Tantalum(III) chloride can form complexes with some ligands as a monomer or dimer.
Complexes include Ta(=C-CMe)(PMe)Cl, [TaCl(P(CHCH)THF]μ-N and [TaClTHF]μ-N (dinitrogen complexes).
As a dimer, complexes include TaCl(SCH) (SCH=tetrahydrothiophene). TaCl(SMe), TaCl(thiane) and TaCl(thiolane) have a double bond between the two tantalum atoms, and two bridging chlorides, and a bridging ligand.