Di-n-butylstannane, polydi-n-butylstannane and the acetylene inserted carbodistannanes were prepared using the methods described in literature [sic]. Their structures were confirmed by NMR analysis. Finally acetylene inserted polydibutylstannane, was prepared in a similar fashion and was evident from its unique 119Sn NMR chemical shift values that were similar to that for (n-Bu)3SnCH=CHSn(n-Bu)₃. A highly unusual head to head dimer (hexamethyl-1,4-diphenyldistannyl-1,3-butadiene) was obtained and characterized by X-ray crystallography. The quantitative conversion of (n-Bu)₃SnH into (n-Bu)₆Sn₂ was achieved by heating the neat (n-Bu)₃SnH under different conditions. This route was extended to a secondary stannane, (n-Bu)₂SnH₂ which yielded evidence (NMR) for H(n-Bu)₂SnSn(n-Bu)₂H, polystannane [(n-Bu)₂Sn]n and various cyclic stannanes [(n-Bu)₂Sn]n = 5, 6. Further evidence for [(n-Bu)₂Sn]n was afforded by GPC where a broad, moderate molecular weight, but highly dispersed polymer was obtained (Mw = 1.8 X 10⁴ Da, PDI = 6.9) and a characteristic UV-Vis absorbance (२max) of ~370 nm observed.