The reaction of the tin(II) (iminophosphinoyl)(thiophosphinoyl)methanediide [(PPh 2=NSiMe 3)(PPh 2=S)CSn:] 2 (1) with AdNCO (Ad = adamantyl), ArNCO (Ar = 2,6-Pr i 2C 6H 3), and [RhCl(cod)] 2 in THF afforded [(PPh 2=NSiMe 3)(PPh 2=S)C{C(O)N(Ad)}Sn:] (2), [(PPh 2=NSiMe 3)(PPh 2=S)C{C(O)N(Ar)}Sn +:] (3), and [(PPh 2=NSiMe 3)(PPh 2=S)C{Rh(cod)}(SnCl)] (4), respectively. Compounds 2-4 have been characterized by NMR spectroscopy and X-ray crystallography. © 2012 American Chemical Society.