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Gas-phase and computational study of identical nickel- and palladium-mediated organic transformations where mechanisms proceeding via MII or MIV oxidation states are determined by ancillary ligands

Citation

Vikse, KL and Khairallah, GN and Ariafard, A and Canty, AJ and O'Hair, RAJ, Gas-phase and computational study of identical nickel- and palladium-mediated organic transformations where mechanisms proceeding via MII or MIV oxidation states are determined by ancillary ligands, Journal of the American Chemical Society, 137, (42) pp. 13588-13593. ISSN 0002-7863 (2015) [Refereed Article]

Copyright Statement

Copyright 2015 American Chemical Society

DOI: doi:10.1021/jacs.5b08044

Abstract

Gas-phase studies utilizing ion–molecule reactions, supported by computational chemistry, demonstrate that the reaction of the enolate complexes [(CH2CO2C,O)M(CH3)] (M = Ni (5a), Pd (5b)) with allyl acetate proceed via oxidative addition to give MIV species [(CH2CO2C,O)M(CH3)(η1-CH2—CH═CH2)(O2CCH3O,O′)] (6) that reductively eliminate 1-butene, to form [(CH2CO2C,O)M(O2CCH3O,O′)] (4). The mechanism contrasts with the MII-mediated pathway for the analogous reaction of [(phen)M(CH3)]+ (1a,b) (phen = 1,10-phenanthroline). The different pathways demonstrate the marked effect of electron-rich metal centers in enabling higher oxidation state pathways. Due to the presence of two alkyl groups, the metal-occupied d orbitals (particularly dz2) in 5 are considerably destabilized, resulting in more facile oxidative addition; the electron transfer from dz2 to the C═C π* orbital is the key interaction leading to oxidative addition of allyl acetate to MII. Upon collision-induced dissociation, 4 undergoes decarboxylation to form 5. These results provide support for the current exploration of roles for NiIV and PdIV in organic synthesis.

Item Details

Item Type:Refereed Article
Keywords:palladium(I), nickel(IV), organonickel, organopalladium, computational chemistry, mas spectrometry
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Ariafard, A (Associate Professor Alireza Ariafard)
Author:Canty, AJ (Professor Allan Canty)
ID Code:104952
Year Published:2015
Web of Science® Times Cited:1
Deposited By:Chemistry
Deposited On:2015-11-30
Last Modified:2017-10-25
Downloads:0

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