Organometallic nucleophiles and Pd: What Makes ZnMe2 Different? Is Au like Zn?

Producción Científica

Bibliographic Details
Authors: Pozo, Juan del, Gioria, Estefania, Casares González, Juan Ángel, Álvarez, Rosana, Espinet Rubio, Pablo
Format: article
Publication Date:2015
Country:España
Institution:Universidad de Valladolid
Repository:UVaDOC. Repositorio Documental de la Universidad de Valladolid
OAI Identifier:oai:uvadoc.uva.es:10324/21739
Online Access:https://doi.org/10.1021/acs.organomet.5b00329
http://uvadoc.uva.es/handle/10324/21739
Access Level:Open access
Keyword:Chemistry
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spelling Organometallic nucleophiles and Pd: What Makes ZnMe2 Different? Is Au like Zn?Pozo, Juan delGioria, EstefaniaCasares González, Juan ÁngelÁlvarez, RosanaEspinet Rubio, PabloChemistryProducción CientíficaThe cis/trans isomerization of [PdMeAr(PR3)2] complexes (Ar = C6F5, C6F3Cl2) can take place spontaneously (via dissociation and topomerization, studied experimentally) or catalyzed by ZnMe2. The later mechanism, studied by DFT methods, involves methyl exchange between Pd and Zn. The study of this catalyzed isomerization shows that, in contrast with the typical acidic behavior of Zn in ZnMeCl, Zn in ZnMe2 (or, more exactly, the ZnMe bond) behaves as a strong basic center, able to attack the relatively high in energy acceptor orbital at Pd in fairly electron rich Pd complexes such as [PdArMeL2] or [PdMe2L2]. This makes the two reagents very different in Negishi couplings. The catalyzed isomerization occurs via transmetalation, thus both processes are connected. A comparison of the Pd/Zn intermediates and transition states with those found previously for Pd/Au transmetalations reveals very similar structures with intermetallic distances in the order of or noticeably shorter than the sum of the vdW radii, regardless of the nature of the metal (metallophilic Au or non metallophillic Zn). These short distances are associated to the involvement of the metals in 3c2e electron deficient bonds during R group transmetalation. In this respect there is a remarkable similarity with the structurally known behavior of main-group electron-deficient compound, which supports a unified view of the transmetalation processes.Ministerio de Economía, Industria y Competitividad (CTQ2013-48406-P)Ministerio de Economía, Industria y Competitividad (CTQ2012-37734)Junta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA256U13)Centro de Supercomputación de Galicia (CESGA, ICTS240-2013 and ICTS257-2014)American Chemical Society2015info:eu-repo/semantics/articleapplication/pdfhttps://doi.org/10.1021/acs.organomet.5b00329http://uvadoc.uva.es/handle/10324/21739reponame:UVaDOC. Repositorio Documental de la Universidad de Valladolidinstname:Universidad de ValladolidInglésinfo:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/4.0/oai:uvadoc.uva.es:10324/217392026-06-13T12:44:47Z
dc.title.none.fl_str_mv Organometallic nucleophiles and Pd: What Makes ZnMe2 Different? Is Au like Zn?
title Organometallic nucleophiles and Pd: What Makes ZnMe2 Different? Is Au like Zn?
spellingShingle Organometallic nucleophiles and Pd: What Makes ZnMe2 Different? Is Au like Zn?
Pozo, Juan del
Chemistry
title_short Organometallic nucleophiles and Pd: What Makes ZnMe2 Different? Is Au like Zn?
title_full Organometallic nucleophiles and Pd: What Makes ZnMe2 Different? Is Au like Zn?
title_fullStr Organometallic nucleophiles and Pd: What Makes ZnMe2 Different? Is Au like Zn?
title_full_unstemmed Organometallic nucleophiles and Pd: What Makes ZnMe2 Different? Is Au like Zn?
title_sort Organometallic nucleophiles and Pd: What Makes ZnMe2 Different? Is Au like Zn?
dc.creator.none.fl_str_mv Pozo, Juan del
Gioria, Estefania
Casares González, Juan Ángel
Álvarez, Rosana
Espinet Rubio, Pablo
author Pozo, Juan del
author_facet Pozo, Juan del
Gioria, Estefania
Casares González, Juan Ángel
Álvarez, Rosana
Espinet Rubio, Pablo
author_role author
author2 Gioria, Estefania
Casares González, Juan Ángel
Álvarez, Rosana
Espinet Rubio, Pablo
author2_role author
author
author
author
dc.subject.none.fl_str_mv Chemistry
topic Chemistry
description Producción Científica
publishDate 2015
dc.date.none.fl_str_mv 2015
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://doi.org/10.1021/acs.organomet.5b00329
http://uvadoc.uva.es/handle/10324/21739
url https://doi.org/10.1021/acs.organomet.5b00329
http://uvadoc.uva.es/handle/10324/21739
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:UVaDOC. Repositorio Documental de la Universidad de Valladolid
instname:Universidad de Valladolid
instname_str Universidad de Valladolid
reponame_str UVaDOC. Repositorio Documental de la Universidad de Valladolid
collection UVaDOC. Repositorio Documental de la Universidad de Valladolid
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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