Jump to main content
Jump to site search

Issue 6, 2000
Previous Article Next Article

Oxidative addition of iodine, iodomethane and iodobenzene to the rhodium phosphino enolate complex[Rh[upper bond 1 start]{Ph2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}(CO)(PPh3)] and carbon monoxide insertion into the resulting Rh–carbon bond of [Rh[upper bond 1 start]{Ph2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}Me(I)(CO)(PPh3)]

Author affiliations

Abstract

The oxidative addition of homo- and heteronuclear molecules XI (X=I, Me, Ph) to the square planar rhodium phosphino enolate complex [Rh[upper bond 1 start]{Ph2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}(CO)(PPh3)] 1 afforded the hexacoordinate Rh(III) complexes [Rh[upper bond 1 start]{Ph2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}X(I)(CO)(PPh3)] (X=Me 2; X=Ph 3; X=I 4). Complex 2 undergoes CO insertion into the Rh–Me bond to afford three isomers of the acetyl species [Rh[upper bond 1 start]{Ph2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}{C(O)Me}(I)(CO)(PPh3)] 5ac. Two of these isomers lose acetyl iodide to regenerate 1 and these transformations were followed by NMR and IR spectroscopic methods. The reaction of 1 with acetyl chloride results in rapid formation of the acetyl complex [Rh[upper bond 1 start]{Ph2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}{C(O)Me}(Cl)(CO)(PPh3)] 6. When left in solution, 6 isomerizes to give two additional isomeric acetyl species. All three isomers rapidly decompose to a Rh(I) species. The crystal structures of 1–3 have been determined by X-ray diffraction. The coordination geometry around the rhodium atom of 2 and 3 is distorted octahedral and the alkyl and halide ligands are in a mutually trans position.

Back to tab navigation

Supplementary files

Publication details

The article was received on 02 Feb 2000, accepted on 27 Mar 2000 and first published on 24 May 2000


Article type: Paper
DOI: 10.1039/B000961J
New J. Chem., 2000,24, 437-445

  •   Request permissions

    Oxidative addition of iodine, iodomethane and iodobenzene to the rhodium phosphino enolate complex [Rh[upper bond 1 start]{Ph2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}(CO)(PPh3)] and carbon monoxide insertion into the resulting Rh–carbon bond of [Rh[upper bond 1 start]{Ph2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}Me(I)(CO)(PPh3)]

    P. Braunstein, Y. Chauvin, J. Fischer, H. Olivier, C. Strohmann and D. V. Toronto, New J. Chem., 2000, 24, 437
    DOI: 10.1039/B000961J

Search articles by author

Spotlight

Advertisements