A new titanium building block for early–late heterometallic complexes; preparation of a new tetrameric metallomacrocycle by self assembly

Abstract

The new titanium dicarboxylate complex Cp*TiMe(OOC)₂py (2) [Cp* = η⁵-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(η²-MeCNR)(OOC)₂py [R = ^tBu (4), 2,6-dimethylphenyl (xylyl) (5)]. The molecular structure of complex 4 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(µ-OH)(COD)]₂ (M = Rh, Ir) to give the corresponding tetranuclear metallomacrocycle derivatives [Cp*Ti{(OOC)₂py}(µ-O)M(COD)]₂ [M = Rh (6); Ir (7)]. The molecular structure of 6 has been established by X-ray diffraction.