title: [(iPr3P)6Rh6H12]2+: a high-hydride content octahedron that bridges the gap between late and early transition metal clusters.
abstract: Treatment of [(iPr3P)2Rh(nbd)][Y] {nbd = norbornadiene, Y = B{3,5-(CF3)2C6H3}4- [B(ArF)4] or 1-H-closo-CB11Me11-} with H2 (ca. 4 atm) results in the isolation, in moderate yield, of the octahedral cluster complex [(iPr3P)6Rh6H12][Y]2 1. The cluster (for both anions) has been characterized by NMR, mass spectroscopy, and X-ray crystallography. These show 1 to have 12 edge-bridging hydrogen atoms, and the structure bears more resemblance to clusters of the early transition metals with pi-donor ligands than those of the late transition metals with pi-acceptor ligands. Intermediate complexes on the route to 1, namely, the nonclassical dihydrogen complexes [(iPr3P)2Rh(H)2(eta2-H2)x][B(ArF)4] (x = 1 or 2), have been observed spectroscopically. The high hydride content of 1 makes it a possible model for nanocluster colloidal Rh(0) catalysts that are used in olefin and arene hydrogenation.
authors.affiliation: Department of Chemistry, University of Bath, Bath, UK, BA2 7AY.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Ingleson
authors.forename: Mary F
authors.initials: MF
authors.lastname: Mahon
authors.forename: Paul R
authors.initials: PR
authors.lastname: Raithby
authors.forename: Andrew S
authors.initials: AS
authors.lastname: Weller