Pentacarbonyliron(0) Photocatalyzed Hydrogenation and Isomerization of Olefins

Mark A. Schroeder; Mark S. Wrighton

doi:10.1021/ja00418a039

Pentacarbonyliron(0) Photocatalyzed Hydrogenation and Isomerization of Olefins

Mark A. Schroeder
, Mark S. Wrighton

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

186 Scopus citations

Abstract

Photocatalyzed alkene isomerization and olefin hydrogenation using Fe(CO)₅ as the photocatalyst have been investigated. Observed quantum efficiency for 1-pentene to 2-pentene isomerization approaches 500, implicating the generation of a thermally active catalyst. The catalytically active species is proposed to be HFe(CO)₃(π-allyl). Olefin hydrogenation occurs under mild conditions, 25°C (1 atm H₂), by irradiation of Fe(CO)₅ in the presence of olefin. At lower temperatures, use of D₂ reveals that deuterium is incorporated into an alkene competitively with alkane formation. Hydrogenation is proposed to proceed through the sequence. H₂Fe(CO)₃(alkene) ⇄ HFe(CO)₃(alkyl) → H₂Fe(CO)₃(alkene) + alkane There is good selectivity for the least sterically hindered alkene, and turnover numbers for Fe exceed 10³ in favorable cases.

Original language	English
Pages (from-to)	551-558
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	98
Issue number	2
DOIs	https://doi.org/10.1021/ja00418a039
State	Published - Jan 1 1976

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title = "Pentacarbonyliron(0) Photocatalyzed Hydrogenation and Isomerization of Olefins",

abstract = "Photocatalyzed alkene isomerization and olefin hydrogenation using Fe(CO)5 as the photocatalyst have been investigated. Observed quantum efficiency for 1-pentene to 2-pentene isomerization approaches 500, implicating the generation of a thermally active catalyst. The catalytically active species is proposed to be HFe(CO)3(π-allyl). Olefin hydrogenation occurs under mild conditions, 25°C (1 atm H2), by irradiation of Fe(CO)5 in the presence of olefin. At lower temperatures, use of D2 reveals that deuterium is incorporated into an alkene competitively with alkane formation. Hydrogenation is proposed to proceed through the sequence. H2Fe(CO)3(alkene) ⇄ HFe(CO)3(alkyl) → H2Fe(CO)3(alkene) + alkane There is good selectivity for the least sterically hindered alkene, and turnover numbers for Fe exceed 103 in favorable cases.",

author = "Schroeder, \{Mark A.\} and Wrighton, \{Mark S.\}",

year = "1976",

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doi = "10.1021/ja00418a039",

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journal = "Journal of the American Chemical Society",

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T1 - Pentacarbonyliron(0) Photocatalyzed Hydrogenation and Isomerization of Olefins

AU - Schroeder, Mark A.

AU - Wrighton, Mark S.

PY - 1976/1/1

Y1 - 1976/1/1

N2 - Photocatalyzed alkene isomerization and olefin hydrogenation using Fe(CO)5 as the photocatalyst have been investigated. Observed quantum efficiency for 1-pentene to 2-pentene isomerization approaches 500, implicating the generation of a thermally active catalyst. The catalytically active species is proposed to be HFe(CO)3(π-allyl). Olefin hydrogenation occurs under mild conditions, 25°C (1 atm H2), by irradiation of Fe(CO)5 in the presence of olefin. At lower temperatures, use of D2 reveals that deuterium is incorporated into an alkene competitively with alkane formation. Hydrogenation is proposed to proceed through the sequence. H2Fe(CO)3(alkene) ⇄ HFe(CO)3(alkyl) → H2Fe(CO)3(alkene) + alkane There is good selectivity for the least sterically hindered alkene, and turnover numbers for Fe exceed 103 in favorable cases.

AB - Photocatalyzed alkene isomerization and olefin hydrogenation using Fe(CO)5 as the photocatalyst have been investigated. Observed quantum efficiency for 1-pentene to 2-pentene isomerization approaches 500, implicating the generation of a thermally active catalyst. The catalytically active species is proposed to be HFe(CO)3(π-allyl). Olefin hydrogenation occurs under mild conditions, 25°C (1 atm H2), by irradiation of Fe(CO)5 in the presence of olefin. At lower temperatures, use of D2 reveals that deuterium is incorporated into an alkene competitively with alkane formation. Hydrogenation is proposed to proceed through the sequence. H2Fe(CO)3(alkene) ⇄ HFe(CO)3(alkyl) → H2Fe(CO)3(alkene) + alkane There is good selectivity for the least sterically hindered alkene, and turnover numbers for Fe exceed 103 in favorable cases.

UR - https://www.scopus.com/pages/publications/0005294076

U2 - 10.1021/ja00418a039

DO - 10.1021/ja00418a039

M3 - Article

AN - SCOPUS:0005294076

SN - 0002-7863

VL - 98

SP - 551

EP - 558

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 2

ER -

Pentacarbonyliron(0) Photocatalyzed Hydrogenation and Isomerization of Olefins

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