The π-basic fragment {WTp(NO)(PMe3)} binds to the aromatic ring of phenyl sulfones in a dihapto fashion. Tungsten complexes of methyl phenyl sulfone (PhSO2Me), diphenylsulfone (PhSO2Ph), and 1-(phenylsulfonyl)pyrrolidine (PhSO2(NC4H8)) were synthesized from the WTp(NO)(PMe3)(η2-anisole) precursor. Complexes of the form WTp(NO)(PMe3)(3,4-η2-PhSO2R) (R= -Me, -Ph, -N(C4H8)) underwent a regio- and stereoselective 1,2-addition reaction involving protonation followed by nucleophilic addition to generate η2-1,3-cyclohexadiene complexes. Subjecting the resulting η2-1,3-cyclohexadiene complexes to another sequence of acid and nucleophile allows access to trisubstituted cyclohexene complexes with complementary substitution patterns. In some cases, elimination of the sulfonyl group occurs, which allows for further functionalization of the resulting π-ligand. Compatible nucleophiles for these addition reactions include enolates, cyanide, amines, and hydrides. Oxidation of the metal allows for the decomplexation of trisubstituted cyclohexene organic products. Full characterization of the new compounds includes two-dimensional NMR, IR, electrochemical, and in some cases, crystallographic data.

Reactivity of phenyl sulfones upon dihapto-coordination to an electron rich tungsten complex

ACS Spring Meeting 2021

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