The goals of this study were to synthesize volatile tin(II) hexafluoroisopropoxide complexes for use as precursors to tin oxide or fluorine-doped tin oxide and to prepare related germanium(II) and lead(II) compounds. M(N(SiMe(3))(2))2 reacts with 2 equiv of R(f)OH (R(f) = CH(CF3)(2)) and 1 equiv of added amine, L, to give M(OR(f))(2)L (M = Ge, L py or H(2)NPh; M = Sn, L = HNMe(2) or py; M = Pb, L p-pyNMe(2)) in high yield. Alternatively, Sn(OR(f))(2)(HNMe(2)) can be prepared by reacting Sn(NMe(2))(2) with R(f)OH. X-ray crystallographic studies of Ge(OR(f))(2)(H(2)NPh) and Sn(OR(f))(HNMe(2)) show they are monomers with trigonal pyramidal geometries. An X-ray structure of the Pb compound shows it is the dimer [Pb(mu-OR(f))(OR(f))(p-pyNMe(2))](2). Pb(NMe(2))(2) reacts with 3 equiv of R(f)OH to give [Me(2)NH(2)][Pb(OR(f))(3)], which an X-ray structure shows is the dimer {[Me(2)NH(2)][Pb(mu-OR(f))(OR(f))(2)]}(2). Both Pb dimers are held together by weak dative Pb-O interactions. Sn(N(SiMe(3))(2))(2) reacts with 2 equiv of R(f)OH in the absence of added amine to give amine-free Sn(OR(f))(2). By analogy to known tin(II) alkoxide and related compounds, Sn(OR(f))2 is proposed to be a dimer with two bridging alkoxide ligands. The tin compounds are volatile solids, an important criterion for their possible use as conventional tin oxide precursors in chemical vapor deposition processes.