Substitution Reactions of Sodium Tetracarbonylcobaltate(1-) with Activated Alkenes. Synthesis, Characterization, and Reactions of Alkene Carbonyl Complexes, Na[Co(CO)4−x(alkene)x] (x = 1 and 2)

Ferenc Ungvàry, Judith Gallucci, Andrew Wojcicki

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Abstract

Reactions of Na[Co(CO)4] with the activated alkenes maleic anhydride (MA), dimethyl maleate (DM), and fumaronitrile (FN) in THF solution under photochemical conditions afford the monosubstituted products Na[Co(CO)3(alkene)]. Under thermal conditions, in THF at reflux, reactions of Na[Co(CO)4] with MA, FN, and dimethyl fumarate (DF) each afford the disubstituted complexes Na[Co(CO)2(alkene)2]. In the corresponding reaction of Na[Co(CO)4] with DM, the alkene undergoes isomerization to give Na[Co(C-0)2(DF)2]. Tetracyanoethylene (TCNE) and Na[Co(CO)4] react even at −60 to 0 °C to furnish Na[Co-(CO)3(TCNE)]. All of the aforementioned complexes were isolated as different THF solvates and characterized by a combination of elemental analysis and IR and 1H and 13C{1H} NMR spectroscopies. They react with CO to yield one or both of Na[Co(CO)3(alkene)] and Na[Co(CO)4] and with other activated alkenes (alkene2) to afford one or both of Na[Co(CO)2(alkene1)(alkene2)] and Na[Co(CO)4−x(alkene2)x] (x = 1 or 2). The reactivities of the various alkenes toward Na[Co(CO)4] and of Na[Co(CO)3(alkene)] and Na-[Co(CO)2(alkene)2] toward CO and alkene2 are compared. The structure of Na[Co(CO)2(DF)2]-THF was elucidated by a single-crystal X-ray diffraction analysis: Space group P1, with α = 13.096 (2) Å, b = 18.287 (2) Å, c = 10.195 (2) Å, α = 90.49 (1)°, β = 91.16 (1)°, γ = 107.24 (1)°, and Z = 4. The structure was solved and refined to R = 0.102 and Rw = 0.069. The compound is a dimer of Na[Co(CO)2(DF)2]-THF, formed by interaction of each Na+ ion with the oxygen atoms of two fumarate C=0 groups from each [Co(C-O)2(DF)2] anion and with the oxygen atom of a THF molecule. The arrangement of these five oxygen donors around the Na+ ion is trigonal bipyramidal, whereas the geometry of the two CO carbons and the midpoints of the two C=C bonds about the Co atom is approximately tetrahedral.

Original languageEnglish
Pages (from-to)3053-3062
Number of pages10
JournalOrganometallics
Volume10
Issue number9
DOIs
Publication statusPublished - Sep 1 1991

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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