Synthesis and characterisation of the benzene butterfly cluster [(η6-C6H6)Ru(R1C2R2)Os3(CO)9](R1= R2= Me, Et or Ph; R1= Me, R2= H, Et or Ph); X-ray crystal structure of [(η6-C6H6)Ru(MeC2Me)Os3(CO)9]

Abstract

Reduction of the triosmium cluster [Os₃(CO)₁₀(R¹C₂R²)](R¹= R²= Me 1a, Et 1b or Ph 1c; R¹= Me, R²= H 1d, Et 1e or Ph 1f) with K–Ph₂CO has yielded the dianionic cluster [Os₃(CO)₉(R¹C₂R²)]^2–2a–2f. When this dianion is treated with HBF₄·Et₂O or [Au(PPh₃)Cl] the compounds [Os₃(CO)₉-(R¹C₂R²)X(Y)](X = Y = H 3a–3f; X = Y = AuPPh₃4a–4f; X = H, Y = AuPPh₃5a–5f) are formed. The dianion 2 also reacts with the dication [Ru(C₆H₆)(MeCN)₃]²⁺ to give the mixed-metal cluster [(η⁶-C₆H₆)Ru(R¹C₂R²)Os₃(CO)₉]6a–6f. Compound 6a(R¹= R²= Me) has been characterised by single-crystal X-ray diffraction analysis and shown to contain a butterfly metal geometry spanned by the Me₂C₂ grouping with a η⁶-C₆H₆ bonded to the ‘wingtip’ ruthenium atom.