Reactivity of the oxime/oximato group in ruthenium(II) complexes.

Oxime targeted reactions of the complexes trans-[(kappa(3)-dapdOH)Ru(CO)(PPh(3))(2)]PF(6) (1) (dapdOH = diacetylpyridinedioxime) and trans-[(kappa(3)-dapmOH)RuCl(PPh(3))(2)]PF(6) (2) (dapmOH = diacetylpyridinemonooxime) with SOCl(2), NaBH(4), or HCHO led into conversion of oxime to oximato, imino, or hydroxymethylimino groups. The reaction products have been characterized by analytical and spectral studies. Molecular structures of the representative homo/heteroleptic oxime/oximato complexes trans-[(kappa(3)-dapdOH)Ru(CO)(PPh(3))(2)]PF(6) (1), trans-[(kappa(3)-dapdO)Ru(CO)(PPh(3))(2)] (11) and oximato/imino complex trans-[(kappa(3)-dapd-NH)Ru(CO)(PPh(3))(2)]PF(6) (13) have been authenticated by single-crystal X-ray diffraction analyses. Structural studies revealed the presence of various oxime/oximato/imino based O-H...O, C-H...O, and N-H...F interactions in the complexes 1, 11, and 13.