Reactions of (1-3-.eta.-vinylcarbene)tricarbonyliron complexes with carbon monoxide or tertiary phosphines. "Insertion" of carbon monoxide into a carbon-metal double bond and reactivities of the formed tricarbonyl(.eta.3:.eta.1-allylacyl)irons

Ozone cleavage of 12 substituted vinyl chlorides (1) in methanol occurred such that the chlorinated moiety of the double bond afforded the carbonyl fragment (i.e. acyl chloride) and the nonchlorinated moiety afforded the carbonyl oxide fragment. All of these fragments underwent secondary reactions: formyl chloride gave carbon monoxide and hydrogen chloride; all other acyl chlorides yielded the corresponding methyl esters. The carbonyl oxides were converted into the corresponding methoxy hydroperoxides. Under the influence of hydrochloric acid unsubstituted and monosubstituted methoxy hydroperoxides were dehydrated to form the corresponding methyl esters, whereas the disubstituted methoxy hydroperoxide of acetone produced the cyclic trimeric peroxide of acetone.

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Reactions of triply bonded dimetal compounds. Reversible addition of carbon monoxide to a hexakis(alkoxy)dimolybdenum compound. A molecule with a carbonyl-bridged metal-metal double bond

Journal of the American Chemical Society ◽

10.1021/ja00475a060 ◽

1978 ◽

Vol 100 (7) ◽

pp. 2256-2257 ◽

Cited By ~ 21

Author(s):

Malcolm H. Chisholm ◽

Raymond L. Kelly ◽

F. Albert Cotton ◽

Michael W. Extine

Keyword(s):

Carbon Monoxide ◽

Double Bond ◽

Compound A ◽

Reversible Addition ◽

Metal Metal

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Divergent Reactivity of CO2 and CO and Related Substrates at the Nickel Carbon Double Bond of (PCcarbeneP)Ni(II) Pincer Complexes

10.26434/chemrxiv.6686585.v1 ◽

2018 ◽

Author(s):

Etienne A. LaPierre ◽

Warren Piers ◽

Chris Gendy

Keyword(s):

Carbon Dioxide ◽

Carbon Monoxide ◽

Double Bond ◽

Transfer Reactions ◽

Pincer Complexes ◽

Pincer Ligand ◽

Group Transfer ◽

Ligand Structure ◽

Carbon Double Bond

The addition of carbon monoxide (CO), carbon dioxide (CO2) and isoelectronic isocyanide and isocyanates to the nickel carbene bond in PCcarbeneP pincer complexes is reported. For CO and CNR, irreversible group transfer reactions are observed, while for CO2, a reversible 2+2 addition to the carbene moiety occurs. The course of the CO and CO2 reactions are strongly affected by the nature of the PCcarbeneP pincer ligand framework and a new more rigid ligand based on a 10,10-dimethyl-9,10-dihydroanthracene core was designed in order to study these reactions, illustrating the profound effect of small changes in ligand structure on reaction outcomes.

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The initial stages of the dehydrogenation and isomeric change of allyl alcohol

Proceedings of the Royal Society of London. Series A, Containing Papers of a Mathematical and Physical Character ◽

10.1098/rspa.1926.0152 ◽

1926 ◽

Vol 113 (764) ◽

pp. 254-258 ◽

Cited By ~ 6

Keyword(s):

Carbon Monoxide ◽

Elevated Temperature ◽

Double Bond ◽

Allyl Alcohol ◽

Catalytic Decomposition ◽

Unsaturated Alcohol ◽

Reaction Products ◽

Brass Tube ◽

Saturated Aldehyde ◽

Lower Temperature

The catalytic decomposition of allyl alcohol has been studied by Ipatiev, who passed the vapour through a brass tube filled with brass filings maintained at 600° C. He found hydrogen and acrolein, some propylene and carbon monoxide, with a little divinyl in the reaction products, showing that under these conditions of elevated temperature very little hydrogenation of the double bond of the unsaturated alcohol takes place. Sabatier and Senderensf used reduced copper as catalyst at temperatures varying from 180-300° C. They found that a yield of over 50 per cent, of propionaldehyde could be obtained and only a little acrolein and hydrogen. The lower temperature seems to favour the production of the saturated aldehyde. The observations of Moureu and Boismenu have shown that acrolein is very appreciably hydrogenated by copper at temperatures between 110 and 250° C. At 300° C. the destruction of the acrolein is very rapid. It is evident, therefore, that there are two reactions to be followed in the initial stages of the dehydrogenation of allyl alcohol by copper CH 2 ═ CH . CH 2 OH— ↗CH 3 . CH 2 . CHO ↘ CH 2 = CH. CHO + H 2 A detailed study was made of these two reactions to attempt to throw light on the state of the adsorbed molecules, and to consider in detail the mechanism of the two reactions and the connection between them.

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