The University of Southampton
University of Southampton Institutional Repository

Can cyclen bind alkali metal azides? a DFT study as a precursor to synthesis

Can cyclen bind alkali metal azides? a DFT study as a precursor to synthesis
Can cyclen bind alkali metal azides? a DFT study as a precursor to synthesis
Can cyclen (1,4,7,10-tetraazacyclododecane) bind alkali metal azides? This question is addressed by studying the geometric and electronic structures of the alkali metal azide-cyclen [M(cyclen)N3] complexes using density functional theory (DFT). The effects of adding a second cyclen ring to form the sandwich alkali metal azide-cyclen [M(cyclen)2N3] complexes are also investigated. N3? is found to bind to a M+(cyclen) template to give both end-on and side-on structures. In the end-on structures, the terminal nitrogen atom of the azide group (N1) bonds to the metal as well as to a hydrogen atom of the cyclen ring through a hydrogen bond in an end-on configuration to the cyclen ring. In the side-on structures, the N3 unit is bonded (in a side-on configuration to the cyclen ring) to the metal through the terminal nitrogen atom of the azide group (N1), and through the other terminal nitrogen atom (N3) of the azide group by a hydrogen bond to a hydrogen atom of the cyclen ring. For all the alkali metals, the N3-side-on structure is lowest in energy. Addition of a second cyclen unit to [M(cyclen)N3] to form the sandwich compounds [M(cyclen)2N3] causes the bond strength between the metal and the N3 unit to decrease. It is hoped that this computational study will be a precursor to the synthesis and experimental study of these new macrocyclic compounds; structural parameters and infrared spectra were computed, which will assist future experimental work.
0947-6539
4469-4482
Bhakhoa, H.
54097e7a-e1d9-4005-b6af-3571672eb586
Rhyman, L.
1a7cf70c-ea81-49d6-809d-c45f3c381cad
Lee, E.P.F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Ramasami, P.
b623c0f0-59ad-49c8-9baa-5cb4fce3008c
Dyke, J.M.
46393b45-6694-46f3-af20-d7369d26199f
Bhakhoa, H.
54097e7a-e1d9-4005-b6af-3571672eb586
Rhyman, L.
1a7cf70c-ea81-49d6-809d-c45f3c381cad
Lee, E.P.F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Ramasami, P.
b623c0f0-59ad-49c8-9baa-5cb4fce3008c
Dyke, J.M.
46393b45-6694-46f3-af20-d7369d26199f

Bhakhoa, H., Rhyman, L., Lee, E.P.F., Ramasami, P. and Dyke, J.M. (2016) Can cyclen bind alkali metal azides? a DFT study as a precursor to synthesis. Chemistry - A European Journal, 22 (13), 4469-4482. (doi:10.1002/chem.201504607).

Record type: Article

Abstract

Can cyclen (1,4,7,10-tetraazacyclododecane) bind alkali metal azides? This question is addressed by studying the geometric and electronic structures of the alkali metal azide-cyclen [M(cyclen)N3] complexes using density functional theory (DFT). The effects of adding a second cyclen ring to form the sandwich alkali metal azide-cyclen [M(cyclen)2N3] complexes are also investigated. N3? is found to bind to a M+(cyclen) template to give both end-on and side-on structures. In the end-on structures, the terminal nitrogen atom of the azide group (N1) bonds to the metal as well as to a hydrogen atom of the cyclen ring through a hydrogen bond in an end-on configuration to the cyclen ring. In the side-on structures, the N3 unit is bonded (in a side-on configuration to the cyclen ring) to the metal through the terminal nitrogen atom of the azide group (N1), and through the other terminal nitrogen atom (N3) of the azide group by a hydrogen bond to a hydrogen atom of the cyclen ring. For all the alkali metals, the N3-side-on structure is lowest in energy. Addition of a second cyclen unit to [M(cyclen)N3] to form the sandwich compounds [M(cyclen)2N3] causes the bond strength between the metal and the N3 unit to decrease. It is hoped that this computational study will be a precursor to the synthesis and experimental study of these new macrocyclic compounds; structural parameters and infrared spectra were computed, which will assist future experimental work.

Text
Manuscript.pdf - Accepted Manuscript
Download (1MB)

More information

Accepted/In Press date: 10 November 2015
e-pub ahead of print date: 16 February 2016
Published date: 18 March 2016
Organisations: Chemistry

Identifiers

Local EPrints ID: 389803
URI: https://eprints.soton.ac.uk/id/eprint/389803
ISSN: 0947-6539
PURE UUID: a050f810-627f-462c-bde1-c0023c5b8bee
ORCID for J.M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

Catalogue record

Date deposited: 15 Mar 2016 15:45
Last modified: 09 Jun 2018 04:01

Export record

Altmetrics

Contributors

Author: H. Bhakhoa
Author: L. Rhyman
Author: E.P.F. Lee
Author: P. Ramasami
Author: J.M. Dyke 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 https://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.

×