Mechanism and Energetics for Dehydrogenation of Methane by Gaseous Iridium Ions
Ir[sup +] has been observed as the most efficient transition-metal ion for dehydrogenation of CH[sub 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[sup...
Gespeichert in:
| Veröffentlicht in: | Organometallics 1994-05, Vol.13 (5), p.1870-1877 |
|---|---|
| Hauptverfasser: | , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 1877 |
|---|---|
| container_issue | 5 |
| container_start_page | 1870 |
| container_title | Organometallics |
| container_volume | 13 |
| creator | Perry, Jason K Ohanessian, Gilles Goddard, William A |
| description | Ir[sup +] has been observed as the most efficient transition-metal ion for dehydrogenation of CH[sub 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[sup +] to change spin easily, (ii) the strength of the Ir-C and Ir-H bonds, and (iii) the ability of Ir[sup +] to form up to four covalent bonds. We show that among transition-metal ions Ir[sup +] is unique in best possessing all these characteristics. The combination of these factors leads to a global minimum for the singlet Ir(H)[sub 2](CH[sub 2])[sup +] 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[sub 4]. 40 refs., 3 figs., 1 tab. |
| doi_str_mv | 10.1021/om00017a050 |
| format | Article |
| fullrecord | <record><control><sourceid>istex_osti_</sourceid><recordid>TN_cdi_osti_scitechconnect_7069403</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>ark_67375_TPS_R8X7VMC8_K</sourcerecordid><originalsourceid>FETCH-LOGICAL-a357t-94970c689d29f3c938bca17e9a36e31f6c4d543000d36e2284cad1a29b26df9a3</originalsourceid><addsrcrecordid>eNpt0MtKAzEUBuAgCtbLyhcIIriQ0VxmkslSatWiRfGGu3CayWhqm5RkCvbtjYyIC1eB5DvhPz9CB5ScUsLoWVgQQqgEUpENNKAVI4UgJd1EA8KkKCTnfBvtpDTLTEjOBuhuYs07eJcWGHyDR97GN9s5k3AbIr6w7-smhjfroXPB49Diie2yt3i6xleQbFglPI6ucasFHgef9tBWC_Nk93_OXfR8OXoaXhe3d1fj4fltAbySXaFKJYkRtWqYarlRvJ4aoNIq4MJy2gpTNlXJc8wmXzBWlwYaCkxNmWjarHbRYf9vSJ3Tybgu72GC99Z0WhKhSsIzOumRiSGlaFu9jG4Bca0p0d-F6T-FZX3U6yUkA_M2gjcu_Y6UlHEiRWZFz1zq7OfvM8QPnSuVlX66f9QP9at8mQxrfZP9ce_BJD0Lq-hzL_8G-ALhJIUW</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Mechanism and Energetics for Dehydrogenation of Methane by Gaseous Iridium Ions</title><source>American Chemical Society Journals</source><creator>Perry, Jason K ; Ohanessian, Gilles ; Goddard, William A</creator><creatorcontrib>Perry, Jason K ; Ohanessian, Gilles ; Goddard, William A</creatorcontrib><description>Ir[sup +] has been observed as the most efficient transition-metal ion for dehydrogenation of CH[sub 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[sup +] to change spin easily, (ii) the strength of the Ir-C and Ir-H bonds, and (iii) the ability of Ir[sup +] to form up to four covalent bonds. We show that among transition-metal ions Ir[sup +] is unique in best possessing all these characteristics. The combination of these factors leads to a global minimum for the singlet Ir(H)[sub 2](CH[sub 2])[sup +] 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[sub 4]. 40 refs., 3 figs., 1 tab.</description><identifier>ISSN: 0276-7333</identifier><identifier>EISSN: 1520-6041</identifier><identifier>DOI: 10.1021/om00017a050</identifier><identifier>CODEN: ORGND7</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>400201 - Chemical & Physicochemical Properties ; 990200 - Mathematics & Computers ; ALCOHOLS ; ALKANES ; CALCULATION METHODS ; CHARGED PARTICLES ; CHEMICAL ACTIVATION ; CHEMICAL BONDS ; CHEMICAL REACTIONS ; Chemistry ; COMPUTERIZED SIMULATION ; DEHYDROGENATION ; ELECTRONIC STRUCTURE ; Exact sciences and technology ; GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE ; HARTREE-FOCK METHOD ; HYDROCARBONS ; HYDROXY COMPOUNDS ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; IONS ; IRIDIUM IONS ; Kinetics and mechanisms ; MANAGEMENT ; METHANE ; METHANOL ; MULTIPLETS ; Organic chemistry ; ORGANIC COMPOUNDS ; PROCESSING ; REACTION INTERMEDIATES ; Reactivity and mechanisms ; SIMULATION ; SYNGAS PROCESS ; TRIPLETS ; WASTE MANAGEMENT ; WASTE PROCESSING</subject><ispartof>Organometallics, 1994-05, Vol.13 (5), p.1870-1877</ispartof><rights>1994 