Reactivity of Dirhodium Analogues of Octaborane-12 and Decaborane-14 towards Transition-Metal Moieties

Building upon the key results of our earlier work on rhodaboranes, we continue to explore the chemistry of two nido-rhodaborane clusters, [(Cp*Rh)2B8H12] (1) and [(Cp*Rh)2B6H10] (2) with [Au(PPh3)Cl] that yielded [(Cp*Rh)2(AuPPh3)2B8H10] (3) and isomeric [(Cp*Rh)2(AuPPh3)2B6H8] (4a,b) respectively. The reactivity of 2 with [Au(PPh3)Cl] was rather unusual. In 3 Au exhibits a regular μ2-bonding mode, while in 4a,b there is a μ3-bonding with a Au–Rh bond. Further, the reactivity of 2 was performed with [Fe2(CO)9] that permitted the isolation of 12-vertex [(Cp*Rh)2B6H6{Fe(CO)2}2{Fe(CO)3}2] (5), 7-vertex [(Cp*Rh)2{Fe(CO)3}2B3H3] (6), and the heterometallic compound [(Cp*Rh)2{Fe(CO)3}2(μ3-CO)2] (7) in moderate to good yields. The cluster core of 5 consists of a 10-vertex isocloso geometry with two additional {Fe(CO)3} vertices capping two trigonal faces. Cluster 6 contains a capped-octahedral geometry, where one of the boron atoms is in the capping position. All of the compounds have been characterized by IR an...

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