Coordination Chemistry Reviews
Coordination Chemistry Reviews
5 years ago

Structure, bonding and reactivity of seven-coordinate allylic Mo(II) and W(II) complexes

Structure, bonding and reactivity of seven-coordinate allylic Mo(II) and W(II) complexes
The family of Mo(II) and W(II) complexes [M(η3‑allyl)X(CO)2(L)2] fragment (X=anion, (L)2 =two monodentate or one bidentate ligand, allyl=C3H5 or substituted allyl) was revisited. A structural search in the CSD afforded 441 molybdenum and 68 tungsten complexes with a pseudo-octahedral geometry (the allyl centroid is taken as one ligand for these purposes) and 18 electrons. Almost all the complexes have the allyl and carbonyls arranged in a facial way, the two carbonyls being cis and lying exo relative to the allyl, but with a fairer distribution between the A (X trans to the allyl) and B isomers (X cis to the allyl). Both A and B, as well as endo and exo species, are fluxional in solution. They may coexist in the solid state and there are examples of exceptions to everything: mer arrangement, trans carbonyls, endo allyl/CO. The A/B conversion is not easy to rationalize, as even an energy decomposition analysis reveals a competition between almost balancing effects. Still a strong π-acceptor as X favors B. This structural fluxionality may contribute to the limited number of applications in catalysis, though many complexes exhibit promising biological activity.

Publisher URL: www.sciencedirect.com/science

DOI: S0010854516303733

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