Synthesis and characterisation of some hexanuclear heterometallic clusters containing arene ligands; the crystal and molecular structures of RuOs5(CO)15(η6-C6H6) and RhOs5(CO)15(η5-C5Me5)

✍ Scribed by Richard K. Henderson; Patricia A. Jackson; Brian F.G. Johnson; Jack Lewis; Paul R. Raithby

• Book ID: 104138776
• Publisher: Elsevier Science
• Year: 1992
• Tongue: English
• Weight: 850 KB
• Volume: 198-200
• Category: Article
• ISSN: 0020-1693
• DOI: 10.1016/s0020-1693(00)92381-8

✦ Synopsis

Treatment of the pentaosmium dianionic cluster [Os5(CO),,]*-(1) with either one equivalent of the dication [Ru($-C,H,)(MeCN),]'+ (2), or one equivalent of [Rh($-C,H,)(MeCN),]'+ (3), in dichloromethane, at 0 "C, affords two isomeric forms of the cluster RuOs,(CO),,($-C,H,) (4), or three isomeric forms of RhOs,(C0)15($-C,Me,) (5), respectively. One isomeric form of each cluster (4a and 5a) has been characterised crystallographically. The structures of 4a and Sa both contain a bicapped tetrahedral metal core in which the heteroatom occupies one of the two capping positions; this is in accord with the geometry predicted for a six metal atom cluster with 84 valence electrons. Reduction of the cluster 4 with K/Ph,CO, in tetrahydrofuran, affords the octahedral dianionic cluster [RuOS~(CO),,(~~-CJ-I,)]~-(6). When this dianion is treated with HBF,*EtzO decomposition occurs, and small amounts of the parent cluster 4 are regenerated. Treatment of 6 with [AuPEt,]Clml[BF,] gives the neutral cluster RuOs,(C0)14($YCSHg)(AuPEt3)2 (7).