MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE

The catalytic activity of systems of type [RuH(CO)(N-N)(PR3)2]+ was evaluated in the hydroformylation reaction of 1-hexene. The observed activity is explained through a reaction mechanism on the basis of the quantum theory. The mechanism included total energy calculations for each of the intermediar...

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Autores principales:	MOYA,SERGIO A, YÁÑEZ-S,MAURICIO, PÉREZ,CATALINA, LÓPEZ,ROSA, ZÚÑIGA,CÉSAR, CÁRDENAS-JIRÓN,GLORIA
Lenguaje:	English
Publicado:	Sociedad Chilena de Química 2016
Materias:	DFT hydroformylation ruthenium homogeneous catalysis
Acceso en línea:	http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072016000400026
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spelling	oai:scielo:S0717-970720160004000262017-01-16MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENEMOYA,SERGIO AYÁÑEZ-S,MAURICIOPÉREZ,CATALINALÓPEZ,ROSAZÚÑIGA,CÉSARCÁRDENAS-JIRÓN,GLORIA DFT hydroformylation ruthenium homogeneous catalysis The catalytic activity of systems of type [RuH(CO)(N-N)(PR3)2]+ was evaluated in the hydroformylation reaction of 1-hexene. The observed activity is explained through a reaction mechanism on the basis of the quantum theory. The mechanism included total energy calculations for each of the intermediaries of the elemental steps considered in the catalytic cycle. The deactivation of the catalyst precursors takes place via dissociation of the polypyridine ligand and the subsequent formation of thermodynamically stable species, such as RuH(CO)3(PPh3)2 and RuH3(CO)(PPh3)2, which interrupt the catalytic cycle. In addition, the theoretical study allows to explain the observed regioselectivity which is defined in two steps: (a) the hydride migration reaction with an anti-Markovnikov orientation to produce the alkyl-linear-complex (3.1a), which is more stable by 19.4 kJ/mol than the Markovnikov orientation (alkyl-branched-complex) (3.1b); (b) the carbon monoxide insertion step generates the carbonyl alkyl-linear specie (4.1a) which is more stable by 9.5 kJ/mol than the alternative species (4.1b), determining the preferred formation of heptanal in the hydroformylation of 1-hexene.info:eu-repo/semantics/openAccessSociedad Chilena de QuímicaJournal of the Chilean Chemical Society v.61 n.4 20162016-12-01text/htmlhttp://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072016000400026en10.4067/S0717-97072016000400026
institution	Scielo Chile
collection	Scielo Chile
language	English
topic	DFT hydroformylation ruthenium homogeneous catalysis
spellingShingle	DFT hydroformylation ruthenium homogeneous catalysis MOYA,SERGIO A YÁÑEZ-S,MAURICIO PÉREZ,CATALINA LÓPEZ,ROSA ZÚÑIGA,CÉSAR CÁRDENAS-JIRÓN,GLORIA MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE
description	The catalytic activity of systems of type [RuH(CO)(N-N)(PR3)2]+ was evaluated in the hydroformylation reaction of 1-hexene. The observed activity is explained through a reaction mechanism on the basis of the quantum theory. The mechanism included total energy calculations for each of the intermediaries of the elemental steps considered in the catalytic cycle. The deactivation of the catalyst precursors takes place via dissociation of the polypyridine ligand and the subsequent formation of thermodynamically stable species, such as RuH(CO)3(PPh3)2 and RuH3(CO)(PPh3)2, which interrupt the catalytic cycle. In addition, the theoretical study allows to explain the observed regioselectivity which is defined in two steps: (a) the hydride migration reaction with an anti-Markovnikov orientation to produce the alkyl-linear-complex (3.1a), which is more stable by 19.4 kJ/mol than the Markovnikov orientation (alkyl-branched-complex) (3.1b); (b) the carbon monoxide insertion step generates the carbonyl alkyl-linear specie (4.1a) which is more stable by 9.5 kJ/mol than the alternative species (4.1b), determining the preferred formation of heptanal in the hydroformylation of 1-hexene.
author	MOYA,SERGIO A YÁÑEZ-S,MAURICIO PÉREZ,CATALINA LÓPEZ,ROSA ZÚÑIGA,CÉSAR CÁRDENAS-JIRÓN,GLORIA
author_facet	MOYA,SERGIO A YÁÑEZ-S,MAURICIO PÉREZ,CATALINA LÓPEZ,ROSA ZÚÑIGA,CÉSAR CÁRDENAS-JIRÓN,GLORIA
author_sort	MOYA,SERGIO A
title	MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE
title_short	MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE
title_full	MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE
title_fullStr	MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE
title_full_unstemmed	MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE
title_sort	mechanistic study of a ruthenium hydride complex of type [ruh(co)(n-n)(pr3)2]+ as catalyst precursor for the hydroformylation reaction of 1-hexene
publisher	Sociedad Chilena de Química
publishDate	2016
url	http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072016000400026
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MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE

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