Insertion of carbon monoxide and alkenes in palladium-carbon bonds of complexes containing rigid bidentate nitrogen ligands: the first example of isolated complexes in stepwise successive insertion reactions on the way to polyketones van Asselt, R.; Gielens, E.E.C.G.; Rulke, R.E.; Vrieze, K.; Elsevier, C.J.
Published in:Journal of the American Chemical Society
DOI:10.1021/ja00082a020Link to publication
Citation for published version (APA):van Asselt, R., Gielens, E. E. C. G., Rulke, R. E., Vrieze, K., & Elsevier, C. J. (1994). Insertion of carbon monoxide and alkenes in palladium-carbon bonds of complexes containing rigid bidentate nitrogen ligands: the first example of isolated complexes in stepwise successive insertion reactions on the way to polyketones. Journal of the American Chemical Society, 116, 977-985. DOI: 10.1021/ja00082a020
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0002-786319411516-0977$04.50/0complexes of the type PdXZ(L-L) (L-L is a chelating phosphorus or nitrogen ligand, X is a weakly or noncoordinating anion). The reaction is proposed to proceed via a perfectly alternating sequence of carbon monoxide and alkene insertions in palladium-carbon bonds (Scheme 1),4b,h An alternative mechanism involving palladium carbene intermediates, explaining the formation of spiroketals as the initial products,4g." has recently been proposed."A lot of experimental2 and theoretical6 research has been devoted to insertion of carbon monoxide in metal-carbon bonds, which can be regarded as a fundamental step in the copolymerization reactions. Studies on square-planar 16-electron complexes of palladium(I1) or platinum(I1) containing phosphine ligands have revealed that insertion of carbon monoxide occurs Alkenes insert readily into palladium-carbon bonds, as demonstrated by numerous examples of the Heck reaction.Io Furthermore, a variety of complexes formed by insertion of (strained) alkenes in palladium-acyl bonds has been isolated.Il From a theoretical study on alkene insertions in platinum-hydride bonds, it appeared that insertion from a four-coordinate intermediate is the preferred reaction pathway.'* Intramolecular insertions of alkynes and alkenes in palladium-carbalkoxy bonds were shown to proceed via a four-coordinate intermediate,Ila but intramolecul...
