Pentanuclear Polyhydride Cluster of Ruthenium with Trigonal-Bipyramidal Geometry. Synthesis and Fluxional Behavior

Abstract

The reaction of the ruthenium diamine complex CpRu(tmeda)Cl (1; Cp ) η 5 -C 5 H 5 ) with LiAlH 4 afforded the novel pentaruthenium cluster Cp 5 Ru 5 H 7 (2) in the tbp geometry. The mixed-ligand cluster Cp 4 Cp*Ru 5 H 7 (4; Cp* ) η 5 -C 5 Me 5 ) was derived in a similar manner from 1 and Cp*Ru(acac) (3). Complex 2 exhibits a new type of fluxional behavior that involves exchange of the CpRu groups among the axial sites and the equatorial sites.

Hydrogenation of N-Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters

“…The combined NMR spectroscopic and crystallographic data support formation of a neutral pentametallic rhodium–hydride cluster, [(η 5 -C 5 Me 5 ) 4 Rh 5 H 7 ] ( 5 ) (Scheme ). Unlike other transition metal clusters containing η 5 -C 5 Me 5 and hydride ligands, the complex has a unique structure comprised of a tetrahedral Rh 4 core with the additional rhodium at the apex. − Three of the rhodium atoms in the core are ligated by η 5 -C 5 Me 5 rings while the other is ligand free and capped by the unique [(η 5 -C 5 Me 5 )­Rh]. The bond distance of Rh4–Rh5 is significantly shorter than the other Rh–Rh bonds.…”

21 Organometallic chemistry of bi- and poly-nuclear complexes

“…Mixed Cp 4 Cp* and C 5 H 4 Me-capped clusters were obtained in similar fashion. 37 Cluster 36 reacts with PH 2 Ph to give the phenylphosphido cluster [Ru 5 (m 4 -PPh)H 5 Cp 5 ] which displays a closo-Ru 5 P octahedral core.…”

Synthesis and structural characterization of ruthenium(II) and iron(II) complexes containing 1,2-di-(2-thienyl)-ethene derived ligands as chromophores

“…All solvents were dried using standard methods [38]. Starting materials were prepared following the methods described in the literature: [Ru(g 5 -C 5 H 5 ) (DPPE)Cl] and [Ru(g 5 -C 5 H 5 )(PPh 3 ) 2 Cl] [39], [Fe(g 5 -C 5 H 5 )(DPPE)I] [12], [Ru(g 5 -C 5 H 5 )(TMEDA)Cl] [40], 1,2-di-(2-thienyl)-ethene [29]. Solid state IR spectra were taken on a Mattson Satellite FTIR spectrophotometer with KBr pellets; only significant bands are cited in the text.…”