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Metallacyclosilanes of Calcium, Yttrium, and Iron

[Image: see text] Utilizing a choice of α,ω-oligosilanylene diides, it is possible to synthesize a number of heterocyclosilanes with heteroelements of calcium, yttrium, and iron by metathesis reactions with respective metal halides CaI(2), YCl(3), and FeBr(2). (29)Si NMR spectroscopic analysis of th...

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Autores principales: Pöcheim, Alexander, Zitz, Rainer, Hönigsberger, Julia, Marschner, Christoph, Baumgartner, Judith
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9644368/
https://www.ncbi.nlm.nih.gov/pubmed/36281990
http://dx.doi.org/10.1021/acs.inorgchem.2c02508
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author Pöcheim, Alexander
Zitz, Rainer
Hönigsberger, Julia
Marschner, Christoph
Baumgartner, Judith
author_facet Pöcheim, Alexander
Zitz, Rainer
Hönigsberger, Julia
Marschner, Christoph
Baumgartner, Judith
author_sort Pöcheim, Alexander
collection PubMed
description [Image: see text] Utilizing a choice of α,ω-oligosilanylene diides, it is possible to synthesize a number of heterocyclosilanes with heteroelements of calcium, yttrium, and iron by metathesis reactions with respective metal halides CaI(2), YCl(3), and FeBr(2). (29)Si NMR spectroscopic analysis of the calcacyclosilanes suggests that these compounds retain a strong oligosilanylene dianion character, which is more pronounced than in the analogous magnesacyclosilanes. As the electronegativity of calcium lies between potassium and magnesium, silyl calcium reagents should be considered as building blocks with an attractive reactivity profile. Reaction of a 1,4-oligosilanylene diide with YCl(3) gave the five-membered yttracyclosilane as an ate-complex with two chlorides still attached to the yttrium atom. Reaction of the obtained compound with two equivalents of NaCp led to another five-membered yttracyclosilane ate-complex with an yttracene fragment. When using a dianionic oligosilanylene ligand containing a siloxane unit, the siloxane oxygen acted as an additional coordination site for Ca and Y. When the same ligand was used to prepare a cyclic 1-ferra-4-oxatetrasilacyclohexane, an analogous transannular interaction between the iron and oxygen atoms is missing.
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spelling pubmed-96443682022-11-15 Metallacyclosilanes of Calcium, Yttrium, and Iron Pöcheim, Alexander Zitz, Rainer Hönigsberger, Julia Marschner, Christoph Baumgartner, Judith Inorg Chem [Image: see text] Utilizing a choice of α,ω-oligosilanylene diides, it is possible to synthesize a number of heterocyclosilanes with heteroelements of calcium, yttrium, and iron by metathesis reactions with respective metal halides CaI(2), YCl(3), and FeBr(2). (29)Si NMR spectroscopic analysis of the calcacyclosilanes suggests that these compounds retain a strong oligosilanylene dianion character, which is more pronounced than in the analogous magnesacyclosilanes. As the electronegativity of calcium lies between potassium and magnesium, silyl calcium reagents should be considered as building blocks with an attractive reactivity profile. Reaction of a 1,4-oligosilanylene diide with YCl(3) gave the five-membered yttracyclosilane as an ate-complex with two chlorides still attached to the yttrium atom. Reaction of the obtained compound with two equivalents of NaCp led to another five-membered yttracyclosilane ate-complex with an yttracene fragment. When using a dianionic oligosilanylene ligand containing a siloxane unit, the siloxane oxygen acted as an additional coordination site for Ca and Y. When the same ligand was used to prepare a cyclic 1-ferra-4-oxatetrasilacyclohexane, an analogous transannular interaction between the iron and oxygen atoms is missing. American Chemical Society 2022-10-25 2022-11-07 /pmc/articles/PMC9644368/ /pubmed/36281990 http://dx.doi.org/10.1021/acs.inorgchem.2c02508 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Pöcheim, Alexander
Zitz, Rainer
Hönigsberger, Julia
Marschner, Christoph
Baumgartner, Judith
Metallacyclosilanes of Calcium, Yttrium, and Iron
title Metallacyclosilanes of Calcium, Yttrium, and Iron
title_full Metallacyclosilanes of Calcium, Yttrium, and Iron
title_fullStr Metallacyclosilanes of Calcium, Yttrium, and Iron
title_full_unstemmed Metallacyclosilanes of Calcium, Yttrium, and Iron
title_short Metallacyclosilanes of Calcium, Yttrium, and Iron
title_sort metallacyclosilanes of calcium, yttrium, and iron
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9644368/
https://www.ncbi.nlm.nih.gov/pubmed/36281990
http://dx.doi.org/10.1021/acs.inorgchem.2c02508
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