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Issue 7, 2006
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Carbonylcarbonyl interactions in first-row transition metal complexes

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Abstract

Carbonylcarbonyl interactions involving Tr–C[double bond, length as m-dash]O moieties (Tr = first-row transition element) have been studied using crystal structure data retrieved from the Cambridge Structural Database and by use of DFT calculations. By comparison with organic ketones, Tr–C[double bond, length as m-dash]O systems show an increased tendency to form close CO⋯CO interactions, with 45% of these forming pairwise interactions in a sheared antiparallel dimer motif and 55% having a perpendicular (single interaction) geometry. The bulky Tr and steric hindrance arising from other ligands at Tr play a significant role in the formation and geometry of the interactions. DFT calculations for the antiparallel dimer indicate that interaction energies for Tr–C[double bond, length as m-dash]O systems are slightly stronger than for organic ketones, and there is evidence of a stronger C[double bond, length as m-dash]O bond dipole in Tr–C[double bond, length as m-dash]O systems. With interaction energies comparable to those for medium strength hydrogen bonds, we conclude that CO⋯CO interactions in Tr–C[double bond, length as m-dash]O species may have a role to play in the design of novel carbonyl-containing inorganic and metal–organic structures.

Graphical abstract: Carbonyl⋯carbonyl interactions in first-row transition metal complexes

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Publication details

The article was received on 26 May 2006, accepted on 26 Jun 2006 and first published on 03 Jul 2006


Article type: Paper
DOI: 10.1039/B607531M
Citation: CrystEngComm, 2006,8, 563-570

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    Carbonylcarbonyl interactions in first-row transition metal complexes

    H. A. Sparkes, P. R. Raithby, E. Clot, G. P. Shields, J. A. Chisholm and F. H. Allen, CrystEngComm, 2006, 8, 563
    DOI: 10.1039/B607531M

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