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

Moya, Sergio A.; Yáñez, Mauricio; Pérez, Catalina; López, Rosa; Zúñiga, César; Cárdenas Jirón, Gloria

dc.creator	Moya, Sergio A.
dc.creator	Yáñez, Mauricio
dc.creator	Pérez, Catalina
dc.creator	López, Rosa
dc.creator	Zúñiga, César
dc.creator	Cárdenas Jirón, Gloria
dc.date	2016-12-10
dc.date.accessioned	2019-11-13T15:11:32Z
dc.date.available	2019-11-13T15:11:32Z
dc.identifier	http://www.jcchems.com/index.php/JCCHEMS/article/view/127
dc.identifier.uri	https://revistaschilenas.uchile.cl/handle/2250/112559
dc.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.	en-US
dc.format	application/pdf
dc.language	eng
dc.publisher	Sociedad Chilena de Química	en-US
dc.relation	http://www.jcchems.com/index.php/JCCHEMS/article/view/127/112
dc.rights	Copyright (c) 2017 Sergio A. Moya, Mauricio Yáñez, Catalina Pérez, Rosa López, César Zúñiga, Gloria Cárdenas Jirón	en-US
dc.rights	https://creativecommons.org/licenses/by-nc-sa/4.0	en-US
dc.source	Journal of the Chilean Chemical Society; Vol 61 No 4 (2016): Journal of the Chilean Chemical Society	en-US
dc.source	0717-9707
dc.source	0717-9324
dc.subject	DFT	en-US
dc.subject	Hydroformylation	en-US
dc.subject	Ruthenium	en-US
dc.subject	Homogeneous catalysis	en-US
dc.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	en-US
dc.type	info:eu-repo/semantics/article
dc.type	info:eu-repo/semantics/publishedVersion

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