The University of Southampton
University of Southampton Institutional Repository

Cationic aza-macrocyclic complexes of germanium(ii) and silicon(iv)

Cationic aza-macrocyclic complexes of germanium(ii) and silicon(iv)
Cationic aza-macrocyclic complexes of germanium(ii) and silicon(iv)
[GeCl2(dioxane)] reacts with the neutral aza-macrocyclic ligands L, L = Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane), Me4cyclen (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane) or Me4cyclam (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and two mol. equiv. of Me3SiO3SCF3 in thf solution to yield the unusual and hydrolytically very sensitive [Ge(L)][O3SCF3]2 as white solids in moderate yield. Using shorter reaction times [Ge(Me3tacn)]Cl2 and [Ge(Me3tacn)]Cl[O3SCF3] were also isolated; the preparation of [Ge(Me4cyclen)][GeCl3]2 is also described. The structures of the Me3tacn complexes show ?3-coordination of the macrocycle, with the anions interacting only weakly to produce very distorted five- or six-coordination at germanium. In contrast, the structure of [Ge(Me4cyclen)][O3SCF3]2 shows no anion interactions, and a distorted square planar geometry at germanium from coordination to the tetra-aza macrocycle. Crystal structures of the Si(IV) complexes, [SiCl3(Me3tacn)]Y (Y = O3SCF3, BArF; [B{3,5-(CF3)2C6H3}4]) and [SiHCl2(Me3tacn)][BArF], obtained from reaction of SiCl4 or SiHCl3 with Me3tacn, followed by addition of either Me3SiO3SCF3 or Na[BArF], contain distorted octahedral cations, with facial ?3-coordinated Me3tacn. The open-chain triamine, Me2NCH2CH2N(Me)CH2CH2NMe2 (pmdta), forms [SiCl3(pmdta)][BArF] and [SiBr3(pmdta)][BArF] under similar conditions, containing mer-octahedral cations.
0300-9246
20898-20905
Everett, Matthew
91318c08-7fac-4eaf-9a59-436cb303cd49
Jolleys, Andrew
29e25ac4-2ff1-4267-8278-a433a94d5c6f
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Pugh, David
9ec61267-ae4d-40d8-bebf-0d603e2588d3
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Everett, Matthew
91318c08-7fac-4eaf-9a59-436cb303cd49
Jolleys, Andrew
29e25ac4-2ff1-4267-8278-a433a94d5c6f
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Pugh, David
9ec61267-ae4d-40d8-bebf-0d603e2588d3
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Everett, Matthew, Jolleys, Andrew, Levason, William, Light, Mark E., Pugh, David and Reid, Gillian (2015) Cationic aza-macrocyclic complexes of germanium(ii) and silicon(iv). Dalton Transactions, 44 (48), 20898-20905. (doi:10.1039/c5dt03941j).

Record type: Article

Abstract

[GeCl2(dioxane)] reacts with the neutral aza-macrocyclic ligands L, L = Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane), Me4cyclen (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane) or Me4cyclam (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and two mol. equiv. of Me3SiO3SCF3 in thf solution to yield the unusual and hydrolytically very sensitive [Ge(L)][O3SCF3]2 as white solids in moderate yield. Using shorter reaction times [Ge(Me3tacn)]Cl2 and [Ge(Me3tacn)]Cl[O3SCF3] were also isolated; the preparation of [Ge(Me4cyclen)][GeCl3]2 is also described. The structures of the Me3tacn complexes show ?3-coordination of the macrocycle, with the anions interacting only weakly to produce very distorted five- or six-coordination at germanium. In contrast, the structure of [Ge(Me4cyclen)][O3SCF3]2 shows no anion interactions, and a distorted square planar geometry at germanium from coordination to the tetra-aza macrocycle. Crystal structures of the Si(IV) complexes, [SiCl3(Me3tacn)]Y (Y = O3SCF3, BArF; [B{3,5-(CF3)2C6H3}4]) and [SiHCl2(Me3tacn)][BArF], obtained from reaction of SiCl4 or SiHCl3 with Me3tacn, followed by addition of either Me3SiO3SCF3 or Na[BArF], contain distorted octahedral cations, with facial ?3-coordinated Me3tacn. The open-chain triamine, Me2NCH2CH2N(Me)CH2CH2NMe2 (pmdta), forms [SiCl3(pmdta)][BArF] and [SiBr3(pmdta)][BArF] under similar conditions, containing mer-octahedral cations.

Full text not available from this repository.

More information

Accepted/In Press date: 6 November 2015
e-pub ahead of print date: 9 November 2015
Published date: 28 December 2015
Organisations: Chemistry

Identifiers

Local EPrints ID: 385721
URI: http://eprints.soton.ac.uk/id/eprint/385721
ISSN: 0300-9246
PURE UUID: a7ff2285-f71a-443e-96c4-186f0853d777
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

Catalogue record

Date deposited: 21 Jan 2016 13:46
Last modified: 18 Feb 2021 16:52

Export record

Altmetrics

Contributors

Author: Matthew Everett
Author: Andrew Jolleys
Author: William Levason ORCID iD
Author: Mark E. Light ORCID iD
Author: David Pugh
Author: Gillian Reid ORCID iD

University divisions

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×