Rate and equilibrium constants for Grignard reaction with alkoxysilanes and ketones

Ploom, Anu; Panov, Dmitri; Järv, Jaak; Tuulmets, Ants

doi:10.1016/j.jorganchem.2008.04.013

Cited by 4 publications

(9 citation statements)

References 12 publications

(21 reference statements)

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“…15 The method is based on understanding that the reaction proceeds through complexation of Grignard reagent with silane, which replaces the donor molecule bound at the magnesium center (Scheme 1). Subsequently, this complex rearranges to reaction products through a four-center transition state.…”

Section: Resultsmentioning

confidence: 99%

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Steric Parameters for Substituents Bound to Atoms of Silicon and Some Other Elements of the Third Period

Ploom

Tuulmets

Järv

2010

Phosphorus, Sulfur, and Silicon and the Related Elements

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The kinetics of a tetraethoxysilane reaction with n-butylmagnesium chloride, stoichiometrically monosolvated with isopropyl ether or with methyl tert-butyl ether, was studied in toluene. The pseudo-first-order rate constants determined at a great excess of Grignard reagent were used for separation of the appropriate equilibrium and rate constants. Equilibrium constants for five alkyl ether ligands at the magnesium center are in an excellent correlation with isosteric E S (Si) parameters. It was concluded that these constants should be applicable to all elements of the third period of the periodic table.

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Section: Resultsmentioning

confidence: 99%

“…The results are collected in Table I together with data obtained in our previous work. 15 According to Eq. (1), the equilibrium constants K should reflect the solvating ability of donors, the strongest of them shifting the equilibrium most to the left (see Scheme 1A).…”

Section: Resultsmentioning

confidence: 99%

Steric Parameters for Substituents Bound to Atoms of Silicon and Some Other Elements of the Third Period

Ploom

Tuulmets

Järv

2010

Phosphorus, Sulfur, and Silicon and the Related Elements

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“…7,8,15,16 It turned out that the well-known Taft equation (Equation 1) implicating terms for inductive (r*s*) and steric (dE S ) effects, differently of carbon compounds, cannot be applied for organosilicon compounds.…”

Section: Scheme 2 Mechanism Of the Grignard Reaction With Alkoxysilanesmentioning

confidence: 99%

“…In a previous paper 16 we have suggested that in dibutyl ether the equilibrium enthalpy DH o can be approximated with the value -48 kJ mol -1 . In Table 1 the corrected values for activation enthalpies, DH≠ corr , are presented.…”

Section: Equationmentioning

confidence: 99%

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Selectivity in the Grignard Reaction with Silanes

Tuulmets¹,

Ploom²,

Panov³

et al. 2010

Synlett

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Selectivity problems in preparation of silanes by Grignard reaction were discussed. A quantitative approach in terms of LFE analysis was proposed. It appeared that the inductive effect controls the rate of replacement more considerably than steric requirements in the transition state. Rates of subsequent substitution reactions at silicon decrease stepwise. Only with methylmagnesium halides are the subsequent steps faster.

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An insight into the C–S coupling mechanism of aryl Grignard reagents with aryl arenesulfonates

Eroğlu

2011

Reac Kinet Mech Cat

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The reaction rate and thermodynamic parameters in the reaction of phenylmagnesium bromide with phenyl tosylate in THF:toluene binary solvents and also in toluene were analyzed. The relative changes in the rate constants are strictly bound to changes in the equilibrium constant of complex formation between the sulfonate and the Grignard reagent by replacement of a donor THF molecule as well as the transfer rate of the carbanion to the sulfonate in the complex. These results provide another support for asynchronous S N a mechanism comprising a four-center transition state mechanism.

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Rate and equilibrium constants for Grignard reaction with alkoxysilanes and ketones

Cited by 4 publications

References 12 publications

Steric Parameters for Substituents Bound to Atoms of Silicon and Some Other Elements of the Third Period

Steric Parameters for Substituents Bound to Atoms of Silicon and Some Other Elements of the Third Period

Selectivity in the Grignard Reaction with Silanes

An insight into the C–S coupling mechanism of aryl Grignard reagents with aryl arenesulfonates

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