Carbon dioxide reaction with allyl complexes

Lactones have also been prepared by the stoichiometric reaction of fj3-allylnickel complexes with carbon dioxide [Eq. (46)] (116). f 3-Allyl-nickelvinylacetate (38) has been suggested as an intermediate in this process. 

Butadiene, which is bound in a n -manner to iron, reacts stoichio-metrically with carbon dioxide to form an allyl carboxylato complex in yields up to 75 % [38]. This allyl complex shows a dynamic behaviour Presumably three isomeric structures exist in solution, two of them with a n"-allyl bonding (Figure 16). Subsequent reactions of the allyl carboxylato complexes yield carboxylic acids. Acidic hydrolysis in methanol at -30°C gives methyl-3-pentenoate and methyl-4-pentenoate in a ratio of 10 1. If the iron allyl complex reacts with further carbon dioxide at 90 C, a second insertion of CO2 into the Fe-C-bond occurs after hydrolysis with hydrochloric acid in methanol the Z- and E-dimethyl esters of 3-hexenedioic acid are formed. 

Codeposition of silver vapor with perfluoroalkyl iodides at -196 °C provides an alternative route to nonsolvated primary perfluoroalkylsilvers [272] Phosphine complexes of trifluaromethylsilver are formed from the reaction of trimethyl-phosphme, silver acetate, and bis(trifluoromethyl)cadmium glyme [755] The per-fluoroalkylsilver compounds react with halogens [270], carbon dioxide [274], allyl halides [270, 274], mineral acids and water [275], and nitrosyl chloride [276] to give the expected products Oxidation with dioxygen gives ketones [270] or acyl halides [270] Sulfur reacts via insertion of sulfur into the carbon-silver bond [270] (equation 188)... 

Reactions of the hydrido(hydroxo) complex 2 with several substrates were examined (Scheme 6-14) [6]. The reactions are fairly complicated and several different types of reachons are observed depending on the substrate. Methyl acrylate and small Lewis bases such as CO, P(OMe)3, BuNC coordinate to the five-coordinated complex 2 affording the corresponding six-coordinate complexes. In reactions with the unsaturated bonds in dimethylacetylenedicarboxylate, carbon dioxide, phenylisocyanate indications for the addition across the O-H bond but not across the Os-OH bond were obtained. In reactions with olefins such as methyl vinyl ketone or allyl alcohol, elimination of a water molecule was observed to afford a hydrido metalla-cyclic compound or a hydrido (ethyl) complex. No OH insertion product was obtained. 

Carbamoyl complexes from metal carbonyls and amines 5.8.2.12.4 Carbanions reactions with alkene complexes 5.8.2.3,4 metal carbonyls 5.8.2.S.5 Carbene complexes by alkene metathesis 5.8.2.3.11 formation 5.8.2.8.5 Carbides alkali metal formation 5.10.2.1 bonding 5.10.2 formation 5.10.2 industrial uses 5.10.2 interstitial formation 5.10.2 Carbometallacycle formation 5.S.2.2.2 Carbometallacycles from n-allyl complexes 5.S.2.3.9 Carbon reaction with alkali metals 5.10.2.1 Carbon dioxide complexes formation 5.8.2.14.1 Carbon monoxide displacement by alkenes 5.8.2.3.1 Carbonyl complexes by ligand exchange 5.8.2.12.2 from carbon monoxide 5.8.2.12.1, 5.8.2.12.2... 

Though carbon-nitrogen bond cleavage reaction is less explored, allylic C-N bond can be cleaved by low valent late transition metal complexes. Treatment of (/x-dinitrogen or carbon dioxide)nickel(O) complexes with allylammonium... 

The reaction between 1,3-dienes and carbon dioxide leads to the formation of carboxylato (ri -allyl)nickel(II) complexes, which may equilibrate with seven-membered ring nickelacycles in which the metal coordinates the allyl in a Ti -fashion (Eq. 5). ... 

Among the various allylic compounds, allylic carbonates are most reactive toward Pd(0) species. The reaction of an allylic carbonate with Pd(0) initially provides a 7r-allyl-palladium carbonate complex, which immediately loses carbon dioxide to form a tt-allylpalladium ethoxide complex irreversibly. Thus, their carbonylation proceeds under mild conditions, namely, at 50 °C under 1-20 atm of carbon monoxide (Scheme... 

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