Synthesis and structure of the first ruthenated benzodiazepines

[{RuCl(cym)}(2)(mu-Cl)(2)] (cym = eta(6)-p-methylisopropylbenzene) serves as precursor to synthesize the two first ruthenated benzodiazepines in which deprotonated diazepam is coordinated to a {RuCl(cym)} fragment. In complex 1, obtained by treatment with diazepam in the presence of NaBPh4 and NEt3, the coordination is through the imine nitrogen and an ortho carbon of the phenyl substituent. In 2, obtained by reaction of deprotonated diazepam with the metal dimer, the coordination is through the imine nitrogen and the adjacent sp(3) carbon of the benzodiazepine.