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|Title:||Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd–C Bond Insertion Reactions with Coordinated Alkynylphosphanes||Authors:||Chen, Shuli
Chiew, Jun Xuan
Pullarkat, Sumod A.
|Keywords:||DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds||Issue Date:||2013||Source:||Chen, S., Chiew, J. X., Pullarkat, S. A., Li, Y., & Leung, P. H. (2013). Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd-C Bond Insertion Reactions with Coordinated Alkynylphosphanes. European Journal of Inorganic Chemistry, 2013(31), 5487-5494.||Series/Report no.:||European Journal of Inorganic Chemistry||Abstract:||Phenylbis(phenylethynyl)phosphane PhP(C≡CPh)2 coordinates regiospecifically to the α-methyl-chiral ortho-platinated and -palladated naphthylamine units at the positions trans to the nitrogen donors. The P→Pt coordination bond is kinetically inert, whereas the P→Pd bond is labile. Upon heating of these phosphane complexes at 70 °C, one of the C≡C bonds in the coordinated PhP(C≡CPh)2 was activated towards an intermolecular Pd–C bond insertion reaction with an external ortho-palladated naphthylamine ring. No intramolecular insertion reaction occurred. In contrast to its palladium analogue, the ortho-platinated ring is not reactive towards coordinated PhP(C≡CPh)2, although it can promote the Pd–C bond insertion reaction. However, despite the high kinetic stability of the P→Pt coordination, the organoplatinum unit is a noticeably weaker activator than its organopalladium counterpart. The chirality of the reacting ortho-metallated naphthylamine ligand exhibited high stereochemical influence on the formation of the new stereogenic phosphorus center during the course of these C–C bond-formation reactions. The coordination chemistry and the absolute stereochemistry of the dimetallic products were determined by single-crystal X-ray crystallographic analysis.||URI:||https://hdl.handle.net/10356/102627
|ISSN:||1434-1948||DOI:||10.1002/ejic.201300834||Rights:||© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.||Fulltext Permission:||none||Fulltext Availability:||No Fulltext|
|Appears in Collections:||SPMS Journal Articles|
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