Cargando…
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...
Autores principales: | , , , , |
---|---|
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 |
_version_ | 1784826726702907392 |
---|---|
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. |
format | Online Article Text |
id | pubmed-9644368 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
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 |
work_keys_str_mv | AT pocheimalexander metallacyclosilanesofcalciumyttriumandiron AT zitzrainer metallacyclosilanesofcalciumyttriumandiron AT honigsbergerjulia metallacyclosilanesofcalciumyttriumandiron AT marschnerchristoph metallacyclosilanesofcalciumyttriumandiron AT baumgartnerjudith metallacyclosilanesofcalciumyttriumandiron |