Synthesis of Oxo- and Sulfido-Bridged Germanium−Ruthenium Complexes and Reactions on the Chalcogenido Bridges

A series of heterodinuclear germanium−ruthenium complexes having sulfido/oxo bridges, Dmp(Dep)Ge(μ-E1)(μ-E2)Ru(η6-arene) (E1, E2 = S, O; arene = benzene, p-cymene; Dmp = 2,6-dimesitylphenyl,
Dep = 2,6-diethylphenyl) were synthesized by the reaction of [Ru(η6-arene)Cl2]2 and the corresponding
diarylgermanedichalcogenoles, Dmp(Dep)Ge(E1H)(E2H). The reaction with tertiary phosphines gave the
corresponding adducts Dmp(Dep)Ge(μ-S)(μ-E)Ru(PR3) (E = S, O; R = Ph, Et), in which the arene
ligand on the ruthenium was replaced by a mesityl group of Dmp. When Dmp(Dep)Ge(μ-S)2Ru(PPh3)
was treated with the Brønsted acids H(OEt2)2BArF4 and HOTf, a sulfido bridge was protonated to afford
[Dmp(Dep)Ge(μ-S)(μ-SH)Ru(PPh3)]X (X = BArF4, OTf). Likewise, the methylation reaction with
Me3OBF4 proceeded at a μ-S, generating [Dmp(Dep)Ge(μ-S)(μ-SMe)Ru(PPh3)](BF4). On the other hand,
protonation of Dmp(Dep)Ge(μ-S)(μ-O)Ru(PPh3) gave a μ-OH complex, [Dmp(Dep)Ge(μ-S)(μ-OH)Ru(PPh3)]+, while the analogous methylation afforded the cationic μ-SMe complex [Dmp(Dep)Ge(μ-SMe)(μ-O)Ru(PPh3)]+.