Oxime targeted reactions of the complexes trans-[(kappa(3)-dapdOH)Ru(CO)(PPh3)(2)]PF6 (1) (dapdOH = diacetylpyridinedioxime) and trans-[(kappa(3)-dapmOH)RuCl(PPh3)(2)]PF6 (2) (dapmOH = diacetylpyridinemonooxime) with SOCl2, NaBH4, 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)]PF6 (1), trans-[(kappa(3)-dapdO)Ru(CO)(PPh3)(2)] (11) and oximato/imino complex trans-[(kappa(3)-dapd-NH)Ru(CO)(PPh3)(2)]PF6 (13) have been authenticated by single-crystal X-ray diffraction analyses. Structural studies revealed the presence of various oxime/oximato/ imino based O-H center dot center dot center dot O, C-H center dot center dot center dot O, and N-H center dot center dot center dot F interactions in the complexes 1, 11, and 13.