Metal-carbon bonds. Part 1.—The pyrolyses of dimethyl mercury and dimethyl cadmium

Price, S. J. W.; Trotman‐Dickenson, A. F.

doi:10.1039/tf9575300939

Cited by 36 publications

(9 citation statements)

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“…3. The falloff with increasing pressure is similar to that previously observed in similar studies with trimethylgalliun~, trimethylindium, and other metallic allcyls (1,2,7,8,9).…”

Section: Results a N D Discussionsupporting

confidence: 76%

The Pyrolysis of Trimethylthallium

Jacko¹,

Price²

1965

Can. J. Chem.

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T h e pyrolysis of trimethylthallium has been studied in a toluene carrier flow system from 458 to 591 O I < using total pressures from 5.6 to 33.0 mm. The progress of the reaction was followed by measuring the amount of methane, ethane, ethylene, and ethylbenzene formed and, in 21 runs, by direct thallium analysis. All preparative and kinetic work was carried out in total darkness where possible. A shielded 10 W lamp was used when some illumination was necessary.The decomposition is approximately 80% heterogeneous in an unconditioned vessel and 1 4 2 7 % heterogeneous in a vessel pretreated with hot 50% H F for 10 min. The reaction proceeds by the simple consecutive release of three methyl radicals. The rate constant depends only slightly on the total pressure in the system so that the activation energy of the homogeneous process, 27.4 kcal/mole, may be equated to D[(CH3)zTI-CH3].

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“…3. The falloff with increasing pressure is similar to that previously observed in similar studies with trimethylgalliun~, trimethylindium, and other metallic allcyls (1,2,7,8,9).…”

Section: Results a N D Discussionsupporting

confidence: 76%

The Pyrolysis of Trimethylthallium

Jacko¹,

Price²

1965

Can. J. Chem.

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“…It had been stored under its own vapor pressure at room temperature. Vapor pressure measurements gave log,, Plmm = 7.61 -1728/T(20 to 40 "C) in agreement with previous results (9,10). The Raman spectrum was checked using a Spectra-Physics model 700 Raman Spectrometer equipped with a He-Ne gas laser.…”

Section: Methodssupporting

confidence: 80%

Determination of Conditions for the Suppression of CH₃ + Sb(CH₃)₂→Sb(CH₃)₃ and Evaluation of D[(CH₃)₂Sb—CH₃]

Price¹,

Richard²

1972

Can. J. Chem.

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The pyrolysis of trimethylantimony has been studied in a toluene carrier flow system over the temperature range 690-803 K (total pressures 3.6-173.4 mm, contact times 1.0-13.5 s, decomposition 3.9-89.5%). The progress of the reaction was followed by measuring the amount of methane, ethane, and ethylbenzene formed. In 23 runs the undecomposed alkyl was also determined. The quantity found was in agreement with that expected from the product analysis if three methyl radicals are released for each molecule undergoing reaction. No heterogeneous reaction was detected.Deuterium labeling led to the conclusion that regeneration of the parent alkyl occurred during the course of the decomposition. This regeneration reaction was effectively eliminated by working at toluene pressures above 150 mm. Least squares analysis of the results obtained under conditions where regeneration should not be important given log,, k1s-I = 15.33 -(55 900 + I 000)/2.3RT The activation energy should be a good approximation to D[(CH,),S&CH,]. Significant decomposition of SbCH, probably does not occur. It seems most likely that free Sb is formed via 2Sb(CH3) + Sb(CH,), + Sb.La pyrolyse du trimtthylantimoine a ete etudiie dans un systeme courant porteur de toluene sur la gamme de temperature de 690-803 "K (pressions totales 3.6-173.4 mm, temps de contact 1.0-13.5 s, decomposition 3.9-89.5%). La progression de la reaction est suivie en mesurant la quantite de methane, d'ethane et d'ethylbenzene formee. Dans 23 essais, le produit alkyle non decompose a ete tgalement determine. La quantitt trouvee etait en accord avec celle attendue Q partir de I'analyse du produit dans le cas ou les trois radicaux methyle sont liberts pour chaque molecule qui subit des changements. Aucune reaction hethogene n'a ete detectee.Le marquage au deuterium amene Q la conclusion que la regeneration du groupe alkyle d'origine se produit durant le temps de la decomposition. Cette reaction de regeneration a ete completement tlimine en travaillant B des pressions de toluene superieures Q 150 mm. L'analyse des resultats par la methode des moindres carres dans des conditions ou la regeneration ne serait pas importante, a donne: log,, k1s-l = 15.33 -(55 900 + 1 000)/2.3RT

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“…moles Cd (CH3) 2 A blank correction of 3 X lop5 mole of methyl radicals was subtracted to allow for decomposition that occurred in the alkyl injection system.…”

Section: Resultsmentioning

confidence: 99%

“…Three previous investigations of the pyrolysis of CdMe2 have been reported (1,2,3). In the first investigation a marked surface reaction was noted but no attempt was made to isolate the homogeneous components of the reaction (1).…”

Section: Introductionmentioning

confidence: 99%