Synthesis, Structure, and Reactivity of Trigonal Bipyramidal Ruthenium(IV) Trialkyl Complexes

The alkylation of [Ru­(NPPh3)­(PPh3)2Cl3] with Me3SiCH2MgCl afforded the RuIV trialkyl complex [Ru­(CH2SiMe3)3(PPh3)­Cl] (1), which exhibits a trigonal bipyramidal geometry with the three alkyl groups occupying the equatorial plane. DFT calculations reveal that 1 possesses a (dxz,dyz) singlet ground state, consistent with the observed diamagnetism of the complex. The electronic spectrum of 1 displayed two absorptions at 455 and 505 nm, which, on the basis of TDDFT calculations, are attributed to metal-centered d–d transitions with a significant contribution from the alkyl ligands. Chloride abstraction of 1 with Ag­(OTf) (OTf– = triflate) provided the triflate complex [Ru­(CH2SiMe3)3(PPh3)­(OTf)] (2) that proved to be a useful starting material for RuIV trialkyl complexes. Substitution of 2 with NaX afforded [Ru­(CH2SiMe3)3(PPh3)­(X)] (X = N3– (3) or SCN– (4)). Treatment of 2 with excess sodium 2,3,5,6-tetrafluorophenoxide (NaORf) in tetrahydrofuran resulted in desilylation of two alkyl groups, and formation of the dimethyl complex [Ru­(CH2SiMe3)­Me2(PPh3)­(ORf)] (5). 2 underwent reductive elimination of the C–C bond with 1,10-phenanthroline (phen) in CH2Cl2 to give cis-[Ru­(phen)2(PPh3)­Cl]­(OTf) (6). The crystal structures of 1, 2, 4, and 5 have been determined.