Electrochemical synthesis of dimeric platinum hydride species responsible for highly regioselective alkene hydroformylation

Abstract
PtL2Cl2 complexes (1)[L2= diop, 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane] have been used as catalyst precursors for alkene hydroformylation after electroreduction using a soluble tin or iron anode, followed by treatment with carbon monoxide–hydrogen; the remarkable regioselectivities for linear aldehyde formation (ca. 98% from hex-1-ene and 90% from styrene) are explained by the production of chelated, bridged platinum hydride cationic species [L2Pt(H)(µ-L2)Pt(H)L2]2+, stabilized by the presence of a polar, highly dissociating solvent.

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