The development of thin film photovoltaics for solar energy conversion is a critical technology for NASA. Thin film photovoltaics promise to provide the high power output, the low weight and packaging volume, and radiation resistance necessary for short and long term space missions. Chemical Vapor Deposition (CVD) has been used for the deposition of thin film photovoltaics. The chalcopyrites, Cu(Ga,In)(S,Se)2, are amongst the most efficient and promising of the semiconductor materials to be used in thin film photovoltaic devices. The deposition of polycrystalline thin-film solar cells is limited by the number of available precursors A series of silylated group 13-16 complexes is presented as potential precursors for CVD preparation of new materials. The reaction of MR3 (M=Ga, In) with HESiR'3 (E = O, S) leads to the formation of [R2M(mu-ESiR'3)]2 complexes in high yields. The physical properties of these precursors are readily modifiable by choice of substituents on the group 13 metal and on silicon The heterobimetallic (thf)2Li(mu-ESiPh3) 2MR2 (E = O, S, Se) complexes were synthesized and fully characterized. In the solid state, these complexes are dimeric with a Li(mu-E)2M ring core. The suitability of the group 13 lithium chalcogenides as precursors for CVD of LiME2 films was explored