thermal controls. The relative sonocatalytic and photocatalytic activities of these carbonyls are in general accord. A variety of terminal alkenes can be sonocatalytically isomerized. Increasing steric hindrance, however, significantly diminishes the observed rates. Alkenes without 6-hydrogens will not serve as substrates. 

A wide variety of five-membered zirconacydes 8 may be formed by the formal co-cycliza-tion of two 7i-components (3 and 6 alkene, alkyne, allene, imine, carbonyl, nitrile) on zir-conocene ( Cp2Zr ) (Scheme 3.2) [2,3,8]. The co-cydization takes place via the r 2-complex 5 of one of the components, which is usually formed by complexation of 3 with a zircono-cene equivalent (path a) ( Cp2Zr itself is probably too unstable to be a true intermediate) or by oxidation on the metal (cyclometallation/p-hydrogen elimination) (path b). Two additional routes to zirconocene r 2-complexes are by the reverse of the co-cyclization reaction (i. e. 8 reverting to 5 or 9 via 7), and by rearrangement of iminoacyl complexes (see Section... 

The photocatalytic hydrogenation of alkenes and dienes by Group 6 metal carbonyls has been investigated in LNG solvents [15]. Photolysis of trans-[M(C0)4(C2H4)2] (M = Cr, Mo, W) in liquid xenon doped with H2 leads to formation of mer-[M(CO)3(C2H4)2(q -H2)] and ds-[M(CO)4(C2H4)(q -H2)]. The q -H2 complexes for M = Cr and Mo are much less stable than those for M = W. The evidence supported -coordination of H2 rather than oxidative addition to give dihy-... 

Sterically hindered alkenes can be hydrogenated at —50°C using triflic acid and a hydride donor.483 In addition to Et3SiH, transition-metal carbonyl hydrides such as HM(CO)3Cp (M = W, Mo, Os) and HMn(CO)5 (M = Mn, Re) are suitable hydride donors. Alkenes that form tertiary carbocation on protonation are hydrogenated in high yields (90-100%), whereas yields for styrenes are lower (50-60%). Alkynes are converted to the corresponding saturated hydrocarbon by using HW(CO)3Cp in combination with triflic acid.484... 

It was discovered by Roelen in 1938 and is the oldest and largest volume catalytic reaction of alkenes, with the conversion of propylene to butyraldehyde being the mosi important. About 5 million tons of aldehydes and aldehyde derivatives (mostly alcohols) are produced annually making the process the most important industrial synthesis using a metal carbonyl complex as a catalyst. The name hydroformylation arises from the fact that in a formal sense a hydrogen atom and. formyl group are added across a double bond. The net result of the process is extension of (he carbon chain by one and introduction of oxygen into the molecule. 

Enzymatically active NADH has been selectively produced by visible light photoreduction of NAD using [Ru(bipy)3]S04 and [Ru(bipy)3]2(S04)3 as sensitizers and triethanolamine as electron donor (Wienkamp and Steckhan). There is continuing interest in the photogeneration of co-ordinatedly unsaturated species from metal carbonyls etc. which can act as or give rise to catalysts, e.g., for cis-trans isomerization and hydrogenation of alkenes. Ger-rity et al. have used chromium hexacarbonyl to make the first quantitative measurements of the distribution of atomic excited states produced by multiphoton dissociation of a metal carbonyl. The distribution of states turns out to be statistical rather than spin- or polarity-difierentiated. The use of perfluoromethylcyclohexane as solvent has enabled Simon and Peters to observe naked Cr(CO)s as a transient from Cr(CO)6. 

A central metal ion usually has a pronounced effect on the reactivity of a coordinated ligand at the coordinated atom or atoms. An important reaction of this type which has synthetic value is the reaction of alkenes and alkynes with hydrogen and carbon monoxide in the presence of a metal carbonyl. This is actually the catalytic process of hydroformylation and, although catalysis is beyond the scope of this work, it is nevertheless of interest from the standpoint of ligand reactivity. The reaction of ethylene with hydrogen and carbon monoxide in the presence of HCo(CO)4 as a catalyst is proposed to proceed (at least formally) through the steps shown 1U13) ... 

Alkene hydrogenation, alkane hydrogenolysis, and methanation of CO are used as test reactions for evaluating the catalytic activity of cluster-derived metal catalysts. Catalysts derived from noble metal carbonyl precursors such... 

The hydroformylation of alkenes is commonly run using soluble metal carbonyl complexes as catalysts but there are some reports of heterogeneously catalyzed reactions of olefins with hydrogen and carbon monoxide. Almost all of these are vapor phase reactions of ethylene or propylene with hydrogen and carbon monoxide catalyzed by rhodium, " 20 ruthenium,nickel, 22,123 cobalt, 23,124 and cobalt-molybdenum 23 catalysts as well as various sulfided metal catalysts. 23,125,126... 

Alkenes are converted to epoxides by oxidation with peroxy acids, and thereby they are protected with regard to certain chemical transformations. Alkaline hydrogen peroxide selectively attacks enone double bonds in the presence of other alkenes. The epoxides can be transformed back to alkenes by reduction-dehydration sequences or using triphenylphosphine, chromous salts, zinc, or sodium iodide and acetic acid. A more advantageous and fairly general method consists, however, of the treatment of epoxides with dimethyl diazomalonate in the presence of catalytic amounts of binuclear rhodium(II) car-boxylate salts. This deoxygenation proceeds under neutral conditions and without isomerization or cy-clopropanation of the liberated alkene (Scheme 97). Furthermore, epoxides can be converted to alkenes with the aid of various metal carbonyl complexes. Thus, they may be nucleophilically opened with... 

Alkene hydrogenation with transition metal carbonyl clusters in ILs has been studied using high-pressure NMR by Dyson and Laurenczy [65]. The clusters showed increased stability in the IL and reactions were up to 3.6-fold faster than in conventional solvents. 

The metal complexes most often studied as polymer-bound catalysts have been Rh(I) complexes, such as analogues of Wilkinson s complex. The catalytic activity of a bound metal complex is nearly the same as that of the soluble analogue. Rhodium complexes are active for alkene hydrogenation, alkene hydroformylation, and, in the presence of CH3I cocatalyst, methanol carbonylation, etc. Polymer supports thus allow the chemistry of homogeneous catalysis to take place with the benefits of an insoluble, easily separated catalyst . ... 

---