Antitumor activity of bent metallocenes: electronic structure analysis using DFT computations.

The antitumor activities of bent metallocenes [Cp-M-Cp](2+) (M = Ti, V, Nb, Mo) and complexes of them with guanine, adenine, thymine and cytosine nucleotides have been probed using electronic structure calculations. DFT/BP86 calculations have revealed that the bent metallocene-nucleotide interaction strongly depends on the stability of the hydrolyzed form of the bent metallocene dichloride [Cp(2)M](2+) species, and in turn the stability of the [Cp(2)M](2+) species strongly depends on the electronic structure of [Cp(2)M](2+). Detailed electronic structure and Walsh energy analyses have been carried out for the hydrolyzed forms of four [Cp-M-Cp](2+) (M = Ti, V, Nb, Mo) species to find out why the bent structure is unusually stable.