Trends in base hydrolysis rates of Chlorocobalt(III) complexes of a series of related Pentaamine ligands

Base hydrolysis kinetics of chloropentaaminecobalt(III) complexes of a range of acyclic and cyclic pentaamine ligands, incorporating the rigid -NH-CH 2 -C(CH 3 )(NH 2 )-CH 2 -NH- motif, which must coordinate facially in octahedral complexes, are analysed in terms of ground state structural influence...

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Main Authors: Baran, Yakup (Author) , Comba, Peter (Author) , Lawrance, Geoffrey A. (Author)
Format: Article (Journal)
Language:English
Published: 2002
In: Inorganic reaction mechanisms
Year: 2002, Volume: 4, Issue: 1-2, Pages: 31-47
ISSN:1607-8470
DOI:10.1080/1028662021000062509
Online Access:Verlag, Pay-per-use, Volltext: http://dx.doi.org/10.1080/1028662021000062509
Verlag, Pay-per-use, Volltext: https://doi.org/10.1080/1028662021000062509
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Author Notes:Yakup Baran, Peter Comba & Geoffrey A. Lawrance
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Summary:Base hydrolysis kinetics of chloropentaaminecobalt(III) complexes of a range of acyclic and cyclic pentaamine ligands, incorporating the rigid -NH-CH 2 -C(CH 3 )(NH 2 )-CH 2 -NH- motif, which must coordinate facially in octahedral complexes, are analysed in terms of ground state structural influences on hydrolysis rates. For complexes without experimental structural data, molecular mechanics was used to predict Co-Cl and Co-N bond distances. The computed strain energies and structural parameters both isomers ( trans and cis ) of all compounds are analysed. Although sterically crowded ligands, which should favour a five-coordinate intermediate, exhibit larger k OH values, only a modest correlation between ground state Co-L distances and hydrolysis rates is found. This suggests that the structures of the transition state and/or of the five-coordinate intermediate is important.
Item Description:Article was published online on 18 Oct 2010
Gesehen am 05.03.2018
Physical Description:Online Resource
ISSN:1607-8470
DOI:10.1080/1028662021000062509