A general high-yield synthetic route to the hexacoordinate silicon porphyrin dichloride complexes trans-(For)SiCl2 {For = the dianions of octaethylporphyrin (OEP), tetraphenylporphyrin (TPP), and tetrakis(p-(trifluoromethyl)phenyl)porphyrin (TTFP)} is reported. Reacting (Por)SiCl2 with SbF3 and AgOTf produces the corresponding difluoro trans-(Por)SiF2 and bis(triflato) trans-(Por)Si(OTf)(2) complexes, respectively. The spectroscopic properties (H-1, F-19, and Si-29 NMR and visible) of these hexacoordinate silicon compounds are surprisingly insensitive to the electron-donating ability of the porphyrin or the nature of the axial substituents. The nature of the porphyrin and the axial substituent do play a role in the reactivity of these silicon complexes. The strong SI-F bond makes the difluorides stable to hydrolysis and methanolysis. The dichlorides, on the other hand, do undergo hydrolysis and methanolysis, the extent of which is determined by the electronics of the porphyrin ring. The strong electron-donating ability of OEP stabilizes (OEP)SiCl2 with respect to hydrolysis and methanolysis. (TTFP)SiCl2, containing the least electron-donating porphyrin, reacts with MeOH to give a mixture of (TTFP)Si(OMe)CI and (TTFP)Si(OMe)(2), whereas (TTP)SiCl2 (TTP = the dianion of tetra-p-tolylporphyrin) reacts with MeOH to give only the monomethoxy derivative. The triflate groups on (OEP)Si(OTf)(2) are more labile than those in the corresponding tetraarylporphyrin complexes and can be displaced by THF to give the cationic species [(OEP)Si(OTf)(THE)]OTf or [(OEP)Si(THF)(2)](OTf)(2).