Synthesis of Group 8−Group 6 Heterotrimetallic Polyhydrido Complexes Having Only a C₅Me₅ Group as Auxiliary Ligand

Abstract

Novel heterotrimetallic polyhydrido complexes containing ruthenium and group 6 metals, (Cp‘Ru)2(Cp‘M)(μ-H)5 (4, M = Mo; 5, M = W) and (Cp‘Ru)(Cp‘W)2(H)7 (6), have been synthesized by the reaction of dimeric ruthenium methoxo complex (Cp‘RuOMe)2 (3) with dinuclear polyhydrido complexes Cp‘Ru(μ-H)3MH3Cp‘ (1, M = Mo; 2, M = W) and (Cp‘WH4)2, respectively. The 1H NMR spectra of 6 exhibit fluxionality stemming from the dynamic motion of the RuW2 core associated with exchange of the coordination sites among the hydrido ligands.

Synthesis of a Heterometallic Trinuclear Cluster Containing Ruthenium and Cobalt and Its Reactivity with Internal Alkynes

“…These studies clearly demonstrated that bond activation was greatly facilitated by the cooperative interaction of the neighboring metal centers with the substrates. Simultaneously, we also developed a rational synthesis of heterometallic polyhydrido clusters composed of [Cp*Ru] (Cp* = η 5 -C 5 Me 5 ) units and units of other transition metals containing a Cp* group, such as Mo, W, Re, Os, Rh, and Ir . These heterometallic clusters are expected to regioselectively activate the substrates because of the anisotropy of the heterometallic cluster core .…”

Organometallic chemistry of bi- and poly-metallic complexes

“…A report concerning the synthesis of novel heterotrimetallic polyhydrido complexes containing ruthenium and oxophilic group 6 metals and the dynamic processes of these complexes in solution has appeared. 94 An elegant synthesis of an undecanuclear heterotrimetallic complex has been reported. The complex is a star-shaped ruthenium species with five ferrocenylterminated arms bridged by trans-platinum fragments.…”

Syntheses and Properties of Triruthenium Polyhydrido Complexes Composed of 1,2,4-tri-tert-butylcyclopentadienyl and p-Cymene Ruthenium Units

“…Condensation reactions using polyhydrido complexes are some of the most reliable methods for preparing polyhydride clusters. However, this method is restricted to the cases where the individual starting polyhydrido complexes are readily available and are stable enough to be handled under normal conditions. − As an alternative method, we recently reported the direct synthesis of polyhydride clusters from metal halides via gentle heating in 2-propanol in the presence of a base. Using this method, a diruthenium tetrahydrido complex, [(Cp ‡ Ru) 2 (μ-H) 4 ] ( 1b , Cp ‡ = 1,2,4-C 5 H 2 t Bu 3 ), was obtained in 98% yield from [Cp ‡ RuCl 2 ] 2 .…”