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Decarboxylative-coupling of allyl acetate catalyzed by group 10 organometallics, [(phen)M(CH3)]+

Citation

Woolley, M and Ariafard, A and Khairallah, GN and Kwan, KH-Y and Donnelly, PS and White, JM and Canty, AJ and Yates, BF and O'Hair, RAJ, Decarboxylative-coupling of allyl acetate catalyzed by group 10 organometallics, [(phen)M(CH3)]+, The Journal of Organic Chemistry, 79, (24) pp. 12056-12069. ISSN 0022-3263 (2014) [Refereed Article]

Copyright Statement

Copyright 2014 American Chemical Society

DOI: doi:10.1021/jo501886w

Abstract

Gas-phase carbon–carbon bond forming reactions, catalyzed by group 10 metal acetate cations [(phen)M(O2CCH3)]+ (where M = Ni, Pd or Pt) formed via electrospray ionization of metal acetate complexes [(phen)M(O2CCH3)2], were examined using an ion trap mass spectrometer and density functional theory (DFT) calculations. In step 1 of the catalytic cycle, collision induced dissociation (CID) of [(phen)M(O2CCH3)]+ yields the organometallic complex, [(phen)M(CH3)]+, via decarboxylation. [(phen)M(CH3)]+ reacts with allyl acetate via three competing reactions, with reactivity orders (% reaction efficiencies) established via kinetic modeling. In step 2a, allylic alkylation occurs to give 1-butene and reform metal acetate, [(phen)M(O2CCH3)]+, with Ni (36%) > Pd (28%) > Pt (2%). Adduct formation, [(phen)M(C6H11O2)]+, occurs with Pt (24%) > Pd (21%) > Ni(11%). The major losses upon CID on the adduct, [(phen)M(C6H11O2)]+, are 1-butene for M = Ni and Pd and methane for Pt. Loss of methane only occurs for Pt (10%) to give [(phen)Pt(C5H7O2)]+. The sequences of steps 1 and 2a close a catalytic cycle for decarboxylative carbon–carbon bond coupling. DFT calculations suggest that carbon–carbon bond formation occurs via alkene insertion as the initial step for all three metals, without involving higher oxidation states for the metal centers.

Item Details

Item Type:Refereed Article
Keywords:organopalladium, mass specrometry, homogeneous catalysis, DFT
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)
Author:Yates, BF (Professor Brian Yates)
ID Code:97547
Year Published:2014
Web of Science® Times Cited:7
Deposited By:Chemistry
Deposited On:2014-12-22
Last Modified:2015-04-28
Downloads:0

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