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CatalyticActivationofMethaneandEthanebyMetal

Compounds

AyusmanSen

DepartmentofChemistry,ThePennsylvaniaStateUniversity,UniversityPark,

PA16802USA

E-mail:asen@

Methaneandethanearethemostabundantandtheleastreactivemembersofthehydro-

carbonfamily,andtheirselectiveconversiontousefulchemicalproductsisofgreatscien-

tific,aswellaspractical,interest.Thisreviewhighlightssomeoftherecentadvancesinthe

areaoflowtemperature,catalytic,activationandfunctionalizationofmethaneandethane.

ParticularemphasishasbeenplacedonC–HandC–Cactivationprocessesleadingtothe

formationofoxygenates.

Keywords:Methane,Ethane,C–Hactivation,C–Cactivation,Oxidation,Catalysis

1Introduction................................81

2ReactionsinStronglyAcidicMedia..................84

3ReactionsinAqueousMedium.....................89

4MiscellaneousRadicalPathways....................90

5ArtificialMonoxygenases........................90

References.....................................93

1

Introduction

Methaneisthemostabundantandtheleastreactivememberofthehydrocarbon

family.Ethanecomessecondinbothcategories.Together,theyconstitute95%

ofnaturalgas,withknownreservesapproachingthatofpetroleum[1].Asignif-

icantportionofthemethaneandethaneproducedisnotutilizedbecauseofthe

difficultyassociatedwiththetransportationofaflammable,low-boilinggas.

Theirpossibleuseasautomobilefuelsisalsolimitedbytheintrinsicdisadvan-

tagesofgaseousfuels,i.e.,lowenergycontentperunitvol