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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 General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. 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...

Both symmetric and nonsymmetric bis(aryl)acenaphthenequinonediimine ligands, featured by substituents in meta-positions of the aryl rings, have been applied for the first time as ancillary ligands for the palladiumcatalyzed CO/vinyl arene copolymerization. The nature and the number of substituents affect both the productivity and the molecular weight of the synthesized copolymers. Palladium complexes containing the nonsymmetric ligands are the most efficient catalysts reported so far for the synthesis of atactic polyketones.

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Stable palladium(0), palladium(II) and platinum(II) complexes containing a new, multifunctional and hemilabile phosphino-imino-pyridyl ligand: Synthesis, characterization and reactivity Rulke, R.E.; Kaasjager, V.E.; Wehman, P.; Elsevier, C.J.; van Leeuwen, P.W.N.M.; Vrieze, K.; Fraanje, J.; Goubitz, K.; Spek, A.L. Published in: Organometallics DOI:10.1021/om9509047Link to publication Citation for published version (APA):Rulke, R. E., Kaasjager, V. E., Wehman, P., Elsevier, C. J., van Leeuwen, P. W. N. M., Vrieze, K., ... Spek, A. L. (1996). Stable palladium(0), palladium(II) and platinum(II) complexes containing a new, multifunctional and hemilabile phosphino-imino-pyridyl ligand: Synthesis, characterization and reactivity. Organometallics, 15, 3022-3031.