Intermolecular insertion of dialkynylphosphanes into the M–C bond of cyclopalladated rings through activation by cyclometallated amines
A series of chiral ortho-platinated and -palladated complexes derived from N,N,α-trimethylbenzylamine has been prepared. The dialkynylphosphane PhP(C CMe)2 coordinated regiospecifically as a P M monodentate ligand to these cyclometallated units in the positions trans to the nitrogen donors of the...
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sg-ntu-dr.10356-1018922020-03-07T12:34:54Z Intermolecular insertion of dialkynylphosphanes into the M–C bond of cyclopalladated rings through activation by cyclometallated amines Chen, Shuli Pullarkat, Sumod A. Li, Yongxin Leung, Pak-Hing School of Physical and Mathematical Sciences A series of chiral ortho-platinated and -palladated complexes derived from N,N,α-trimethylbenzylamine has been prepared. The dialkynylphosphane PhP(C CMe)2 coordinated regiospecifically as a P M monodentate ligand to these cyclometallated units in the positions trans to the nitrogen donors of the metallacycles. Upon introduction of selected chirality on the benzylamine unit and subsequent monitoring by using NMR spectroscopy, the P Pt bond was found to be thermodynamically stable and kinetically inert. The P Pd bond must be kinetically labile since the palladium complexes readily undergo a facile ligand redistribution process. Nevertheless, both ortho-metallated units activated one of the C C bonds towards an intermolecular Pd–C bond insertion reaction into another cyclopalladated ring. No intramolecular insertion reaction occurred within the same molecule. Coordination of PhP(C CMe)2 to the ortho-palladated unit also protected the organopalladium ring from intermolecular attack by other coordinated dialkynylphosphanes. The Pt–C bonds in cycloplatinated rings are not reactive toward the insertion reaction, although they are good reaction activators for coordinated dialkynylphosphanes. 2013-07-11T02:23:06Z 2019-12-06T20:46:22Z 2013-07-11T02:23:06Z 2019-12-06T20:46:22Z 2012 2012 Journal Article Chen, S., Pullarkat, S. A., Li, Y., Leung, P.-H. (2012). Intermolecular insertion of dialkynylphosphanes into the M–C bond of cyclopalladated rings through activation by cyclometallated amines. European Journal of Inorganic Chemistry, 2012(11), 1823-1831. https://hdl.handle.net/10356/101892 http://hdl.handle.net/10220/11162 10.1002/ejic.201101343 en European journal of inorganic chemistry © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. |
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A series of chiral ortho-platinated and -palladated complexes
derived from N,N,α-trimethylbenzylamine has been prepared.
The dialkynylphosphane PhP(C CMe)2 coordinated
regiospecifically as a P M monodentate ligand to these cyclometallated units in the positions trans to the nitrogen donors of the metallacycles. Upon introduction of selected chirality on the benzylamine unit and subsequent monitoring by
using NMR spectroscopy, the P Pt bond was found to be
thermodynamically stable and kinetically inert. The P Pd
bond must be kinetically labile since the palladium complexes
readily undergo a facile ligand redistribution process. Nevertheless, both ortho-metallated units activated one of
the C C bonds towards an intermolecular Pd–C bond insertion
reaction into another cyclopalladated ring. No intramolecular
insertion reaction occurred within the same molecule.
Coordination of PhP(C CMe)2 to the ortho-palladated unit
also protected the organopalladium ring from intermolecular
attack by other coordinated dialkynylphosphanes. The Pt–C
bonds in cycloplatinated rings are not reactive toward the
insertion reaction, although they are good reaction activators
for coordinated dialkynylphosphanes. |
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School of Physical and Mathematical Sciences |
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School of Physical and Mathematical Sciences Chen, Shuli Pullarkat, Sumod A. Li, Yongxin Leung, Pak-Hing |
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Chen, Shuli Pullarkat, Sumod A. Li, Yongxin Leung, Pak-Hing |
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Chen, Shuli Pullarkat, Sumod A. Li, Yongxin Leung, Pak-Hing Intermolecular insertion of dialkynylphosphanes into the M–C bond of cyclopalladated rings through activation by cyclometallated amines |
author_sort |
Chen, Shuli |
title |
Intermolecular insertion of dialkynylphosphanes into the M–C bond of cyclopalladated rings through activation by cyclometallated amines |
title_short |
Intermolecular insertion of dialkynylphosphanes into the M–C bond of cyclopalladated rings through activation by cyclometallated amines |
title_full |
Intermolecular insertion of dialkynylphosphanes into the M–C bond of cyclopalladated rings through activation by cyclometallated amines |
title_fullStr |
Intermolecular insertion of dialkynylphosphanes into the M–C bond of cyclopalladated rings through activation by cyclometallated amines |
title_full_unstemmed |
Intermolecular insertion of dialkynylphosphanes into the M–C bond of cyclopalladated rings through activation by cyclometallated amines |
title_sort |
intermolecular insertion of dialkynylphosphanes into the m–c bond of cyclopalladated rings through activation by cyclometallated amines |
publishDate |
2013 |
url |
https://hdl.handle.net/10356/101892 http://hdl.handle.net/10220/11162 |
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1681045129686679552 |