Carbon-Hydrogen Bond Activation by Triruthenium Carbonyl Species during Carbon Monoxide Promoted Elimination of 4,5-Dihydroacenaphthylene from [(μ2

η1: η5-C12H10)Ru3H 2(CO)7]: Implication of Reaction Intermediates

Hideo Nagashima, Akihiro Suzuki, Mitsuharu Nobata, Katsuyuki Aoki, Kenji Itoh

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Abstract

Oxidative addition of a vinylic C-H bond occurred during the CO-promoted elimination of 4,5-dihydroacenaphthylene (3) from [(μ2 : η1 : η5-C12H10)Ru3H 2(CO)7] (2) in CH2Cl2. The product, [(μ3 : η1 : η2 : η2-C12H9)Ru3H(CO)9] (4), was isolated and characterized by spectroscopy and crystallography. The carbonylation of a deuterium-labelled complex, [(μ2 : η1 : η5-C12H8D2)Ru3D 2(CO)7] (2-d4), under the same conditions as that from 2 to 3 in CH2Cl2 afforded 4,5-dideuterioacenaphthylene (3-d2) and [(μ3 : η1 : η2 : η2-C12H7D2)Ru 3H(CO)9] (4-d2). The lack of incorporation of deuterium atoms into the ruthenium hydride in 4-d2 suggested that dissociation of D2 from the triruthenium moiety in 2-d4 induced the oxidative addition of the vinylic C-H bond. Further carbonylation of 4 did not occur under the same conditions as the reaction from 2 to 4, but gave 3 in moderate yields under higher CO pressure (8 atm) at 50 - 100 °C. These results suggest that 4 was not directly involved in the CO promoted elimination of 3 from 2, but was closely related to the actual intermediates. Possible reaction mechanisms are discussed.

Original languageEnglish
Pages (from-to)2231-2237
Number of pages7
JournalBulletin of the Chemical Society of Japan
Volume70
Issue number9
DOIs
Publication statusPublished - Jan 1 1997

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Reaction intermediates
Carbon Monoxide
Hydrogen bonds
Carbon
Chemical activation
Carbonylation
Deuterium
Crystallography
Ruthenium
Hydrides
Spectroscopy
Atoms

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

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title = "Carbon-Hydrogen Bond Activation by Triruthenium Carbonyl Species during Carbon Monoxide Promoted Elimination of 4,5-Dihydroacenaphthylene from [(μ2: η1: η5-C12H10)Ru3H 2(CO)7]: Implication of Reaction Intermediates",
abstract = "Oxidative addition of a vinylic C-H bond occurred during the CO-promoted elimination of 4,5-dihydroacenaphthylene (3) from [(μ2 : η1 : η5-C12H10)Ru3H 2(CO)7] (2) in CH2Cl2. The product, [(μ3 : η1 : η2 : η2-C12H9)Ru3H(CO)9] (4), was isolated and characterized by spectroscopy and crystallography. The carbonylation of a deuterium-labelled complex, [(μ2 : η1 : η5-C12H8D2)Ru3D 2(CO)7] (2-d4), under the same conditions as that from 2 to 3 in CH2Cl2 afforded 4,5-dideuterioacenaphthylene (3-d2) and [(μ3 : η1 : η2 : η2-C12H7D2)Ru 3H(CO)9] (4-d2). The lack of incorporation of deuterium atoms into the ruthenium hydride in 4-d2 suggested that dissociation of D2 from the triruthenium moiety in 2-d4 induced the oxidative addition of the vinylic C-H bond. Further carbonylation of 4 did not occur under the same conditions as the reaction from 2 to 4, but gave 3 in moderate yields under higher CO pressure (8 atm) at 50 - 100 °C. These results suggest that 4 was not directly involved in the CO promoted elimination of 3 from 2, but was closely related to the actual intermediates. Possible reaction mechanisms are discussed.",
author = "Hideo Nagashima and Akihiro Suzuki and Mitsuharu Nobata and Katsuyuki Aoki and Kenji Itoh",
year = "1997",
month = "1",
day = "1",
doi = "10.1246/bcsj.70.2231",
language = "English",
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pages = "2231--2237",
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TY - JOUR

T1 - Carbon-Hydrogen Bond Activation by Triruthenium Carbonyl Species during Carbon Monoxide Promoted Elimination of 4,5-Dihydroacenaphthylene from [(μ2

T2 - η1: η5-C12H10)Ru3H 2(CO)7]: Implication of Reaction Intermediates

AU - Nagashima, Hideo

AU - Suzuki, Akihiro

AU - Nobata, Mitsuharu

AU - Aoki, Katsuyuki

AU - Itoh, Kenji

PY - 1997/1/1

Y1 - 1997/1/1

N2 - Oxidative addition of a vinylic C-H bond occurred during the CO-promoted elimination of 4,5-dihydroacenaphthylene (3) from [(μ2 : η1 : η5-C12H10)Ru3H 2(CO)7] (2) in CH2Cl2. The product, [(μ3 : η1 : η2 : η2-C12H9)Ru3H(CO)9] (4), was isolated and characterized by spectroscopy and crystallography. The carbonylation of a deuterium-labelled complex, [(μ2 : η1 : η5-C12H8D2)Ru3D 2(CO)7] (2-d4), under the same conditions as that from 2 to 3 in CH2Cl2 afforded 4,5-dideuterioacenaphthylene (3-d2) and [(μ3 : η1 : η2 : η2-C12H7D2)Ru 3H(CO)9] (4-d2). The lack of incorporation of deuterium atoms into the ruthenium hydride in 4-d2 suggested that dissociation of D2 from the triruthenium moiety in 2-d4 induced the oxidative addition of the vinylic C-H bond. Further carbonylation of 4 did not occur under the same conditions as the reaction from 2 to 4, but gave 3 in moderate yields under higher CO pressure (8 atm) at 50 - 100 °C. These results suggest that 4 was not directly involved in the CO promoted elimination of 3 from 2, but was closely related to the actual intermediates. Possible reaction mechanisms are discussed.

AB - Oxidative addition of a vinylic C-H bond occurred during the CO-promoted elimination of 4,5-dihydroacenaphthylene (3) from [(μ2 : η1 : η5-C12H10)Ru3H 2(CO)7] (2) in CH2Cl2. The product, [(μ3 : η1 : η2 : η2-C12H9)Ru3H(CO)9] (4), was isolated and characterized by spectroscopy and crystallography. The carbonylation of a deuterium-labelled complex, [(μ2 : η1 : η5-C12H8D2)Ru3D 2(CO)7] (2-d4), under the same conditions as that from 2 to 3 in CH2Cl2 afforded 4,5-dideuterioacenaphthylene (3-d2) and [(μ3 : η1 : η2 : η2-C12H7D2)Ru 3H(CO)9] (4-d2). The lack of incorporation of deuterium atoms into the ruthenium hydride in 4-d2 suggested that dissociation of D2 from the triruthenium moiety in 2-d4 induced the oxidative addition of the vinylic C-H bond. Further carbonylation of 4 did not occur under the same conditions as the reaction from 2 to 4, but gave 3 in moderate yields under higher CO pressure (8 atm) at 50 - 100 °C. These results suggest that 4 was not directly involved in the CO promoted elimination of 3 from 2, but was closely related to the actual intermediates. Possible reaction mechanisms are discussed.

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U2 - 10.1246/bcsj.70.2231

DO - 10.1246/bcsj.70.2231

M3 - Article

VL - 70

SP - 2231

EP - 2237

JO - Bulletin of the Chemical Society of Japan

JF - Bulletin of the Chemical Society of Japan

SN - 0009-2673

IS - 9

ER -