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Issue 8, 2014
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The effect of remote substitution on the formation of preferential isomers of cobalt(iii)-tetrazolate complexes by microwave assisted cycloaddition

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Abstract

The 1,3-dipolar cycloaddition reaction of cis-[Co(N3)2(en)2]NO31 with different organonitriles (NCR) under focussed microwave irradiation produced bis-tetrazolate complexes [Co(N4CR)2(en)2](NO3). Interestingly, in the case of 3-cyano pyridine the reaction produced both cis- and trans-isomers (cis-2 and trans-2), whereas for 4-cyano pyridine the compound obtained was exclusively cis (cis-3) and for 4-bromobenzonitrile it was only the trans- (trans-4) compound which was isolated. This indicates a probable role of remote substitution of the phenyl ring in dictating the formation of the preferential isomer. When starting from the trans-isomer of the diazido complex (trans-[Co(N3)2(en)2]ClO4, 1a), upon reacting with different nitriles a mixture of cis- and trans-isomers of [Co(N4CR)2(en)2]ClO4 was produced in each case, with a greater preference towards cis-geometry [R = 4-NC5H4 (cis-5 and trans-5), 4-BrC6H4 (cis-6 and trans-6) and C6H5 (cis-7 and trans-7)]. The preferential formation of the cis-analogue of compound trans-4 when starting from the trans-precursor was quite curious. A theoretical investigation of compounds trans-4 and cis-6 reveals that the greater stability of the trans-complex 4 may arise from additional van der Waals interactions in the solid state because of the presence of an extra DMF molecule as solvent of crystallization. However, an interacting counter-anion and a probable halogen–halogen interaction may also contribute to the formation of preferential isomers for cycloaddition complexes, even in the solution state.

Graphical abstract: The effect of remote substitution on the formation of preferential isomers of cobalt(iii)-tetrazolate complexes by microwave assisted cycloaddition

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Article information


Submitted
02 Jul 2014
Accepted
18 Jul 2014
First published
24 Jul 2014

Inorg. Chem. Front., 2014,1, 599-610
Article type
Paper
Author version available

The effect of remote substitution on the formation of preferential isomers of cobalt(III)-tetrazolate complexes by microwave assisted cycloaddition

M. Saha, R. Nasani, M. Das, S. M. Mobin, B. Pathak and S. Mukhopadhyay, Inorg. Chem. Front., 2014, 1, 599
DOI: 10.1039/C4QI00089G

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