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Mechanism and Energetics for Dehydrogenation of Methane by Gaseous Iridium Ions

Perry, Jason K. and Ohanessian, Gilles and Goddard, William A., III (1994) Mechanism and Energetics for Dehydrogenation of Methane by Gaseous Iridium Ions. Organometallics, 13 (5). pp. 1870-1877. ISSN 0276-7333.

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Ir^+ has been observed as the most efficient transition-metal ion for dehydrogenation of CH_4 in the gas phase. We carried out theoretical studies of the complete reaction profile for this process and find three salient factors responsible for the high reactivity: (i) the ability of Ir^+ to change spin easily, (ii) the strength of the Ir-C and Ir-H bonds, and (iii) the ability of Ir^+ to form up to four covalent bonds. We show that among transition-metal ions Ir^+ is unique in best possessing all three characteristics. The combination of these factors leads to a global minimum for the singlet Ir(H)_2(CH_2)^+ structure, which plays an important role in the activation. On the basis of these results, we suggest solution-phase analogues that may also activate CH_4.

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Goddard, William A., III0000-0003-0097-5716
Additional Information:© 1994 American Chemical Society. Received July 1, 1993. We wish to thank Professor J. L. Beauchamp for pointing out the special property of Ir^+ for forming IrCH_2^+ from CH_4. We also thank Dr. K. K. Irikura and Mr. E. P. Bierwagen for helpful discussions. J.K.P. acknowledges a graduate fellowship from BP America (Dr. Jim Burrington). This research was supported by the NSF (Grant No. CH91-100284). We also want to thank the NSF-Pittsburgh Supercomputing Center for a Cray allocation. The facilities of the MSC used in these studies are supported by the NSF-GCAG, DOE-AICD, Allied-Signal, Asahi Chemical, Asahi Glass, BF Goodrich, BP America, Chevron, Teijin Ltd., Vestar, Xerox, Hughes, and the Beckman Institute.
Funding AgencyGrant Number
NSFCHE 91-100284
Department of Energy (DOE)UNSPECIFIED
Hughes Research LaboratoriesUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Issue or Number:5
Record Number:CaltechAUTHORS:20180521-131822964
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Official Citation:Mechanism and Energetics for Dehydrogenation of Methane by Gaseous Iridium Ions Jason K. Perry, Gilles Ohanessian, and William A. Goddard III Organometallics 1994 13 (5), 1870-1877 DOI: 10.1021/om00017a050
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86506
Deposited By: George Porter
Deposited On:21 May 2018 20:34
Last Modified:03 Oct 2019 19:44

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