Making and breaking bonds in a solid-state compound greatly influences physical properties. A well-known playground for such bonding manipulation is the ThCr2Si2-type structure AT(2)X(2), allowing a collapse transition where a X-X dimer forms by a chemical substitution or external stimuli. Here, we report a pressure-induced collapse transition in the structurally related BaTi(2)Pn(2)O (Pn = As, Sb) at a transition pressure P-c of similar to 15 GPa. The Pn-Pn bond formation is related with Pn-p band filling, which is controlled by charge transfer from the Ti-3d band. At P-c, the Sb-Sb distance in BaTi2Sb2O shrinks due to bond formation, but interestingly, the Sb-Sb expands with increasing pressure above P-c. This expansion, which was not reported in ThCr2Si2-type compounds, may arise from heteroleptic coordination geometry around titanium, where a compression of the Ti-O bond plays a role. Electrical resistivity measurements of BaTi2Sb2O up to 55 GPa revealed an increasing trend of the superconducting transition temperature with pressure. This study presents structure motifs that allow flexible bonding manipulation and property control with heteroleptic coordination geometry.