Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds

Secondary arsines were observed to decomplex strongly chelating phosphapalladacycles rapidly under mild conditions. As-H bond migration led to ortho-protonation of the C,P ligand. On the other hand, N-H and P-H bonds in amine and phosphine analogues were acidified under the same conditions and no li...

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Main Authors: Tay, Wee Shan, Li, Yongxin, Pullarkat, Sumod A., Leung, Pak-Hing
Other Authors: School of Physical and Mathematical Sciences
Format: Article
Language:English
Published: 2022
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Online Access:https://hdl.handle.net/10356/155198
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Institution: Nanyang Technological University
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spelling sg-ntu-dr.10356-1551982022-02-15T05:05:12Z Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds Tay, Wee Shan Li, Yongxin Pullarkat, Sumod A. Leung, Pak-Hing School of Physical and Mathematical Sciences Science::Chemistry Phosphorus Compounds Protonation Secondary arsines were observed to decomplex strongly chelating phosphapalladacycles rapidly under mild conditions. As-H bond migration led to ortho-protonation of the C,P ligand. On the other hand, N-H and P-H bonds in amine and phosphine analogues were acidified under the same conditions and no ligand decomplexation of the metallacycle was observed. Subsequently, secondary arsines bearing the As-H bond were applied in deuteration by directed ortho-metalation (DoM) and decomplexation strategies. In the former, HAsPh2 was a convenient deuterium shuttle which facilitated the ortho-deuteration of DoM-palladacycle intermediates under neutral conditions. High deuterium incorporation (>99%) was achieved without specialized preformed deuterating agents. In the latter, HAsPh2 afforded the preligands of monomeric, dimeric, bidentate, and tridentate complexes of Pd in excellent yields of 95-98% within 30 min at room temperature. Key reaction steps for the intramolecular insertion of As-H into the Pd-C bond were outlined, and the effects of regioisomerism on the ortho-protonation pathway were evaluated. Nanyang Technological University W.S.T. acknowledges NTU for the award of a research scholarship. Grant M4080454 is acknowledged for funding this work. 2022-02-15T05:05:12Z 2022-02-15T05:05:12Z 2020 Journal Article Tay, W. S., Li, Y., Pullarkat, S. A. & Leung, P. (2020). Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds. Organometallics, 39(1), 182-188. https://dx.doi.org/10.1021/acs.organomet.9b00723 0276-7333 https://hdl.handle.net/10356/155198 10.1021/acs.organomet.9b00723 2-s2.0-85076999449 1 39 182 188 en M4080454 Organometallics © 2019 American Chemical Society. All rights reserved.
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Science::Chemistry
Phosphorus Compounds
Protonation
spellingShingle Science::Chemistry
Phosphorus Compounds
Protonation
Tay, Wee Shan
Li, Yongxin
Pullarkat, Sumod A.
Leung, Pak-Hing
Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds
description Secondary arsines were observed to decomplex strongly chelating phosphapalladacycles rapidly under mild conditions. As-H bond migration led to ortho-protonation of the C,P ligand. On the other hand, N-H and P-H bonds in amine and phosphine analogues were acidified under the same conditions and no ligand decomplexation of the metallacycle was observed. Subsequently, secondary arsines bearing the As-H bond were applied in deuteration by directed ortho-metalation (DoM) and decomplexation strategies. In the former, HAsPh2 was a convenient deuterium shuttle which facilitated the ortho-deuteration of DoM-palladacycle intermediates under neutral conditions. High deuterium incorporation (>99%) was achieved without specialized preformed deuterating agents. In the latter, HAsPh2 afforded the preligands of monomeric, dimeric, bidentate, and tridentate complexes of Pd in excellent yields of 95-98% within 30 min at room temperature. Key reaction steps for the intramolecular insertion of As-H into the Pd-C bond were outlined, and the effects of regioisomerism on the ortho-protonation pathway were evaluated.
author2 School of Physical and Mathematical Sciences
author_facet School of Physical and Mathematical Sciences
Tay, Wee Shan
Li, Yongxin
Pullarkat, Sumod A.
Leung, Pak-Hing
format Article
author Tay, Wee Shan
Li, Yongxin
Pullarkat, Sumod A.
Leung, Pak-Hing
author_sort Tay, Wee Shan
title Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds
title_short Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds
title_full Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds
title_fullStr Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds
title_full_unstemmed Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds
title_sort divergent reactivity of phosphapalladacycles toward e-h (e = n, p, as) bonds
publishDate 2022
url https://hdl.handle.net/10356/155198
_version_ 1725985799096238080