Deactivation of the chlorosulfonate ion coordinated to pentaamminecobalt(III)

Fairlie, DP, Dutton, BH, Mckeon, JA and Jackson, WG (2002) Deactivation of the chlorosulfonate ion coordinated to pentaamminecobalt(III). Inorganic Reaction Mechanisms, 4 3-4: 197-208. doi:10.1080/1028662021000062626

Author Fairlie, DP
Dutton, BH
Mckeon, JA
Jackson, WG
Title Deactivation of the chlorosulfonate ion coordinated to pentaamminecobalt(III)
Journal name Inorganic Reaction Mechanisms   Check publisher's open access policy
ISSN 1028-6624
Publication date 2002-01-01
Sub-type Article (original research)
DOI 10.1080/1028662021000062626
Open Access Status Not Open Access
Volume 4
Issue 3-4
Start page 197
End page 208
Total pages 12
Place of publication Abingdon
Publisher Taylor & Francis Ltd
Language eng
Abstract The synthesis and properties of [(NH3)(5) CoOSO2Cl](ClO4 ) (2) are described. This complex is one of the most reactive cobalt(III) species ever isolated (t(1/2) 10 s; 25degreesC; 0.1 M HClO4). In water it yields [(NH3)(5-) CoOSO3](+) , [(NH3)(5) CoOH2](3+) and [(NH3)(5) CoCl](2+) . The first two of these products come from the expected direct S-Cl and Co-O cleavages. The chloro complex arises via intramolecular linkage isomerisation to the transient [(NH3)(5)Co-ClSO3](2+) species which then cleaves the S-Cl bond. Considerable attention is given to the characterisation of the Co-O3SCl species, including reaction in O-17-H2O where the NMR spectra confirm Co-(17) OSO3 , Co-(OH2)-O-17 and free (OSO32-)-O-17 products. The reactions have been studied also in aqueous base, 0.1 M HClO4 and Me2SO where the same reactions are observed but in quite different proportions. In liquid ammonia, with or without added NH4+ , no O-bonded sulphamate complex [(NH3)(5)CoOSO2NH2](2+) arising from direct S-Cl cleavage is observed. The linkage isomerisation pathway is more pronounced in the absence of base, and this is usual. Mechanisms are discussed in relation to the analogous Co(III)-FSO3- chemistry and to the hydrolysis reactions of the free FSO3- and ClSO3- anions. The most remarkable result is that the ClSO3- ion (and likely FSO3- as well) is substantially deactivated on coordination to Co(III), and such protection is most unusual and no doubt the reason for a successful isolation of the complex of a ligand which hydrolyses in millisec. It can be recovered substantially intact by rapid recrystallisation from water.
Keyword Chemistry, Inorganic & Nuclear
oxygen NMR
Linkage Isomerization
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collections: Excellence in Research Australia (ERA) - Collection
Institute for Molecular Bioscience - Publications
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Created: Sat, 26 Jan 2008, 01:48:32 EST