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Mechanism for Activation of Molecular Oxygen by cis- and trans-(Pyridine)_2Pd(OAc)H: Pd^0 versus Direct Insertion

Keith, Jason M. and Goddard, William A., III (2009) Mechanism for Activation of Molecular Oxygen by cis- and trans-(Pyridine)_2Pd(OAc)H: Pd^0 versus Direct Insertion. Journal of the American Chemical Society, 131 (4). pp. 1416-1425. ISSN 0002-7863.

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We use quantum mechanics to elucidate the mechanism for the reaction of molecular oxygen with palladium−hydride complexes, (pyridine)_2−PdII(H)OAc, in toluene, focusing specifically on the direct insertion pathway of dioxygen into the Pd−H bond and pathways proceeding through a Pd^0 intermediate for both cis and trans starting configurations as well as with the assistance of an extra HOAc molecule We report the potential energy surfaces and structures for each of these pathways. This is the first examination of these two mechanisms for both cis and trans isomers of a system employing two monodentate ligands. It is the first case of acid-assisted reductive elimination from a square planar Pd−H. The calculated mechanisms indicate that cis/trans isomerization is feasible and demonstrates that the Pd^0 pathway is favored for both cis (ΔΔH = 2.2 kcal/mol, ΔΔG = 9.3 kcal/mol) and trans cases (HOAc-assisted; ΔΔH = −2.6 kcal/mol, ΔΔG = 5.8 kcal/mol) demonstrating that the presence of two monodentate ligands changes the mechanism from that of the bidentate case.

Item Type:Article
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Keith, Jason M.0000-0002-5292-397X
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2009 American Chemical Society. Received May 29, 2008; Publication Date (Web): January 9, 2009. This research was partly funded by the DOE (DE-AC02-06CH11357 and DE-FG01-04ER04-20), NSF (CTS-0608889 and CMMI-072870), and Chevron Corporation. The facilities used were funded by Grants from ARO-DURIP and ONR-DURIP. Supporting Information: Tables of geometries, ZPE and solvent corrections, and absolute energies of intermediates, as well as geometries, ZPE and solvent corrections, absolute energies, and imaginary frequencies of transition states. This material is available free of charge via the Internet at
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-06CH11357
Department of Energy (DOE)DE-FG01-04ER04-20
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Issue or Number:4
Record Number:CaltechAUTHORS:20090828-124100444
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:15413
Deposited By: George Porter
Deposited On:09 Sep 2009 22:56
Last Modified:28 Feb 2020 00:00

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