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a357t-94970c689d29f3c938bca17e9a36e31f6c4d543000d36e2284cad1a29b26df9a3</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/om00017a050$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/om00017a050$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,776,780,881,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=4123076$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/7069403$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Perry, Jason K</creatorcontrib><creatorcontrib>Ohanessian, Gilles</creatorcontrib><creatorcontrib>Goddard, William A</creatorcontrib><title>Mechanism and Energetics for Dehydrogenation of Methane by Gaseous Iridium Ions</title><title>Organometallics</title><addtitle>Organometallics</addtitle><description>Ir[sup +] has been observed as the most efficient transition-metal ion for dehydrogenation of CH[sub 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[sup +] to change spin easily, (ii) the strength of the Ir-C and Ir-H bonds, and (iii) the ability of Ir[sup +] to form up to four covalent bonds. We show that among transition-metal ions Ir[sup +] is unique in best possessing all these characteristics. The combination of these factors leads to a global minimum for the singlet Ir(H)[sub 2](CH[sub 2])[sup +] 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[sub 4]. 40 refs., 3 figs., 1 tab.</description><subject>400201 - Chemical & Physicochemical Properties</subject><subject>990200 - Mathematics & Computers</subject><subject>ALCOHOLS</subject><subject>ALKANES</subject><subject>CALCULATION METHODS</subject><subject>CHARGED PARTICLES</subject><subject>CHEMICAL ACTIVATION</subject><subject>CHEMICAL BONDS</subject><subject>CHEMICAL REACTIONS</subject><subject>Chemistry</subject><subject>COMPUTERIZED SIMULATION</subject><subject>DEHYDROGENATION</subject><subject>ELECTRONIC STRUCTURE</subject><subject>Exact sciences and technology</subject><subject>GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE</subject><subject>HARTREE-FOCK METHOD</subject><subject>HYDROCARBONS</subject><subject>HYDROXY COMPOUNDS</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>IONS</subject><subject>IRIDIUM IONS</subject><subject>Kinetics and mechanisms</subject><subject>MANAGEMENT</subject><subject>METHANE</subject><subject>METHANOL</subject><subject>MULTIPLETS</subject><subject>Organic chemistry</subject><subject>ORGANIC COMPOUNDS</subject><subject>PROCESSING</subject><subject>REACTION INTERMEDIATES</subject><subject>Reactivity and mechanisms</subject><subject>SIMULATION</subject><subject>SYNGAS PROCESS</subject><subject>TRIPLETS</subject><subject>WASTE MANAGEMENT</subject><subject>WASTE PROCESSING</subject><issn>0276-7333</issn><issn>1520-6041</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1994</creationdate><recordtype>article</recordtype><recordid>eNpt0MtKAzEUBuAgCtbLyhcIIriQ0VxmkslSatWiRfGGu3CayWhqm5RkCvbtjYyIC1eB5DvhPz9CB5ScUsLoWVgQQqgEUpENNKAVI4UgJd1EA8KkKCTnfBvtpDTLTEjOBuhuYs07eJcWGHyDR97GN9s5k3AbIr6w7-smhjfroXPB49Diie2yt3i6xleQbFglPI6ucasFHgef9tBWC_Nk93_OXfR8OXoaXhe3d1fj4fltAbySXaFKJYkRtWqYarlRvJ4aoNIq4MJy2gpTNlXJc8wmXzBWlwYaCkxNmWjarHbRYf9vSJ3Tybgu72GC99Z0WhKhSsIzOumRiSGlaFu9jG4Bca0p0d-F6T-FZX3U6yUkA_M2gjcu_Y6UlHEiRWZFz1zq7OfvM8QPnSuVlX66f9QP9at8mQxrfZP9ce_BJD0Lq-hzL_8G-ALhJIUW</recordid><startdate>19940501</startdate><enddate>19940501</enddate><creator>Perry, Jason K</creator><creator>Ohanessian, Gilles</creator><creator>Goddard, William A</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19940501</creationdate><title>Mechanism and Energetics for Dehydrogenation of Methane by Gaseous Iridium Ions</title><author>Perry, Jason K ; Ohanessian, Gilles ; Goddard, William A</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a357t-94970c689d29f3c938bca17e9a36e31f6c4d543000d36e2284cad1a29b26df9a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1994</creationdate><topic>400201 - Chemical & Physicochemical Properties</topic><topic>990200 - Mathematics & Computers</topic><topic>ALCOHOLS</topic><topic>ALKANES</topic><topic>CALCULATION METHODS</topic><topic>CHARGED PARTICLES</topic><topic>CHEMICAL