Chemistry of Ru(& ⁶‐1,3,5‐cyclooctatriene)(η²‐dimethyl fumarate)₂

The chemistry of a novel zerovalent Ru complex, Ru(eta6-cot)(eta2-dmfm)2 (1) (cot=1,3,5-cyclooctatriene; dmfm=dimethyl fumarate), is reviewed with a focus on its reactivity toward phosphines, amines, and H2O, as well as arenes and p-quinones. A variety of novel zerovalent Ru complexes were synthesized from Ru(eta6-cot)(eta2-dmfm)2 (1), and it was shown that the complexes preferably bear both electron-donating and -accepting ligands simultaneously to exhibit thermodynamic stability. The first isolable zerovalent Ru aqua complexes were successfully prepared, and in these complexes, the generation of a chiral center on the O atom of the coordinated H2O was disclosed. In addition, the characteristic catalytic activity of 1 in organic synthesis was considered by reviewing recently developed novel reactions: (i) dimerization of 2,5-norbornadiene to pentacyclo[6.6.0.0(2,6).0(3,13).0(10,14)]tetradeca-4,11-diene (PCTD), (ii) intramolecular hydroamination of aminoalkynes to cyclic imines, (iii) formal [4+2] cycloaddition of alkynes with dmfm to trans-4-cyclohexene-1,2-dicarboxylates, and (iv) co-dimerization of dihydrofurans with alpha,beta-unsaturated esters to 2-alkylidenetetrahydrofurans. The products obtained here are expected to be used as novel functional organic monomers.