Chiral metal complexes 40. The sterically mediated hydrolysis of a coordinated imine

Michael A. Cox, Paul D. Newman, Frederick S. Stephens, Robert S. Vagg*, Peter A. Williams

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    15 Citations (Scopus)

    Abstract

    Reaction of pyridine-2-carboxaldehyde-N-phenylimine (pcp), with Λ-β-[Co(R,R-picchxn)Cl2]+ in aqueous solution (R,R-picchxn=N,N′-di(2-picolyl)-1R, 2R-diaminocyclohexane) results in the formation of a Λ-β-[Co(R,R-picchxn)(pcp)]3+ species, as one of two major products. The other species is the ternary complex containing the anionic hydrolysis product hydroxy(2-pyridyl)methanol (hpm), Λ-β2-[Co(R,R-picchxn)(hpm)]2+, which was crystallized as its diperchlorate monohydrate salt, and its structure determined by single-crystal X-ray diffraction. Λ-β2-[Co(R,R-picchxn)(hpm)](ClO4)2·H2O is orthorhombic, a =9.171(2), b = 17.771(3), c = 17.785(4) Å, space group P212121, with Z=4. The structure was refined to a final R value of 0.061 for 1822 unique reflections with I> 3σ(I). This shows that, in this compound, hpm coordinates stereospecifically (R) to Co in the solid state. However, two diastereoisomers are observed using NMR methods when the complex is dissolved in dmso. The study illustrates the need to take into account the existence of derived diol species in metal-aldehyde systems.

    Original languageEnglish
    Pages (from-to)191-196
    Number of pages6
    JournalInorganica Chimica Acta
    Volume221
    Issue number1-2
    DOIs
    Publication statusPublished - 15 Jun 1994

    Keywords

    • chiral ligand complexes
    • cobalt complexes
    • crystal structures
    • hydrolysis
    • imine complexes

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