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Title: Organometallic nucleophiles and Pd: What Makes ZnMe2 Different? Is Au like Zn?
Authors: Pozo, Juan del
Gioria, Estefanía
Casares González, Juan Ángel
Álvarez, Rosana
Espinet Rubio, Pablo
Issue Date: 2015
Publisher: American Chemical Society
Description: Producción Científica
Citation: Organometallics, 2015, 34 (13), pp 3120–3128
Abstract: The 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.
Keywords: Chemistry
ISSN: ISSN: 0276-7333
Peer Review: SI
DOI: 10.1021/acs.organomet.5b00329
Sponsor: 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)
Language: eng
Rights: info:eu-repo/semantics/openAccess
Appears in Collections:CINQUIMA - Artículos de revista
DEP63 - Artículos de revista

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