Preparation and characterisation of mixed bismuth and ruthenium clusters; X-ray crystal structures of [Ru3(µ-H)3(CO)9(µ3-Bi)], [Ru3(CO)9(µ3-Bi)2], and [Ru4(CO)12(µ4-Bi)2]

Abstract

The inclusion of naked bismuth atoms into carbonyl cluster compounds of ruthenium has been achieved with the use of bismuth(III) nitrate pentahydrate, Bi(NO₃)₃·5H₂O, as the bismuth containing reagent. We report the high-yield synthesis of [Ru₃(µ-H)₃(CO)₉(µ₃-Bi)](1) from the reaction of Bi(NO₃)₃·5H₂O with [NBu₄][Ru₄H₃(CO)₁₂], the preparation of (1) and [Ru₃(CO)₉(µ₃-Bi)₂](2) from Bi(NO₃)₃·5H₂O and Na[Ru₃H(CO)₁₁], and the preparation of [Ru₄(CO)₁₂(µ₄-Bi)₂](3) from Bi(NO₃)₃·5H₂O and [Ru₃(CO)₁₂] in KOH–MeOH solution. The determination of the X-ray crystal structures of (1), (2), and (3) show that (1) has a slightly distorted tetrahedral heavy-metal framework with three hydrides, each bridging a Ru–Ru edge, that (2) has a trigonal-bipyramidal structure with the Ru₃ ring capped above and below by µ₃-Bi atoms, and that (3) has a square-bipyramidal metal framework with the Ru atoms defining the equatorial square plane and the Bi atoms symmetrically µ₄-capping at the axial positions.