Ruthenium and osmium carbonyl clusters incorporating stannylene and stannyl ligands

Abstract

The reaction of [Ru₃(CO)₁₂] with Ph₃SnSPh in refluxing benzene furnished the bimetallic Ru–Sn compound [Ru₃(CO)₈(μ-SPh)₂(μ₃-SnPh₂)(SnPh₃)₂] 1 which consists of a SnPh₂ stannylene bonded to three Ru atoms to give a planar tetra-metal core, with two peripheral SnPh₃ ligands. The stannylene ligand forms a very short bond to one Ru atom [Sn–Ru 2.538(1) Å] and very long bonds to the other two [Sn–Ru 3.074(1) Å]. The germanium compound [Ru₃(CO)₈(μ-SPh)₂(μ₃-GePh₂)(GePh₃)₂] 2 was obtained from the reaction of [Ru₃(CO)₁₂] with Ph₃GeSPh and has a similar structure to that of 1 as evidenced by spectroscopic data. Treatment of [Os₃(CO)₁₀(MeCN)₂] with Ph₃SnSPh in refluxing benzene yielded the bimetallic Os–Sn compound [Os₃(CO)₉(μ-SPh)(μ₃-SnPh₂)(MeCN)(η¹-C₆H₅)] 3. Cluster 3 has a superficially similar planar metal core, but with a different bonding mode with respect to that of 1. The Ph₂Sn group is bonded most closely to Os(2) and Os(3) [2.786 and 2.748 Å respectively] with a significantly longer bond to Os(1), 2.998 Å indicating a weak back-donation to the Sn. The reaction of the bridging dppm compound [Ru₃(CO)₁₀(μ-dppm)] with Ph₃SnSPh afforded [Ru₃(CO)₆(μ-dppm)(μ₃-S)(μ₃-SPh)(SnPh₃)] 5. Compound 5 contains an open triangle of Ru atoms simultaneously capped by a sulfido and a PhS ligand on opposite sides of the cluster with a dppm ligand bridging one of the Ru–Ru edges and a Ph₃Sn group occupying an axial position on the Ru atom not bridged by the dppm ligand.