ic7b02040_si_001.pdf (2.95 MB)

Tin and Lead Phosphanido Complexes: Reactivity with Chalcogens

Download (2.95 MB)
journal contribution
posted on 30.11.2017, 12:48 by Eric C. Y. Tam, David C. Apperley, J. David Smith, Martyn P. Coles, J. Robin Fulton
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-iPr2C6H3}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.