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Article: Understanding the reactivity difference of metal boryl complexes toward alkanes and arenes: A density functional study on the functionalizations of methane and benzene by CpM(CO) n(BO 2C 2H 2) (M = Fe, Ru, W)

TitleUnderstanding the reactivity difference of metal boryl complexes toward alkanes and arenes: A density functional study on the functionalizations of methane and benzene by CpM(CO) n(BO 2C 2H 2) (M = Fe, Ru, W)
Authors
Issue Date2003
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 2003, v. 22 n. 3, p. 473-480 How to Cite?
AbstractReaction mechanisms of the methane and benzene functionalizations (borylation) by CpFe(CO)(BO 2C 2H 2) and CpW(CO) 2(BO 2C 2H 2) have been investigated with the aid of B3LYP density functional theory calculations. The results show that the functionalizations by the Fe boryl complex favor a one-step mechanism with an oxidatively added transition state, while the functionalizations by the tungsten boryl complex only proceed by a two-step mechanism. The significant barrier difference between the functionalizations of methane and benzene by the Fe complex and the small barrier difference between the functionalizations by the W complex from our calculations are in good agreement with the experimental observation in a series of photochemical reactions of the transition-metal boryl complexes with alkanes and arenes. Cp*W(CO) 3Bcat′ (Bcat′ = B-1,2-O 2C 6H 2-3,5-Me 2) has comparable reactivity toward both alkanes and arenes, while the iron boryl complexes Cp′Fe(CO) 2Bcat (Cp′ = Cp, Cp*; Bcat = B-1,2-O 2C 6H 4) are very reactive toward the aromatic C-H bonds of arenes and are unreactive toward the alkane C-H bonds. The distinct barriers between the functionalizations of methane and benzene by the Fe complex can be explained by the significant stabilization interaction between the "empty" boron p orbital of the boryl group and the π orbitals of the benzene ring in the oxidatively added transition state for the iron - benzene system. The types of B⋯C interactions become unimportant in the functionalization of benzene by the tungsten boryl complex because the functionalization proceeds via a two-step mechanism. For the purpose of comparison, a mechanistic study on the functionalizations of methane and benzene by the model complex CpRu(CO)(BO 2C 2H 2) has also been done.
Persistent Identifierhttp://hdl.handle.net/10722/167777
ISSN
2015 Impact Factor: 4.186
2015 SCImago Journal Rankings: 2.043
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLam, WHen_US
dc.contributor.authorLin, Zen_US
dc.date.accessioned2012-10-08T03:11:25Z-
dc.date.available2012-10-08T03:11:25Z-
dc.date.issued2003en_US
dc.identifier.citationOrganometallics, 2003, v. 22 n. 3, p. 473-480en_US
dc.identifier.issn0276-7333en_US
dc.identifier.urihttp://hdl.handle.net/10722/167777-
dc.description.abstractReaction mechanisms of the methane and benzene functionalizations (borylation) by CpFe(CO)(BO 2C 2H 2) and CpW(CO) 2(BO 2C 2H 2) have been investigated with the aid of B3LYP density functional theory calculations. The results show that the functionalizations by the Fe boryl complex favor a one-step mechanism with an oxidatively added transition state, while the functionalizations by the tungsten boryl complex only proceed by a two-step mechanism. The significant barrier difference between the functionalizations of methane and benzene by the Fe complex and the small barrier difference between the functionalizations by the W complex from our calculations are in good agreement with the experimental observation in a series of photochemical reactions of the transition-metal boryl complexes with alkanes and arenes. Cp*W(CO) 3Bcat′ (Bcat′ = B-1,2-O 2C 6H 2-3,5-Me 2) has comparable reactivity toward both alkanes and arenes, while the iron boryl complexes Cp′Fe(CO) 2Bcat (Cp′ = Cp, Cp*; Bcat = B-1,2-O 2C 6H 4) are very reactive toward the aromatic C-H bonds of arenes and are unreactive toward the alkane C-H bonds. The distinct barriers between the functionalizations of methane and benzene by the Fe complex can be explained by the significant stabilization interaction between the "empty" boron p orbital of the boryl group and the π orbitals of the benzene ring in the oxidatively added transition state for the iron - benzene system. The types of B⋯C interactions become unimportant in the functionalization of benzene by the tungsten boryl complex because the functionalization proceeds via a two-step mechanism. For the purpose of comparison, a mechanistic study on the functionalizations of methane and benzene by the model complex CpRu(CO)(BO 2C 2H 2) has also been done.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallicsen_US
dc.relation.ispartofOrganometallicsen_US
dc.titleUnderstanding the reactivity difference of metal boryl complexes toward alkanes and arenes: A density functional study on the functionalizations of methane and benzene by CpM(CO) n(BO 2C 2H 2) (M = Fe, Ru, W)en_US
dc.typeArticleen_US
dc.identifier.emailLam, WH:chsue@hku.hken_US
dc.identifier.authorityLam, WH=rp00719en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/om020901ben_US
dc.identifier.scopuseid_2-s2.0-0037416035en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0037416035&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume22en_US
dc.identifier.issue3en_US
dc.identifier.spage473en_US
dc.identifier.epage480en_US
dc.identifier.isiWOS:000180689000015-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridLam, WH=26642862800en_US
dc.identifier.scopusauthoridLin, Z=7404230177en_US

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