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

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 the...

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Main Authors: Chen, Shuli, Chiew, Jun Xuan, Pullarkat, Sumod A., Li, Yongxin, Leung, Pak-Hing
Other Authors: School of Physical and Mathematical Sciences
Format: Article
Language:English
Published: 2014
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Online Access:https://hdl.handle.net/10356/102627
http://hdl.handle.net/10220/19112
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Institution: Nanyang Technological University
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spelling sg-ntu-dr.10356-1026272020-03-07T12:34:52Z Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd–C Bond Insertion Reactions with Coordinated Alkynylphosphanes Chen, Shuli Chiew, Jun Xuan Pullarkat, Sumod A. Li, Yongxin Leung, Pak-Hing School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds 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. 2014-04-04T06:44:32Z 2019-12-06T20:57:51Z 2014-04-04T06:44:32Z 2019-12-06T20:57:51Z 2013 2013 Journal Article 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. 1434-1948 https://hdl.handle.net/10356/102627 http://hdl.handle.net/10220/19112 10.1002/ejic.201300834 en European Journal of Inorganic Chemistry © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
institution Nanyang Technological University
building NTU Library
country Singapore
collection DR-NTU
language English
topic DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds
spellingShingle DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds
Chen, Shuli
Chiew, Jun Xuan
Pullarkat, Sumod A.
Li, Yongxin
Leung, Pak-Hing
Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd–C Bond Insertion Reactions with Coordinated Alkynylphosphanes
description 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.
author2 School of Physical and Mathematical Sciences
author_facet School of Physical and Mathematical Sciences
Chen, Shuli
Chiew, Jun Xuan
Pullarkat, Sumod A.
Li, Yongxin
Leung, Pak-Hing
format Article
author Chen, Shuli
Chiew, Jun Xuan
Pullarkat, Sumod A.
Li, Yongxin
Leung, Pak-Hing
author_sort Chen, Shuli
title Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd–C Bond Insertion Reactions with Coordinated Alkynylphosphanes
title_short Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd–C Bond Insertion Reactions with Coordinated Alkynylphosphanes
title_full Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd–C Bond Insertion Reactions with Coordinated Alkynylphosphanes
title_fullStr Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd–C Bond Insertion Reactions with Coordinated Alkynylphosphanes
title_full_unstemmed Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd–C Bond Insertion Reactions with Coordinated Alkynylphosphanes
title_sort stability and reactivity of cyclometallated naphthylamine complexes in pd–c bond insertion reactions with coordinated alkynylphosphanes
publishDate 2014
url https://hdl.handle.net/10356/102627
http://hdl.handle.net/10220/19112
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