Issue 18, 2000
From the journal:

Journal of the Chemical Society, Dalton Transactions

Conversion of some substituted phenols to the corresponding masked thiophenols, synthesis of a dinickel(II) dithiolate macrocyclic complex and isolation of some metal- and ligand-based oxidation products

Sally Brooker,*a   Graham B. Caygill,a   Paul D. Croucher,a   Tony C. Davidson,a   Derrick L. J. Clive,b   Stephen R. Magnuson,b   Stephen P. Cramercd  and  Corie Y. Ralstoncd  

* Corresponding authors

a Department of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
E-mail: sbrooker@alkali.otago.ac.nz

b Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada

c Department of Applied Science, University of California at Davis, Davis, USA

d Lawrence Berkeley National Laboratory, Energy and Environment Division, Berkeley, USA

Abstract

A modified preparation of the masked thiolate head unit S-(2,6-diformyl-4-methylphenyl) dimethylthiocarbamate 6 is detailed and two new masked thiolate head units, S-(2,6-diformyl-4-tert-butylphenyl) dimethylthiocarbamate 7 and S-(2-formylphenyl) dimethylthiocarbamate 8, are prepared by this method. The synthesis, crystal structure, NMR spectra and electrochemical properties of the first macrocyclic complex to be derived from 7, [Ni2L1](ClO4)2, are discussed. Oxidation of [Ni2L2](CF3SO3)2 (L22− is derived from 6 and 1,3-diaminopropane) with cerium(IV) ammonium nitrate led to the precipitation of the black complex [Ni2L2][Ce(NO3)6], which is believed to contain a single nickel(III) centre. This complex decomposes in DMF over time (≈24 hours) to form the red dinickel(II) complex [Ni2L2](NO3)2·2DMF which has been structurally characterised. Oxidation of [Ni2L3](CF3SO3)2 (L32− is derived from 6 and 1,4-diaminobutane) with I2 results in ligand oxidation forming the metal free macrocycle (L3′)2+ which contains two five membered isothiazole rings. This is confirmed by the X-ray crystal structure determinations of (L3′)(I3)2 and (L3′)(I)2(I2)5.

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Article information

DOI
https://doi.org/10.1039/B004214P
Article type
Paper
Submitted
26 May 2000
Accepted
25 Jul 2000
First published
23 Aug 2000

J. Chem. Soc., Dalton Trans., 2000, 3113-3121

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Conversion of some substituted phenols to the corresponding masked thiophenols, synthesis of a dinickel(II) dithiolate macrocyclic complex and isolation of some metal- and ligand-based oxidation products

S. Brooker, G. B. Caygill, P. D. Croucher, T. C. Davidson, D. L. J. Clive, S. R. Magnuson, S. P. Cramer and C. Y. Ralston, J. Chem. Soc., Dalton Trans., 2000, 3113 DOI: 10.1039/B004214P

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