Synthesis and molecular structures of cymantrenecarboxylate derivatives of titanium(Iv) and vanadium(III). cyclopentadienyl complexes and of copper(II) and manganese(II) lutidine complexes

The reactions of dimethyltitanocene borohydride and vanadocene with cymantrenecarboxylic acid CymCOOH gave the monomer (C5H4Me)2Ti(OOCCym)2 (I) and dimer (C5H5)V(OOCCym)4V(C5H5) (II), respectively. Treatment of Cu(II) cymantrenylcarboxylate with excess lutidine gives the monomer (C7H9N)2Cu(COOCym)2 (III). The reaction of lutidine with a mixture of Cu(II) and Mn(II) bis-cymantrenecarboxylates affords the heterometallic trinuclear complex (C7H9N)Cu(OOCCym)3Mn(OOCCym)3Cu(C7H9N) (IV). The structures of I–IV were established by X-ray diffraction. In I and III, the cymantrenecarboxylate groups are terminal and in II and IV, they are bridging, which is also manifested as characteristic OCO stretching bands in the IR spectra.