Metathesis of alkanes and related reactions

Handle URI:
http://hdl.handle.net/10754/561450
Title:
Metathesis of alkanes and related reactions
Authors:
Basset, Jean-Marie ( 0000-0003-3166-8882 ) ; Copéret, Christophe; Soulivong, Daravong; Taoufik, Mostafa; Thivolle-Cazat, Jean
Abstract:
(Figure Presented) The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, (=SiO)2TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of aluminasupported tungsten hydride, W(H)3/Al 2O3, which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis of olefins or the selective transformation of ethylene into propylene. Alkane metathesis represents a powerful tool for making progress in a variety of areas, perhaps most notably in the petroleum and petrochemical fields. Modern civilization is currently confronting a host of problems that relate to energy production and its effects on the environment, and judicious application of alkane metathesis to the processing of fuels such as crude oil and natural gas may well afford solutions to these difficulties. © 2010 American Chemical Society.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)
Publisher:
American Chemical Society (ACS)
Journal:
Accounts of Chemical Research
Issue Date:
16-Feb-2010
DOI:
10.1021/ar900203a
Type:
Article
ISSN:
00014842
Sponsors:
The effort of many co-workers whose names appear in some of the references are gratefully acknowledged. Financial support was provided by CNRS, CPE-Lyon, the Rhone-Alpes region, and the BASF and BP Companies.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorBasset, Jean-Marieen
dc.contributor.authorCopéret, Christopheen
dc.contributor.authorSoulivong, Daravongen
dc.contributor.authorTaoufik, Mostafaen
dc.contributor.authorThivolle-Cazat, Jeanen
dc.date.accessioned2015-08-02T09:11:39Zen
dc.date.available2015-08-02T09:11:39Zen
dc.date.issued2010-02-16en
dc.identifier.issn00014842en
dc.identifier.doi10.1021/ar900203aen
dc.identifier.urihttp://hdl.handle.net/10754/561450en
dc.description.abstract(Figure Presented) The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, (=SiO)2TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of aluminasupported tungsten hydride, W(H)3/Al 2O3, which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis of olefins or the selective transformation of ethylene into propylene. Alkane metathesis represents a powerful tool for making progress in a variety of areas, perhaps most notably in the petroleum and petrochemical fields. Modern civilization is currently confronting a host of problems that relate to energy production and its effects on the environment, and judicious application of alkane metathesis to the processing of fuels such as crude oil and natural gas may well afford solutions to these difficulties. © 2010 American Chemical Society.en
dc.description.sponsorshipThe effort of many co-workers whose names appear in some of the references are gratefully acknowledged. Financial support was provided by CNRS, CPE-Lyon, the Rhone-Alpes region, and the BASF and BP Companies.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleMetathesis of alkanes and related reactionsen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalAccounts of Chemical Researchen
dc.contributor.institutionUniversité de Lyon 1, Institut de Chimie de Lyon, Bâtiment 308F, 43 Blvd. du 11 Novembre 1918, F-69616 Villeurbanne Cedex, Franceen
kaust.authorBasset, Jean-Marieen
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