Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd-C Bond Insertion Reactions with Coordinated Alkynylphosphanes
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ArticleKAUST Department
KAUST Catalysis Center (KCC)Date
2013-09-17Online Publication Date
2013-09-17Print Publication Date
2013-11-04Permanent link to this record
http://hdl.handle.net/10754/594189
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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. The asymmetric monoinsertion of PhP(C≡CPh)2 coordinated to a cyclometallated N,N-dimethyl naphthyl/benzylamine template into the Pd-C bonds of N,N-dimethylnaphthylamine palladacycles has been demonstrated for the synthesis of a variety of new P-stereogenic homo- or heterodimetallic complexes. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Citation
Chen S, Chiew JX, Pullarkat SA, 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: 5487–5494. Available: http://dx.doi.org/10.1002/ejic.201300834.Publisher
WileyRelations
Is Supplemented By:- [Dataset]
Chen, S., Chiew, J. X., Pullarkat, S. A., Li, Y., & Leung, P.-H. (2013). CCDC 940295: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10kg34. DOI: 10.5517/cc10kg34 HANDLE: 10754/624225 - [Dataset]
Chen, S., Chiew, J. X., Pullarkat, S. A., Li, Y., & Leung, P.-H. (2013). CCDC 940296: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10kg45. DOI: 10.5517/cc10kg45 HANDLE: 10754/624226 - [Dataset]
Chen, S., Chiew, J. X., Pullarkat, S. A., Li, Y., & Leung, P.-H. (2013). CCDC 940297: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10kg56. DOI: 10.5517/cc10kg56 HANDLE: 10754/624227 - [Dataset]
Chen, S., Chiew, J. X., Pullarkat, S. A., Li, Y., & Leung, P.-H. (2013). CCDC 940298: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10kg67. DOI: 10.5517/cc10kg67 HANDLE: 10754/624228 - [Dataset]
Chen, S., Chiew, J. X., Pullarkat, S. A., Li, Y., & Leung, P.-H. (2013). CCDC 940299: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10kg78. DOI: 10.5517/cc10kg78 HANDLE: 10754/624229
ae974a485f413a2113503eed53cd6c53
10.1002/ejic.201300834