Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/62187
Title: Can cyclen bind alkali metal azides? A DFT study as a precursor to synthesis
Authors: Bhakhoa, H
Rhyman, L
Lee, EPF
Ramasami, P
Dyke, JM
Keywords: Alkali metals
Azides
Density functional calculations
Host-guest chemistry
Sandwich complexes
Issue Date: 2016
Publisher: Wiley-VCH
Source: Chemistry - a European journal, 2016, v. 22, no. 13, p. 4469-4482 How to cite?
Journal: Chemistry - a European journal 
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.
URI: http://hdl.handle.net/10397/62187
ISSN: 0947-6539
EISSN: 1521-3765
DOI: 10.1002/chem.201504607
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