The coordination chemistry and reactivity of amino-dithiaphospholanes with rhodium, iridium, and ruthenium

Novel amino-dithiaphospholane complexes of ruthenium, iridium, and rhodium were synthesized, and their properties were studied. Reaction of the new amino-dithiaphospholane (RS)2PNR2′ (R = binaphthyl, R′ = CH2Ph, (rac)-4) with [RuCl2(p-cymene)]2 afforded [RuCl2(p-cymene)((rac)-4)] in 67% isolated yield. Similarly, the new amino-dithiaphospholanes (RS)2PNR2′ (R = cyclohexyl, (rac)-7) and (RS)2PNR2′ (R = phenyl, 9) gave upon reaction with [RhCl(CO)2]2 and [IrCp∗Cl2]2 the novel complexes [RhCl(CO)(L)2] and [IrCp∗Cl2(L)] (L = (rac)-7, 9) in 61-96% yields. The ruthenium complex is catalytically active for the etherification of propargylic alcohols with methanol and ethanol (8-48 h, 90 °C, 40-85% isolated yields).