Cargando…

Dinuclear and tetranuclear group 10 metal complexes constructed from linear tetrasilane comprising both Si-H and Si-Si moieties

The activation of Si-H bonds and/or Si-Si bonds in organosilicon compounds by transition-metal species plays a crucial role for the production of functional organosilicon compounds. Although group-10-metal species are frequently used to activate Si-H and/or Si-Si bonds, so far, systematic investigat...

Descripción completa

Detalles Bibliográficos
Autores principales: Umehara, Yoshihiko, Usui, Ryosuke, Wada, Yoshimasa, Sunada, Yusuke
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10185686/
https://www.ncbi.nlm.nih.gov/pubmed/37188952
http://dx.doi.org/10.1038/s42004-023-00892-8
_version_ 1785042410794909696
author Umehara, Yoshihiko
Usui, Ryosuke
Wada, Yoshimasa
Sunada, Yusuke
author_facet Umehara, Yoshihiko
Usui, Ryosuke
Wada, Yoshimasa
Sunada, Yusuke
author_sort Umehara, Yoshihiko
collection PubMed
description The activation of Si-H bonds and/or Si-Si bonds in organosilicon compounds by transition-metal species plays a crucial role for the production of functional organosilicon compounds. Although group-10-metal species are frequently used to activate Si-H and/or Si-Si bonds, so far, systematic investigation to clarify the preferences of these metal species with respect to the activation of Si-H and/or Si-Si bonds remain elusive. Here, we report that platinum(0) species that bear isocyanide or N-heterocyclic-carbene (NHC) ligands selectively activates the terminal Si-H bonds of the linear tetrasilane Ph(2)(H)SiSiPh(2)SiPh(2)Si(H)Ph(2) in a stepwise manner, whereby the Si-Si bonds remain intact. In contrast, analogous palladium(0) species are preferably inserted into the Si-Si bonds of the same linear tetrasilane, whereby the terminal Si-H bonds remain intact. Substitution of the terminal hydride groups in Ph(2)(H)SiSiPh(2)SiPh(2)Si(H)Ph(2) with chloride groups leads to the insertion of platinum(0) isocyanide into all Si-Si bonds to afford an unprecedented zig-zag Pt(4) cluster.
format Online
Article
Text
id pubmed-10185686
institution National Center for Biotechnology Information
language English
publishDate 2023
publisher Nature Publishing Group UK
record_format MEDLINE/PubMed
spelling pubmed-101856862023-05-17 Dinuclear and tetranuclear group 10 metal complexes constructed from linear tetrasilane comprising both Si-H and Si-Si moieties Umehara, Yoshihiko Usui, Ryosuke Wada, Yoshimasa Sunada, Yusuke Commun Chem Article The activation of Si-H bonds and/or Si-Si bonds in organosilicon compounds by transition-metal species plays a crucial role for the production of functional organosilicon compounds. Although group-10-metal species are frequently used to activate Si-H and/or Si-Si bonds, so far, systematic investigation to clarify the preferences of these metal species with respect to the activation of Si-H and/or Si-Si bonds remain elusive. Here, we report that platinum(0) species that bear isocyanide or N-heterocyclic-carbene (NHC) ligands selectively activates the terminal Si-H bonds of the linear tetrasilane Ph(2)(H)SiSiPh(2)SiPh(2)Si(H)Ph(2) in a stepwise manner, whereby the Si-Si bonds remain intact. In contrast, analogous palladium(0) species are preferably inserted into the Si-Si bonds of the same linear tetrasilane, whereby the terminal Si-H bonds remain intact. Substitution of the terminal hydride groups in Ph(2)(H)SiSiPh(2)SiPh(2)Si(H)Ph(2) with chloride groups leads to the insertion of platinum(0) isocyanide into all Si-Si bonds to afford an unprecedented zig-zag Pt(4) cluster. Nature Publishing Group UK 2023-05-15 /pmc/articles/PMC10185686/ /pubmed/37188952 http://dx.doi.org/10.1038/s42004-023-00892-8 Text en © The Author(s) 2023 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Umehara, Yoshihiko
Usui, Ryosuke
Wada, Yoshimasa
Sunada, Yusuke
Dinuclear and tetranuclear group 10 metal complexes constructed from linear tetrasilane comprising both Si-H and Si-Si moieties
title Dinuclear and tetranuclear group 10 metal complexes constructed from linear tetrasilane comprising both Si-H and Si-Si moieties
title_full Dinuclear and tetranuclear group 10 metal complexes constructed from linear tetrasilane comprising both Si-H and Si-Si moieties
title_fullStr Dinuclear and tetranuclear group 10 metal complexes constructed from linear tetrasilane comprising both Si-H and Si-Si moieties
title_full_unstemmed Dinuclear and tetranuclear group 10 metal complexes constructed from linear tetrasilane comprising both Si-H and Si-Si moieties
title_short Dinuclear and tetranuclear group 10 metal complexes constructed from linear tetrasilane comprising both Si-H and Si-Si moieties
title_sort dinuclear and tetranuclear group 10 metal complexes constructed from linear tetrasilane comprising both si-h and si-si moieties
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10185686/
https://www.ncbi.nlm.nih.gov/pubmed/37188952
http://dx.doi.org/10.1038/s42004-023-00892-8
work_keys_str_mv AT umeharayoshihiko dinuclearandtetranucleargroup10metalcomplexesconstructedfromlineartetrasilanecomprisingbothsihandsisimoieties
AT usuiryosuke dinuclearandtetranucleargroup10metalcomplexesconstructedfromlineartetrasilanecomprisingbothsihandsisimoieties
AT wadayoshimasa dinuclearandtetranucleargroup10metalcomplexesconstructedfromlineartetrasilanecomprisingbothsihandsisimoieties
AT sunadayusuke dinuclearandtetranucleargroup10metalcomplexesconstructedfromlineartetrasilanecomprisingbothsihandsisimoieties