Tin and Lead Phosphanido Complexes: Reactivity with Chalcogens

The reactivity of tin and lead phosphanido complexes with chalogens is reported. The addition of sulfur to [(BDI)­MPCy₂] (M = Sn, Pb; BDI = CH­{(CH₃)­CN-2,6-<i>i</i>Pr₂C₆H₃}₂) results in the formation of phosphinodithioates [(BDI)­MSP­(S)­Cy₂] regardless of the conditions; however, when selenium is added to [(BDI)­MPCy₂], a selenium insertion product, phosphinoselenoite [(BDI)­MSePCy₂], can be isolated. This compound readily reacts with additional selenium to form the phosphinodiselenoate complex [(BDI)­MSeP­(Se)­Cy₂]. In contrast, the addition of selenium to [(BDI)­SnP­(SiMe₃)₂] results in the formation of the heavy ether [(BDI)­SnSeSiMe₃]. Differences in the solution and solid-state molecular species of tin phosphinoselenoite and phosphinodiselenoate complexes were probed using multinuclear solution and solid-state NMR spectroscopy