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(mu-E-1)(mu-E-2)Ru(eta(6)-arene) (E-1, E-2 = S, O; arene) benzene, p-cymene; Dmp = 2,6-dimesitylphenyl, Dep) 2,6-diethylphenyl) were synthesized by the reaction of [Ru(eta(6)-arene)Cl-2](2) and the corresponding diarylgermanedichalcogenoles, Dmp(Dep)Ge((EH)-H-1)((EH)-H-2). The reaction with tertiary phosphines gave the corresponding adducts Dmp(Dep)Ge(mu-S)(mu-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(mu-S)(2)Ru(PPh3) was treated with the Bronsted acids H(OEt2)(2)BAr4F and HOTf, a sulfido bridge was protonated to afford [Dmp(Dep)Ge(mu-S)(mu-SH)Ru(PPh3)]X (X = BAr4F, OTf). Likewise, the methylation reaction with Me3OBF4 proceeded at a mu-S, generating [Dmp(Dep)Ge(mu-S)(mu-SMe)Ru(PPh3)](BF4). On the other hand, protonation of Dmp(Dep)Ge(mu-S)(mu-O)Ru(PPh3) gave a mu-OH complex, [Dmp(Dep)Ge(mu-S)(mu-OH)Ru(PPh3)](+), while the analogous methylation afforded the cationic mu-SMe complex [Dmp(Dep)Ge(mu-SMe)(mu-O)Ru(PPh3)](+).