Pressure-Assisted Hetero- and Homodialkylation of Sulfide in [Pt-2(mu-S)(2)(dppp)(2)]: One-Pot Conversion of {Pt-2(mu-S)(2)} into {Pt-2(SR)(2)} and {Pt-2(SR)(SR')}

Abstract

Heterodialkylation of [Pt2(-S)2(dppp)2] (dppp=Ph2P(CH2)3PPh2) was achieved under high pressure (10 kbar). This enabled the synthesis of rare diplatinum complexes with structurally diverse thiolate bridges, such as [Pt2(-SC5H10CO2CH2CH3)(-SC3H7)-(dppp)2](PF6)2, which was crystallographically identified. Complete homodialkylation was also achieved under similar conditions (6 kbar at room temperature), thus permitting the isolation of [Pt2(-SC2H4CO2CH2CH3)2(dppp)2]-(PF6)2. The isolation of these complexes extends the applications of high-pressure chemistry to thiolato homo- and heterobridged complexes that are otherwise not accessible.