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Synthesis, Structure and Electrochemical Properties of Triarylamine Bridged Dicobaltdicarbon Tetrahedrane Clusters

Man, WY; Vincent, KB; Spencer, HJ; Yufit, DS; Howard, JAK; Low, PJ

Synthesis, Structure and Electrochemical Properties of Triarylamine Bridged Dicobaltdicarbon Tetrahedrane Clusters Thumbnail


Authors

WY Man

KB Vincent

HJ Spencer

DS Yufit

JAK Howard

PJ Low



Abstract

The reaction of [Co2(CO)6(dppm)] (1) with the ethynyl substituted triarylamines [N(C6H4-4-C≡CSiMe3)(C6H4Me-4)2] (2) or [N(C6H4-4-C≡CSiMe3)2(C6H4Me-4)] (3) affords [{Co2(CO)4(dppm)}{μ-(Me3SiC2-4-C6H4)N(C6H4Me-4)2}] (4) or a mixture of [Co2{μ-Me3SiC2-4-C6H4N(C6H4-4-C≡CSiMe3)(C6H4Me-4)}(CO)4(dppm)] (5) and [{Co2(CO)4(dppm)}2{μ-(Me3SiC2-4-C6H4)2N(C6H4Me-4)}] (6), respectively. A combination of electrochemical measurements in different electrolytes, and IR and NIR spectroscopic studies of these compounds, which feature both organometallic and organic redox active groups, indicates that the cluster centres are oxidised at significantly less positive potentials than the triarylamine moieties. Reaction of 6 with one or two equivalents of [Fe(η-C5H4COMe)Cp]PF6 gives [6][PF6]n (n = 1, 2), which are best described in terms of cluster-localised oxidation processes. Despite the presence of the substantial differences in the first and second cluster based oxidations in 6 (up to 220 mV in CH2Cl2/0.1 M [NBu4][BAr4F]), there is little ground state delocalisation between the cluster centres through the triarylamine bridge. The stabilisation of [6]+ with respect to disproportionation can be attributed to electrostatic effects.

Citation

Man, W., Vincent, K., Spencer, H., Yufit, D., Howard, J., & Low, P. (2012). Synthesis, Structure and Electrochemical Properties of Triarylamine Bridged Dicobaltdicarbon Tetrahedrane Clusters. Journal of Cluster Science, 23(3), 853-872. https://doi.org/10.1007/s10876-012-0482-y

Journal Article Type Article
Publication Date Sep 1, 2012
Deposit Date Aug 13, 2013
Publicly Available Date Aug 15, 2013
Journal Journal of Cluster Science
Print ISSN 1040-7278
Electronic ISSN 1572-8862
Publisher Springer
Peer Reviewed Peer Reviewed
Volume 23
Issue 3
Pages 853-872
DOI https://doi.org/10.1007/s10876-012-0482-y
Keywords Cobalt-alkyne, Electron transfer, Electrochemistry, Spectroelectrochemistry, Mixed valence.
Public URL https://durham-repository.worktribe.com/output/1451960

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Copyright Statement
The original publication is available at www.springerlink.com





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