Synthesis of the tetraruthenium carbido cluster [Ru4(H)2C(CO)12]via mixed ruthenium–gold carbido intermediates; X-ray crystal structures of [Ru4C(CO)12(AuPMe2Ph)2], [Ru4C(CO)12(I)(AuPEt3)], and [Ru4(H)C(CO)12(AuPPh3]

Abstract
The action of CO on the pentanuclear carbido cluster [Ru5C(CO)14(AuPR3)2][PR3= PEt3(2), PMe2Ph (3)](80 atm, 60 °C) affords the tetranuclear carbido cluster [Ru4C(CO)12(AuPR3)2][PR3= PEt3(4) PPh3(5), PMe2Ph (6)], which exhibits a carbide-centred, ‘butterfly’ Ru4C core with both the ‘wing-tip’ and ‘hinge’ Ru atoms bridged by AuPR3 groups; the ‘hinge’ bridging AuPR3 group may be replaced by reaction with I2 or HI to give [Ru4C(CO)12(I)(AuPR3)][PR3= PEt3(7), PPh3(8)] and [Ru4(H)C(CO)12(AuPR3)][PR3= PEt3(9), PPh3(10)], respectively, and the subsequent reaction of (9) and (10) with [BH4] removes the remaining AuPR3 group, acidification affording the tetraruthenium carbide [Ru4(H)2C(CO)12](11)

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