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Activation of C–H Bonds in Pt^+ + x CH_4 Reactions, where x = 1–4: Identification of the Platinum Dimethyl Cation

Wheeler, Oscar W. and Salem, Michelle and Gao, Amanda and Bakker, Joost M. and Armentrout, P. B. (2016) Activation of C–H Bonds in Pt^+ + x CH_4 Reactions, where x = 1–4: Identification of the Platinum Dimethyl Cation. Journal of Physical Chemistry A, 120 (31). pp. 6216-6227. ISSN 1089-5639. http://resolver.caltech.edu/CaltechAUTHORS:20160831-125445720

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Abstract

Activation of C–H bonds in the sequential reactions of Pt^+ + x(CH_4/CD_4), where x = 1–4, have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy and theoretical calculations. Pt^+ cations are formed by laser ablation and exposed to controlled amounts of CH_4/CD_4 leading to [Pt,xC,(4x-2)H/D]^+ dehydrogenation products. Irradiation of these products in the 400–2100 cm^(–1) range leads to CH_4/CD_4 loss from the x = 3 and 4 products, whereas PtCH_2^+/PtCD_2^+ products do not decompose at all, and x = 2 products dissociate only when formed from a higher order product. The structures of these complexes were explored theoretically at several levels of theory with three different basis sets. Comparison of the experimental and theoretical results indicate that the species formed have a Pt(CH_3)_2^+(CH_4)_(x-2)/Pt(CD_3)_2^+(CD_4)_(x-2) binding motif for x = 2–4. Thus, reaction of Pt^+ with methane occurs by C–H bond activation to form PtCH_2^+, which reacts with an additional methane molecule by C–H bond activation to form the platinum dimethyl cation. This proposed reaction mechanism is consistent with theoretical explorations of the potential energy surface for reactions of Pt^+ with one and two methane molecules.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1021/acs.jpca.6b05361DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acs.jpca.6b05361PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acs.jpca.6b05361PublisherSupporting Information
Alternate Title:Activation of C–H Bonds in Pt+ + x CH4 Reactions, where x = 1–4: Identification of the Platinum Dimethyl Cation
Additional Information:© 2016 American Chemical Society. Received: May 27, 2016; Revised: July 14, 2016; Published: July 20, 2016. We gratefully acknowledge the Stichting voor Fundamenteel Onderzoek der Materie (FOM) for the support of the FELIX Laboratory. Additional financial assistance was provided by the National Science Foundation, Grant Nos. CHE-1359769 and OISE-1357887. Finally, the Center for High Performance Computing (CHPC) at the University of Utah is acknowledged for their generous allocation of computing time. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Stichting voor Fundamenteel Onderzoek der Materie (FOM)UNSPECIFIED
NSFCHE-1359769
NSFOISE-1357887
Record Number:CaltechAUTHORS:20160831-125445720
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160831-125445720
Official Citation:Activation of C–H Bonds in Pt+ + x CH4 Reactions, where x = 1–4: Identification of the Platinum Dimethyl Cation Oscar W. Wheeler, Michelle Salem, Amanda Gao, Joost M. Bakker, and P. B. Armentrout The Journal of Physical Chemistry A 2016 120 (31), 6216-6227 DOI: 10.1021/acs.jpca.6b05361
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70074
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:31 Aug 2016 22:13
Last Modified:31 Aug 2016 22:13

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