The Redistribution Reaction. VII. Alkyl Compounds of Mercury, Tin, Silicon and Zinc

Calingaert, George; Soroos, Harold; Hnizda, Vincent

doi:10.1021/ja01862a032

Cited by 37 publications

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“…Nor froin the present findings would the system be expected t o be clean. One may expect the following reactions t o occur: Reaction [2] has been demonstrated in the present report (reaction [3] has been discovered, though not yet reported) from this laboratory. The equilibrium of reaction [4] will be strongly to the left, if RHgX is present only a s a slight contaminant of R2Hg.…”

Section: R-h~-r'mentioning

confidence: 50%

The Redistribution Reaction of Bis-Mercurials

French¹,

Inamoto²,

Wright³

1964

Can. J. Chem.

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The de~netalation of diorganosubstituted mercury con~pounds is catalyzed by peroxides. When organonlercuric salts are present this demetalation leads to formation of mercurous salt plus mercury. This latter combination has been found to be a catalyst for the redistribution reaction of bis-mercurials. I t is suggested that all previously reported catalysts for this reaction operate by formation of the mercurous salt -mercury combination. Equilibration studies with this co~nbinatioll a s catalyst indicate that random exchange is not general for the redistribution reaction of mercury compounds.The equilibration of organic substituent groups among mixtures of bis-organolead, organotin, and organomercurials has been summarized (1) by Calingaert, who coined the name "redistribution reaction" originally for the equilibration of tetraalkyllead compounds in which the substituents were homologous or structurally isomeric (2). He applied the name also to the simpler equilibration of bis-mercurials (3).Obviously these reactions are, a t most, "distributions"; the redundancy was unfortunate but a t least it accentuated Calingaert's discovery that the "redistribution" was statistically random and unrelated to the structure of the substituent groups. Also, he demonstrated t h a t the redistribution was catalyzed by metal halides and organometallic halides, including those related to the organometallic compounds that he was "redistributing".Despite the mass of evidence relating to the redistribution reaction and its catalysis, we have found that for bis-mercurials i t is quite erratic. For example, 4-cyclohexylmercuritoluene is recovered unchanged when it is treated in solvents such a s methanol, petroleum ether, benzene, or dioxane with 1-5 inole % of the recommended (3) catalysts: boron fluoride etherate, aluminum chloride, magnesium bromide hydrate, zinc chloride, and cyclohexylmercuric chloride a t room temperature. On the other hand, a moderately pure sample decomposes when heated without either solvent or any of the recommended catalysts, giving bis-4-tolylinercury. Likewise, for one operator, 2-butylmercuri-4-toluene in inethanol or petroleum ether has been heated under reflux for 15 h without alteration in presence of mercuric bromide or 2-butylmerc~iric bromide. For another, a methanol solution of the substance has reacted in 8 h under reflux without added catalyst to give a 42Yo yield of bis-4-tolylinercury and a 47Yo yield of bis-2-butylmercury. Similar anomalies have been found for benzylinercuriethane.Part of the reason for this lack of reliability has become evident during our attempts to isolate and preserve bis-cyclohexyln~ercury in a pure state for determination of its dielectric constant (4). T h e instability of this substance is apparent in its use (5) a s a catalyst in the hoinopolar polyn~erization of vinyl acetate. We find that the recently crystallized white substance turns grey within a n hour in air. If it is vacuum distilled immediately after crystallization, some decomposition occurs during t...

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Section: R-h~-r'mentioning

confidence: 50%

The Redistribution Reaction of Bis-Mercurials

French¹,

Inamoto²,

Wright³

1964

Can. J. Chem.

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“…Chem.. Anal. Ed., 20, 1034(1948. ( 19) H. Gilman, B. Hofferth, H. W. Melvin, Jr., and G. E. Dunn, This Journal, 72, 5767 (1950).…”

Section: Methodsmentioning

confidence: 99%

Cleavage Reactions of Some Organopolysilanes

Wittenberg¹,

George²,

Gilman³

1959

J. Am. Chem. Soc.

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“…105 Chlorosilanes rearrange similarly (equation 83) 106 but require more vigorous conditions, with the methylchlorosilanes more reluctant to randomise (equations 8 4 and 85). 105 Chlorosilanes rearrange similarly (equation 83) 106 but require more vigorous conditions, with the methylchlorosilanes more reluctant to randomise (equations 8 4 and 85).…”

Section: P R E P a R A T I O N Of Si-c Bonds 141981mentioning

confidence: 99%

Organosilanes

Armitage

1982

Comprehensive Organometallic Chemistry

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The Redistribution Reaction. VII. Alkyl Compounds of Mercury, Tin, Silicon and Zinc

Cited by 37 publications

References 0 publications

The Redistribution Reaction of Bis-Mercurials

The Redistribution Reaction of Bis-Mercurials

Cleavage Reactions of Some Organopolysilanes

Organosilanes

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