ACTIVATION</topic><topic>CHEMICAL BONDS</topic><topic>CHEMICAL REACTIONS</topic><topic>Chemistry</topic><topic>COMPUTERIZED SIMULATION</topic><topic>DEHYDROGENATION</topic><topic>ELECTRONIC STRUCTURE</topic><topic>Exact sciences and technology</topic><topic>GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE</topic><topic>HARTREE-FOCK METHOD</topic><topic>HYDROCARBONS</topic><topic>HYDROXY COMPOUNDS</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>IONS</topic><topic>IRIDIUM IONS</topic><topic>Kinetics and mechanisms</topic><topic>MANAGEMENT</topic><topic>METHANE</topic><topic>METHANOL</topic><topic>MULTIPLETS</topic><topic>Organic chemistry</topic><topic>ORGANIC COMPOUNDS</topic><topic>PROCESSING</topic><topic>REACTION INTERMEDIATES</topic><topic>Reactivity and mechanisms</topic><topic>SIMULATION</topic><topic>SYNGAS PROCESS</topic><topic>TRIPLETS</topic><topic>WASTE MANAGEMENT</topic><topic>WASTE PROCESSING</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Perry, Jason K</creatorcontrib><creatorcontrib>Ohanessian, Gilles</creatorcontrib><creatorcontrib>Goddard, William A</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>Organometallics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Perry, Jason K</au><au>Ohanessian, Gilles</au><au>Goddard, William A</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Mechanism and Energetics for Dehydrogenation of Methane by Gaseous Iridium Ions</atitle><jtitle>Organometallics</jtitle><addtitle>Organometallics</addtitle><date>1994-05-01</date><risdate>1994</risdate><volume>13</volume><issue>5</issue><spage>1870</spage><epage>1877</epage><pages>1870-1877</pages><issn>0276-7333</issn><eissn>1520-6041</eissn><coden>ORGND7</coden><abstract>Ir[sup +] has been observed as the most efficient transition-metal ion for dehydrogenation of CH[sub 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[sup +] to change spin easily, (ii) the strength of the Ir-C and Ir-H bonds, and (iii) the ability of Ir[sup +] to form up to four covalent bonds. We show that among transition-metal ions Ir[sup +] is unique in best possessing all these characteristics. The combination of these factors leads to a global minimum for the singlet Ir(H)[sub 2](CH[sub 2])[sup +] 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[sub 4]. 40 refs., 3 figs., 1 tab.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/om00017a050</doi><tpages>8</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0276-7333 |
| ispartof | Organometallics, 1994-05, Vol.13 (5), p.1870-1877 |
| issn | 0276-7333 1520-6041 |
| language | eng |
| recordid | cdi_osti_scitechconnect_7069403 |
| source | American Chemical Society Journals |
| subjects | 400201 - Chemical & Physicochemical Properties 990200 - Mathematics & Computers ALCOHOLS ALKANES CALCULATION METHODS CHARGED PARTICLES CHEMICAL ACTIVATION CHEMICAL BONDS CHEMICAL REACTIONS Chemistry COMPUTERIZED SIMULATION DEHYDROGENATION ELECTRONIC STRUCTURE Exact sciences and technology GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE HARTREE-FOCK METHOD HYDROCARBONS HYDROXY COMPOUNDS INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY IONS IRIDIUM IONS Kinetics and mechanisms MANAGEMENT METHANE METHANOL MULTIPLETS Organic chemistry ORGANIC COMPOUNDS PROCESSING REACTION INTERMEDIATES Reactivity and mechanisms SIMULATION SYNGAS PROCESS TRIPLETS WASTE MANAGEMENT WASTE PROCESSING |
| title | Mechanism and Energetics for Dehydrogenation of Methane by Gaseous Iridium Ions |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-01T15%3A44%3A40IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-istex_osti_&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Mechanism%20and%20Energetics%20for%20Dehydrogenation%20of%20Methane%20by%20Gaseous%20Iridium%20Ions&rft.jtitle=Organometallics&rft.au=Perry,%20Jason%20K&rft.date=1994-05-01&rft.volume=13&rft.issue=5&rft.spage=1870&rft.epage=1877&rft.pages=1870-1877&rft.issn=0276-7333&rft.eissn=1520-6041&rft.coden=ORGND7&rft_id=info:doi/10.1021/om00017a050&rft_dat=%3Cistex_osti_%3Eark_67375_TPS_R8X7VMC8_K%3C/istex_osti_%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true |