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Issue 6, 2000
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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)]

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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.

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Supplementary files

Article information


Submitted
02 Feb 2000
Accepted
27 Mar 2000
First published
24 May 2000

New J. Chem., 2000,24, 437-445
Article type
Paper

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

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