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Using Functionalized Silyl Ligands To Suppress Solvent Coordination to Silyl Lanthanide(II) Complexes
[Image: see text] The reaction of the potassium 1,3-trisilanediide Me(2)Si[Si(Me(3)Si)(2)K](2) with SmI(2) and YbI(2) was found to give the respective disilylated complexes Me(2)Si[Si(Me(3)Si)(2)](2)Sm·2THF and Me(2)Si[Si(Me(3)Si)(2)](2)Yb·2THF. Desolvation of coordinated solvent molecules in these...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2017
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5415877/ https://www.ncbi.nlm.nih.gov/pubmed/28398724 http://dx.doi.org/10.1021/acs.inorgchem.7b00420 |
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author | Zitz, Rainer Hlina, Johann Aghazadeh Meshgi, Mohammad Krenn, Heinz Marschner, Christoph Szilvási, Tibor Baumgartner, Judith |
author_facet | Zitz, Rainer Hlina, Johann Aghazadeh Meshgi, Mohammad Krenn, Heinz Marschner, Christoph Szilvási, Tibor Baumgartner, Judith |
author_sort | Zitz, Rainer |
collection | PubMed |
description | [Image: see text] The reaction of the potassium 1,3-trisilanediide Me(2)Si[Si(Me(3)Si)(2)K](2) with SmI(2) and YbI(2) was found to give the respective disilylated complexes Me(2)Si[Si(Me(3)Si)(2)](2)Sm·2THF and Me(2)Si[Si(Me(3)Si)(2)](2)Yb·2THF. Desolvation of coordinated solvent molecules in these complexes made their handling difficult. However, using a number of functionalized silanide ligands, complexes with a diminished number or even no coordinated solvent molecules were obtained ((R(3)Si)(2)Ln(THF)(x) (x = 0–3)). The structures of all new lanthanide compounds were determined by X-ray single-crystal structure analysis. NMR spectroscopic analysis of some Yb–silyl complexes pointed at highly ionic interactions between the silyl ligands and the lanthanides. This bonding picture was supported by DFT calculations at the B3PW91/Basis1 level of theory. Detailed theoretical analysis of a disilylated Eu(II) complex suggests that its singly occupied molecular orbitals (SOMOs) are very close in energy to the ligand silicon lone pairs (HOMO), and SQUID magnetometry measurements of the complex showed a deviation from the expected behavior for a free Eu(II) ion, which might be due to a ligand–metal interaction. |
format | Online Article Text |
id | pubmed-5415877 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-54158772017-05-05 Using Functionalized Silyl Ligands To Suppress Solvent Coordination to Silyl Lanthanide(II) Complexes Zitz, Rainer Hlina, Johann Aghazadeh Meshgi, Mohammad Krenn, Heinz Marschner, Christoph Szilvási, Tibor Baumgartner, Judith Inorg Chem [Image: see text] The reaction of the potassium 1,3-trisilanediide Me(2)Si[Si(Me(3)Si)(2)K](2) with SmI(2) and YbI(2) was found to give the respective disilylated complexes Me(2)Si[Si(Me(3)Si)(2)](2)Sm·2THF and Me(2)Si[Si(Me(3)Si)(2)](2)Yb·2THF. Desolvation of coordinated solvent molecules in these complexes made their handling difficult. However, using a number of functionalized silanide ligands, complexes with a diminished number or even no coordinated solvent molecules were obtained ((R(3)Si)(2)Ln(THF)(x) (x = 0–3)). The structures of all new lanthanide compounds were determined by X-ray single-crystal structure analysis. NMR spectroscopic analysis of some Yb–silyl complexes pointed at highly ionic interactions between the silyl ligands and the lanthanides. This bonding picture was supported by DFT calculations at the B3PW91/Basis1 level of theory. Detailed theoretical analysis of a disilylated Eu(II) complex suggests that its singly occupied molecular orbitals (SOMOs) are very close in energy to the ligand silicon lone pairs (HOMO), and SQUID magnetometry measurements of the complex showed a deviation from the expected behavior for a free Eu(II) ion, which might be due to a ligand–metal interaction. American Chemical Society 2017-04-11 2017-05-01 /pmc/articles/PMC5415877/ /pubmed/28398724 http://dx.doi.org/10.1021/acs.inorgchem.7b00420 Text en Copyright © 2017 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
spellingShingle | Zitz, Rainer Hlina, Johann Aghazadeh Meshgi, Mohammad Krenn, Heinz Marschner, Christoph Szilvási, Tibor Baumgartner, Judith Using Functionalized Silyl Ligands To Suppress Solvent Coordination to Silyl Lanthanide(II) Complexes |
title | Using Functionalized Silyl Ligands To Suppress Solvent
Coordination to Silyl Lanthanide(II) Complexes |
title_full | Using Functionalized Silyl Ligands To Suppress Solvent
Coordination to Silyl Lanthanide(II) Complexes |
title_fullStr | Using Functionalized Silyl Ligands To Suppress Solvent
Coordination to Silyl Lanthanide(II) Complexes |
title_full_unstemmed | Using Functionalized Silyl Ligands To Suppress Solvent
Coordination to Silyl Lanthanide(II) Complexes |
title_short | Using Functionalized Silyl Ligands To Suppress Solvent
Coordination to Silyl Lanthanide(II) Complexes |
title_sort | using functionalized silyl ligands to suppress solvent
coordination to silyl lanthanide(ii) complexes |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5415877/ https://www.ncbi.nlm.nih.gov/pubmed/28398724 http://dx.doi.org/10.1021/acs.inorgchem.7b00420 |
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