Synthesis and Characterization of Simple Hydroxo- and Amido-Bridged Cobalt(iii) Dinuclear Ions Missing from the Alfred Werner Collection*

W. Gregory Jackson

doi:10.1071/CH09330

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Synthesis and Characterization of Simple Hydroxo- and Amido-Bridged Cobalt(iii) Dinuclear Ions Missing from the Alfred Werner Collection*

W. Gregory Jackson ^A

+ Author Affiliations

- Author Affiliations

^A School of Physical, Environmental and Mathematical Sciences, Chemistry, The University of New South Wales, Australian Defence Force Academy (UNSW@ADFA), Northcott Drive, Canberra, ACT 2600, Australia. Email: g.jackson@adfa.edu.au

Australian Journal of Chemistry 62(10) 1308-1317 https://doi.org/10.1071/CH09330
Submitted: 11 June 2009 Accepted: 7 September 2009 Published: 13 October 2009

Abstract

The unsymmetrical N,O-dibridging NO₂^– group in the threo (‘rac’) or erythro (‘meso’) isomers of [(en)₂Co(μ-NH₂,μ-NO₂)Co(en)₂]⁴⁺ is cleaved in hot triflic acid to yield a complex that is predominantly meso. This reacts in water to yield the new meso-[(en)₂Co(μ-NH₂,μ-OH)Co(en)₂]⁴⁺ ion. The reactions of the threo- and erythro-μ-NO₂^– isomers in basic (0.1 M) aqueous solution are each retentive, giving the rac- and meso-[(en)₂Co(μ-NH₂,μ-OH)Co(en)₂]⁴⁺ ions as products, respectively. The optically resolved erythro complex gives the achiral meso isomer, which completes the threo/rac and erythro/meso chemical correlations between the two series of dinuclear complexes; the meso synthesis completes the pair – the meso- and rac-[(en)₂Co(μ-NH₂,μ-OH)Co(en)₂]⁴⁺ ions. In HCl, stable μ-Cl, μ-NH₂ dinuclear ions are formed from these μ-NH₂, μ-OH complexes, with retention. The peroxo or superoxo ions rac-[Co(en)₂(μ-NH₂,μ-O₂)Co(en)₂]ⁿ⁺ react with Sn^II to produce symmetrically bridged intermediates that decay to the common and new meso-[(en)₂Co(μ-NH₂,μ-OH)Co(en)₂]⁴⁺ isomer on reaction in Me₂SO. Both the rac and meso isomers of the μ-hydroxo-μ-peroxo complexes are also reduced by Sn^II to give intermediates that in Me₂SO decay to the respective diols with retention. The new rac-[Co(en)₂(μ-OH)₂Co(en)₂]⁴⁺ and meso-[(en)₂Co(μ-NH₂,μ-OH)Co(en)₂]⁴⁺ isomers complete the characterization of rac/meso pairs in both systems. The corresponding μ-sulfate pairs are also reported.

References

^* Dedicated to my friend and colleague Alan McLeod Sargeson.

Synthesis and Characterization of Simple Hydroxo- and Amido-Bridged Cobalt(iii) Dinuclear Ions Missing from the Alfred Werner Collection*

Abstract

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