Deeth, Robert J.. (2006) A theoretical rationale for the formation, structure and spin state of pentacyanochromate(II). European Journal of Inorganic Chemistry, Volume 2006 (Number 13). pp. 2551-2555. ISSN 1434-1948

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Abstract

The pentacyanochromate(II) complex is unusual in two respects. Firstly, it is one of the few homoleptic cyanide species with a high-spin ground state. Secondly, it was synthesised during an attempt to make the hexacoordinate complex. A combination of qualitative ligand field theory and quantitative density functional theory including solvation effects is applied to rationalise these observations. The spin state depends on the d orbital energy differences and how the promotion energy, PE, associated with a change in spin state compares to the d-d spin pairing energy, SPE. The calculations show that PE > SPE for octahedral [Cr-II(CN)(6)](4-), hence it has a spin triplet S = 1 ground state, while PE < SPE for [Cr-II(CN)(5)](3-), hence it is high spin with S = 2. The hexacyanide is stabilised in aqueous solution by solvation. In less polar solvents such as acetonitrile, the unfavourable electrostatic interactions dominate and the reaction stops at the pentacyano complex. In both complexes, the cyanide behaves as a strong-field ligand and is both a good sigma donor and pi acceptor.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Chemistry
Journal or Publication Title:	European Journal of Inorganic Chemistry
Publisher:	Wiley-VCH Verlag GMBH
ISSN:	1434-1948
Date:	3 July 2006
Volume:	Volume 2006
Number:	Number 13
Number of Pages:	5
Page Range:	pp. 2551-2555
Identification Number:	10.1002/ejic.200600137
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
URI:	http://wrap.warwick.ac.uk/id/eprint/33315

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