Organometallic compounds with oxygen

For a monograph, sec Brilkina Shushunov Reactions of Organometallic Compounds with Oxygen and Peroxides, CRC Press Boca Raton, FL, 1969. For a review, sec Wardcll Paterson, in Hartley Palai, Ref. I. vol. 2, 1985 pp. 219-338. pp. 311-316. 

Brilkina T.G, Shushunov V.A, Reactions of Organometallic Compounds with Oxygen and Peroxides, Nauka, Moscow, 1966... 

A131. T. G. Brilkina and V. A. Shushunov, Reactions of Organometallic Compounds with Oxygen and Peroxides. Iliffe Books, London, 1969. 234 pp. A translation of "Reaktsii metalloorganicheskikh soedinenii s kislorodom i perekisyami, Nauka, Moscow, 1966. 

Berlin, L.E. (Tr. Nauch. Inst. Moscow 1958 49, cited in Brilkina, T.G. Shushunov, V.A., Reactions of Organometallic Compounds with Oxygen and Peroxides, Iliffe, London 1969, p. 158). 

There are many examples of organometallic compounds containing oxygen atoms as ligands an appreciable number of these resulted from reactions with O2. Early work has been reviewed by Bottomley and Sutin [ 17]. Thus we concentrate on more recent reports, and those of particular interest. 

Few detailed mechanistic studies of reactions of organolithium reagents are known, apparently because of the high specific rate constants exhibited by most of these processes, coupled with the sensitivity of these organometallic compounds toward oxygen and water. Nevertheless the last several years have afforded much data which indicate the direction that research in reaction mechanisms in this area, as well as in others, is taking or should take. Specifically, they first involve the problems of structure and the effect of solvent on structure 1-14). This area has been reviewed by Brown (i). 

The known organometallic compounds with bonds between the rare earth metals and oxygen are shown in table 35. 

By coincidence, the oxygen problem is related to our present question. In the late 18th century, molecular oxygen (02) was a revolutionary discovery for chemists because of its involvement in oxidation, and because of the demonstration that a gas reacts chemically with liquids and solids. On the other hand, nitrogen gas (N2) is, as was already known at that time, inert towards most other chemicals, in particular towards all purely organic compounds (i. e., not organometallic compounds). 

Most other organometallic compounds also react with oxygen. Aryllithium reagents have been converted to phenols by treatment with oxygen. Trialkylboranes and alkyldichloroboranes (RBCI2) can be conveniently converted to hydroperoxides by... 

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