The Redistribution Reaction. V. R<sub>4</sub>Pb Compounds

Calingaert, George; Beatty, Harold A.; Soroos, Harold

doi:10.1021/ja01862a030

Cited by 36 publications

(12 citation statements)

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“…For example, in one run in which 72 moles of isopropylmagnesium chloride was allowed to react with 57 moles of t-amyl chloride, the yield of 2,3,3-trimethylpentane was only 21 percent. Credit is due Doctors Calingaert, Beatty, and Soroos [9] for the discovery of this improvement in technic, which they made in connection with a similar reaction .…”

Section: Aliphatic Hydrocarbonsmentioning

confidence: 98%

Preparation and physical properties of several aliphatic hydrocarbons and intermediates

Howard¹,

Mears²,

Fookson³

et al. 1947

J. RES. NATL. BUR. STAN.

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In t he co urse of a contin uin g investigation of the knock rat in gs of alip hatic hydrocarbons, pu re paraffin s and olefins have been prepared in quantities suffi cien t for en gin e teBts. Thi s reports describes the m eth ods of preparation a nd purification of t hree pcntancs. four hcxane , t hree heptanes, ro ur octanes, e igh t nonanes, seven decancs, fou r hexe nes, fi ve octenes, s ix nonenes, s ix dccencs, and a number of alcohoL, ketones, esters, and alky l hal ides . Most of t hese compounds were hi ghly pu r ified . Phys ical co nstants m casured include f rcez in g point, bo iling po in t, and its va ri ation w ith press ure, rcfractive index, a nd d ensity, and t hcir variations with temperat ure. **

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Section: Aliphatic Hydrocarbonsmentioning

confidence: 98%

Preparation and physical properties of several aliphatic hydrocarbons and intermediates

Howard¹,

Mears²,

Fookson³

et al. 1947

J. RES. NATL. BUR. STAN.

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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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“…The dismutation starting with [Et 3 PbB(CN) 3 ] − ( 1 Et ) in water is unprecedented and the selective accessibility of 2 Et , 3 Et , and 4 is unexpected, as well. Redistributions of tetraalkyl and aryllead(IV) compounds typically occur in the presence of Lewis acid catalysts and require high temperatures and result in complex mixtures of organyl lead(IV) compounds [45–47] . Most likely, the separation of PbEt 4 from the reaction mixture is the driving force for the dismutations yielding the tricyanoborylplumbate anions.…”

Section: Resultsmentioning

confidence: 99%

Dismutation of Tricyanoboryllead Compounds: The Homoleptic Tetrakis(tricyanoboryl)plumbate Tetraanion

et al. 2022

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A series of unprecedently air‐stable (tricyanoboryl)plumbate anions was obtained by the reaction of the boron‐centered nucleophile B(CN)32− with triorganyllead halides. Salts of the anions [R3PbB(CN)3]− (R=Ph, Et) were isolated and found to be stable in air at room temperature. In the case of Me3PbHal (Hal=Cl, Br), a mixture of the anions [Me4−nPb{B(CN)3}n]n− (n=1, 2) was obtained. The [Et3PbB(CN)3]− ion undergoes stepwise dismutation in aqueous solution to yield the plumbate anions [Et4−nPb{B(CN)3}n]n− (n=1–4) and PbEt4 as by‐product. The reaction rate increases with decreasing pH value of the aqueous solution or by bubbling O2 through the reaction mixture. Adjustment of the conditions allowed the selective formation and isolation of salts of all anions of the series [Et4−nPb{B(CN)3}n]n− (n=2–4) including the homoleptic tetraanion [Pb{B(CN)3}4]4−.

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The Redistribution Reaction. V. R₄Pb Compounds

Cited by 36 publications

References 0 publications

Preparation and physical properties of several aliphatic hydrocarbons and intermediates

Preparation and physical properties of several aliphatic hydrocarbons and intermediates

The Redistribution Reaction of Bis-Mercurials

Dismutation of Tricyanoboryllead Compounds: The Homoleptic Tetrakis(tricyanoboryl)plumbate Tetraanion

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The Redistribution Reaction. V. R4Pb Compounds

Cited by 36 publications

References 0 publications

Preparation and physical properties of several aliphatic hydrocarbons and intermediates

Preparation and physical properties of several aliphatic hydrocarbons and intermediates

The Redistribution Reaction of Bis-Mercurials

Dismutation of Tricyanoboryllead Compounds: The Homoleptic Tetrakis(tricyanoboryl)plumbate Tetraanion

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The Redistribution Reaction. V. R₄Pb Compounds