Tris(Butadiene) Compounds versus Butadiene Oligomerization in Second-Row Transition Metal Chemistry: Effects of Increased Ligand Fields

The geometries, energetics, and preferred spin states of the second-row transition metal tris(butadiene) complexes (C(4)H(6))(3)M (M = Zr–Pd) and their isomers, including the experimentally known very stable molybdenum derivative (C(4)H(6))(3)Mo, have been examined by density functional theory. Such low-energy structures are found to have low-spin singlet and doublet spin states in contrast to the corresponding derivatives of the first-row transition metals. The three butadiene ligands in the lowest-energy (C(4)H(6))(3)M structures of the late second-row transition metals couple to form a C(12)H(18) ligand that binds to the central metal atom as a hexahapto ligand for M = Pd but as an octahapto ligand for M = Rh and Ru. However, the lowest-energy (C(4)H(6))(3)M structures of the early transition metals have three separate tetrahapto butadiene ligands for M = Zr, Nb, and Mo or two tetrahapto butadiene ligands and one dihapto butadiene ligand for M = Tc. The low energy of the experimentally known singlet (C(4)H(6))(3)Mo structure contrasts with the very high energy of its experimentally unknown singlet chromium (C(4)H(6))(3)Cr analog relative to quintet (C(12)H(18))Cr isomers with an open-chain C(12)H(18) ligand.