The new titanium dicarboxylate complex Cp*TiMe(OOC)2py (2) [Cp*=eta5-C5Me5; (OOC)2py = 2,6-pyridinedicarboxylate] has been synthesized. The reaction of complex 2 with water renders [Cp*Ti(OOC)2py]2O (3). The molecular structure of 3 has been studied by X-ray diffraction methods. Complex 2 reacts with isocyanides to yield the respective iminoacyl derivatives Cp*Ti(eta2-MeCNR)(OOC)2py [R=tBu (4), 2,6-dimethylphenyl (xylyl) (5)]. The molecular structure of complex4 has been established by X-ray diffraction. Compound 2 has been employed as a new building block for the preparation of new early-late heterometallic compounds; it reacts with [M(mu-OH)(COD)]2 (M = Rh, Ir) to give the corresponding tetranuclear metallomacrocycle derivatives [Cp*Ti{(OOC)(2)py}(mu-O)M(COD)]2 [M = Rh (6); Ir (7)]. The molecular structure of 6 has been established by X-ray diffraction.