Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd-C Bond Insertion Reactions with Coordinated Alkynylphosphanes

Handle URI:
http://hdl.handle.net/10754/594189
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.; Li, Yongxin; Leung, Pak Hing
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. 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.
KAUST Department:
KAUST Catalysis Center (KCC)
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:
Wiley-Blackwell
Journal:
European Journal of Inorganic Chemistry
Issue Date:
17-Sep-2013
DOI:
10.1002/ejic.201300834
Type:
Article
ISSN:
1434-1948
Is Supplemented By:
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:http://hdl.handle.net/10754/624225; 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:http://hdl.handle.net/10754/624226; 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:http://hdl.handle.net/10754/624227; 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:http://hdl.handle.net/10754/624228; 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:http://hdl.handle.net/10754/624229
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorChen, Shulien
dc.contributor.authorChiew, Jun Xuanen
dc.contributor.authorPullarkat, Sumod A.en
dc.contributor.authorLi, Yongxinen
dc.contributor.authorLeung, Pak Hingen
dc.date.accessioned2016-01-19T13:23:28Zen
dc.date.available2016-01-19T13:23:28Zen
dc.date.issued2013-09-17en
dc.identifier.citationChen 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.en
dc.identifier.issn1434-1948en
dc.identifier.doi10.1002/ejic.201300834en
dc.identifier.urihttp://hdl.handle.net/10754/594189en
dc.description.abstractPhenylbis(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.en
dc.publisherWiley-Blackwellen
dc.subjectDialkynylphosphanesen
dc.subjectHeterometallic complexesen
dc.subjectInsertionen
dc.subjectMetallacyclesen
dc.subjectPalladiumen
dc.titleStability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd-C Bond Insertion Reactions with Coordinated Alkynylphosphanesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalEuropean Journal of Inorganic Chemistryen
dc.contributor.institutionDivision of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 637616 Singapore, Singaporeen
kaust.authorChen, Shulien
dc.relation.isSupplementedByChen, 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/cc10kg34en
dc.relation.isSupplementedByDOI:10.5517/cc10kg34en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624225en
dc.relation.isSupplementedByChen, 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/cc10kg45en
dc.relation.isSupplementedByDOI:10.5517/cc10kg45en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624226en
dc.relation.isSupplementedByChen, 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/cc10kg56en
dc.relation.isSupplementedByDOI:10.5517/cc10kg56en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624227en
dc.relation.isSupplementedByChen, 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/cc10kg67en
dc.relation.isSupplementedByDOI:10.5517/cc10kg67en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624228en
dc.relation.isSupplementedByChen, 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/cc10kg78en
dc.relation.isSupplementedByDOI:10.5517/cc10kg78en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624229en
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.