Formation of a manganese alkyl complex as an intermediate in the ring-opening hydroformylation of α-cyclopropylstyrene by HMn(CO)5

R Morris Bullock, Brian J. Rappoli

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4 Citations (Scopus)

Abstract

The reaction of α-clopropylstyrene (CPS) with HMn(CO)5 can result in either hydrogenation or hydroformylation. The hydrogenation occurs by a previously established pathway involving sequential hydrogen atom transfers from the metal hydride to the organic substrate, and is the predominant reaction observed with samples of HMn(CO)5 that have been thoroughly dried and purified using P2O5. With samples of HMn(CO)5 that have been not been treated with P2O5, the reaction that occurs with CPS is ring-opening hydroformylation, leading to the isolation of Mn2(CO)91-HCOCH2CH2CHC(Ph)CH3). The detailed procedures for preparation and handling of HMn(CO)5 that are reported in this paper enable the hydroformylation reaction to be reproducible observed as the predominant reaction. An induction period of a few hours is typically observed in the hydroformylation, but addition of Mn2(CO)91-tolualdehyde) eliminates the induction period. The hydroformylation reaction is inhibited by CO (1 atm). The manganese alkyl complex (CO)5MnCH2CH2CHC(Ph)CH3 is an intermediate in the hydroformylation. The details of the mechanism of formation of this alkyl complex from CPS and HMn(CO)s are not completely understood, but several mechanistic possibilities are considered.

Original languageEnglish
Pages (from-to)345-368
Number of pages24
JournalJournal of Organometallic Chemistry
Volume429
Issue number3
DOIs
Publication statusPublished - May 26 1992

Fingerprint

phosphorus pentoxide
Hydroformylation
Hydrogenation
Manganese
manganese
rings
Hydrogen
Metals
hydrogenation
induction
metal hydrides
Hydrides
hydrogen atoms
isolation

ASJC Scopus subject areas

  • Biochemistry
  • Chemical Engineering (miscellaneous)
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Science (miscellaneous)
  • Materials Chemistry

Cite this

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title = "Formation of a manganese alkyl complex as an intermediate in the ring-opening hydroformylation of α-cyclopropylstyrene by HMn(CO)5",
abstract = "The reaction of α-clopropylstyrene (CPS) with HMn(CO)5 can result in either hydrogenation or hydroformylation. The hydrogenation occurs by a previously established pathway involving sequential hydrogen atom transfers from the metal hydride to the organic substrate, and is the predominant reaction observed with samples of HMn(CO)5 that have been thoroughly dried and purified using P2O5. With samples of HMn(CO)5 that have been not been treated with P2O5, the reaction that occurs with CPS is ring-opening hydroformylation, leading to the isolation of Mn2(CO)9(η1-HCOCH2CH2CHC(Ph)CH3). The detailed procedures for preparation and handling of HMn(CO)5 that are reported in this paper enable the hydroformylation reaction to be reproducible observed as the predominant reaction. An induction period of a few hours is typically observed in the hydroformylation, but addition of Mn2(CO)9(η1-tolualdehyde) eliminates the induction period. The hydroformylation reaction is inhibited by CO (1 atm). The manganese alkyl complex (CO)5MnCH2CH2CHC(Ph)CH3 is an intermediate in the hydroformylation. The details of the mechanism of formation of this alkyl complex from CPS and HMn(CO)s are not completely understood, but several mechanistic possibilities are considered.",
author = "Bullock, {R Morris} and Rappoli, {Brian J.}",
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T1 - Formation of a manganese alkyl complex as an intermediate in the ring-opening hydroformylation of α-cyclopropylstyrene by HMn(CO)5

AU - Bullock, R Morris

AU - Rappoli, Brian J.

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Y1 - 1992/5/26

N2 - The reaction of α-clopropylstyrene (CPS) with HMn(CO)5 can result in either hydrogenation or hydroformylation. The hydrogenation occurs by a previously established pathway involving sequential hydrogen atom transfers from the metal hydride to the organic substrate, and is the predominant reaction observed with samples of HMn(CO)5 that have been thoroughly dried and purified using P2O5. With samples of HMn(CO)5 that have been not been treated with P2O5, the reaction that occurs with CPS is ring-opening hydroformylation, leading to the isolation of Mn2(CO)9(η1-HCOCH2CH2CHC(Ph)CH3). The detailed procedures for preparation and handling of HMn(CO)5 that are reported in this paper enable the hydroformylation reaction to be reproducible observed as the predominant reaction. An induction period of a few hours is typically observed in the hydroformylation, but addition of Mn2(CO)9(η1-tolualdehyde) eliminates the induction period. The hydroformylation reaction is inhibited by CO (1 atm). The manganese alkyl complex (CO)5MnCH2CH2CHC(Ph)CH3 is an intermediate in the hydroformylation. The details of the mechanism of formation of this alkyl complex from CPS and HMn(CO)s are not completely understood, but several mechanistic possibilities are considered.

AB - The reaction of α-clopropylstyrene (CPS) with HMn(CO)5 can result in either hydrogenation or hydroformylation. The hydrogenation occurs by a previously established pathway involving sequential hydrogen atom transfers from the metal hydride to the organic substrate, and is the predominant reaction observed with samples of HMn(CO)5 that have been thoroughly dried and purified using P2O5. With samples of HMn(CO)5 that have been not been treated with P2O5, the reaction that occurs with CPS is ring-opening hydroformylation, leading to the isolation of Mn2(CO)9(η1-HCOCH2CH2CHC(Ph)CH3). The detailed procedures for preparation and handling of HMn(CO)5 that are reported in this paper enable the hydroformylation reaction to be reproducible observed as the predominant reaction. An induction period of a few hours is typically observed in the hydroformylation, but addition of Mn2(CO)9(η1-tolualdehyde) eliminates the induction period. The hydroformylation reaction is inhibited by CO (1 atm). The manganese alkyl complex (CO)5MnCH2CH2CHC(Ph)CH3 is an intermediate in the hydroformylation. The details of the mechanism of formation of this alkyl complex from CPS and HMn(CO)s are not completely understood, but several mechanistic possibilities are considered.

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