14-Electron metal complexes stabilized by M...η³-H₂C agostic interactions (original) (raw)

2005, Acta Crystallographica Section A

The coordination of inert C-H bonds to a transition metal center is of fundamental interest for stoichiometric and catalytic reactions, with particular regard to the problem of alkane functionalization via C-H bond activation. Unfortunately, information on the nature of the primary adduct is still very scarce, since saturated hydrocarbons are notoriously very poor ligands. By use of the phosphine PR 2 (2,6-Me 2 C 6 H 3) (R = Ph, Cy), bearing two methyl groups in the ortho position, rare examples of 14-electron Ru(II) and Pt(II) complexes have been isolated [1]. Solid state studies, using both X-ray and neutron diffraction techniques, reveal that nonclassical M••• 3-H 2 C agostic interactions take place and this result is in agreement with a structural survey on Cambridge databank, data in solution and a computational analysis. The reactivity of these complexes is reported, as well as the use of the Ru system as precursor for the preparation of highly active transfer hydrogenation catalysts.

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