Synthesis and reactions at CoCH2 and CC bonds of cobalt-propargyl complexes

F. Ungváry, Andrew Wojcicki

Research output: Contribution to journalArticle

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Abstract

The first cobalt-propargyl complexes RCCCH2Co(CO)3PPh3 (1: R = Me (a), Ph (b), CH2Cl (c)) were prepared by reaction of NaCo(CO)3PPh3 with RCCCH2X (X = Cl or Br) in THF at ca. -20°C. Also synthesized, by treatment of NaCo(CO)4 in diethyl ether under CO at -20 to 0°C with one equivalent of each PPh3 and RCCCH2X in that order, were the first examples of metal acylpropargyl complexes, RCCCH2C(O)Co(CO)3PPh3 (2). Both 1 and 2 were characterized by elemental analysis and IR and NMR (1H, 13C{1H}, and 31P{1H}) spectroscopy and shown to adopt C3v structures. 1a,1b undergo carbonylation to 2a,2b in THF or CH2Cl2 solution at 0°C under 1 atm of CO; the reverse reaction occurs at room temperature when Ar is passed into solutions of 2a,2b in THF. The carbonylation reactions represent the first examples of insertion of CO into a propargyl carbon-to-metal linkage. 1a,1b undergo [3 + 2] cycloaddition reactions with (CN)2CC(CN)2 and SO2 to afford CH2C(CN)2C(CN)2C(R)CCo(CO)3PPh3 (3a,3b) and CH2OS(O)C(Me)CCo(CO)3PPh3 (4a), respectively.

Original languageEnglish
Pages (from-to)95-104
Number of pages10
JournalJournal of Organometallic Chemistry
Volume396
Issue number1
DOIs
Publication statusPublished - Oct 9 1990

Fingerprint

Carbonylation
Cobalt
cobalt
Cycloaddition
Coordination Complexes
Cycloaddition Reaction
synthesis
Metal complexes
Ether
Ethers
Spectrum Analysis
Carbon
Metals
Nuclear magnetic resonance
Spectroscopy
diethyl ether
Temperature
cycloaddition
Chemical analysis
linkages

ASJC Scopus subject areas

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

Cite this

Synthesis and reactions at CoCH2 and CC bonds of cobalt-propargyl complexes. / Ungváry, F.; Wojcicki, Andrew.

In: Journal of Organometallic Chemistry, Vol. 396, No. 1, 09.10.1990, p. 95-104.

Research output: Contribution to journalArticle

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abstract = "The first cobalt-propargyl complexes RCCCH2Co(CO)3PPh3 (1: R = Me (a), Ph (b), CH2Cl (c)) were prepared by reaction of NaCo(CO)3PPh3 with RCCCH2X (X = Cl or Br) in THF at ca. -20°C. Also synthesized, by treatment of NaCo(CO)4 in diethyl ether under CO at -20 to 0°C with one equivalent of each PPh3 and RCCCH2X in that order, were the first examples of metal acylpropargyl complexes, RCCCH2C(O)Co(CO)3PPh3 (2). Both 1 and 2 were characterized by elemental analysis and IR and NMR (1H, 13C{1H}, and 31P{1H}) spectroscopy and shown to adopt C3v structures. 1a,1b undergo carbonylation to 2a,2b in THF or CH2Cl2 solution at 0°C under 1 atm of CO; the reverse reaction occurs at room temperature when Ar is passed into solutions of 2a,2b in THF. The carbonylation reactions represent the first examples of insertion of CO into a propargyl carbon-to-metal linkage. 1a,1b undergo [3 + 2] cycloaddition reactions with (CN)2CC(CN)2 and SO2 to afford CH2C(CN)2C(CN)2C(R)CCo(CO)3PPh3 (3a,3b) and CH2OS(O)C(Me)CCo(CO)3PPh3 (4a), respectively.",
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