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Synthesis and isomerisation of two metallated N,O-complexes of ruthenium: Models for the Murai reaction


Reference:

Jazzar, R. F. R., Varrone, M., Burrows, A. D., Macgregor, S. A., Mahon, M. F. and Whittlesey, M. K., 2006. Synthesis and isomerisation of two metallated N,O-complexes of ruthenium: Models for the Murai reaction. Inorganica Chimica Acta, 359 (3), pp. 815-820.

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Abstract

Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh3)2(CO)(NC4H3C(O)CH3)H] {cis-N,H (1) and trans-N,H (2)} were prepd. as models for catalytic intermediates in the Murai reaction. Complex 2 isomerizes to 1 upon heating via a dissociative pathway (Delta H .dbldag. = 195 +- 41 kJ mol-1; Delta S .dbldag. = 232 +- 62 J mol-1 K-1); the mechanism of this process was modeled using d. functional calcns. Complex 2 displays moderate catalytic activity for the Murai coupling of 2'-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions.

Details

Item Type Articles
CreatorsJazzar, R. F. R., Varrone, M., Burrows, A. D., Macgregor, S. A., Mahon, M. F. and Whittlesey, M. K.
Uncontrolled Keywordsmolecular structure (of isomeric ruthenium(ii) n, o-coordinated acetylpyrrolyl hydrido carbonyl bis(phosphine) complex related to murai coupling catalysts), o-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complexes as models for catalytic intermediates in murai coupling reaction), o-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complexes), crystal structure ruthenium acetylpyrrolyl hydride carbonyl phosphine isomer, o-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complex isomers as models for catalytic intermediates in murai coupling reaction), transition state structure (in isomerization of ruthenium(ii) n, ruthenium acetylpyrrolyl hydride carbonyl phosphine complex prepn structure isomerization, isomerization (of ruthenium(ii) n, isomerization ruthenium acetylpyrrolyl hydride carbonyl phosphine complex thermodn, isomerization enthalpy (of isomeric ruthenium(ii) n, activation entropy (for isomerization of isomeric ruthenium(ii) n, crystal structure, murai coupling catalyst intermediate ruthenium acetylpyrrolyl hydride carbonyl phosphine, coupling reaction catalysts (murai, prepn. of ruthenium(ii) n
DepartmentsFaculty of Science > Chemistry
RefereedYes
StatusPublished
ID Code4697

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