On the mechanism and regioselectivity of alkane photocarbonylation catalyzed by Rh(PMe3)2(CO)Cl

Glen P. Rosini, Keming Zhu, Alan S Goldman

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

Photochemical carbonylation of hexane catalyzed by Rh(PMe3)2(CO)Cl (1) is found to proceed via at least two different mechanisms. One requires a secondary photochemical reaction and gives primarily (ca. 98%) linear aldehyde, while the other is radical-based, much less regioselective, and apparently involves only one photochemical step. In accord with this mechanistic understanding, it has proven possible to find conditions leading simultaneously to high photoefficiency and regioselectivity, and greatly increased chemical yields. The presumed photointermediate in the two-photoprocess pathway has been photochemically generated at low temperature and characterized by NMR spectroscopy.

Original languageEnglish
Pages (from-to)115-121
Number of pages7
JournalJournal of Organometallic Chemistry
Volume504
Issue number1-2
Publication statusPublished - Nov 29 1995

Fingerprint

Carbonylation
Regioselectivity
Alkanes
Photochemical reactions
Hexanes
Carbon Monoxide
Hexane
Aldehydes
aldehydes
photochemical reactions
Paraffins
alkanes
Nuclear magnetic resonance spectroscopy
Magnetic Resonance Spectroscopy
nuclear magnetic resonance
Temperature
spectroscopy

Keywords

  • Alkane activation
  • Carbonylation
  • Photochemistry
  • Rhodium

ASJC Scopus subject areas

  • Materials Chemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Biochemistry

Cite this

On the mechanism and regioselectivity of alkane photocarbonylation catalyzed by Rh(PMe3)2(CO)Cl. / Rosini, Glen P.; Zhu, Keming; Goldman, Alan S.

In: Journal of Organometallic Chemistry, Vol. 504, No. 1-2, 29.11.1995, p. 115-121.

Research output: Contribution to journalArticle

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