Theoretical description (MP2/6-311G* and B3LYP/6-311G*) is presented for hypovalent titanium alkoxide model compounds showing linear angle Ti-O-C angles. This feature is explained by the existence of a polarized triple Ti-O bond. In contrast, a series of 18 electron germanium derivatives displaying bent angle Ge-O-C angles contain polarized single Ge-O bonds. The nature of the Ti-O and Ge-O bonds is established by means of natural bond order (NBO), atoms-in-molecules theory (AIM), and electron localization function (ELF) analyses.