Chemistry of the interaction of some metal carbonyl clusters with metal oxide surfaces. [CpFe(CO)]4, Cp3Ni3(CO)2, and [CpNi(CO)]2 on alumina

Article abstract of DOI:10.1021/om50001a021

The nature of the interactions between [CpFe(CO)]₄, Cp₃Ni₃(CO)₂, and [CpNi(CO)]₂ with nearly fully dehydroxylated alumina were investigated by infrared spectroscopy, gas evolution, and other chemical means. A donor-acceptor interaction occurs between a carbonyl oxygen and the surface Al³⁺ in the case of [CpFe(CO)]₄ and Cp₃Ni₃(CO)₂ and possibly in the case of [CpNi(CO)]₂. The stability of these simple surfaces adducts increases in the order [CpNi(CO)]₂ < Cp₃Ni₃(CO)₂ < [CpFe(CO)]₄ with the γ-Al₂O₃-[CpFe(CO)]₄ adduct being stable for weeks and the adduct with [CpNi(CO)]₂ rapidly decomposing to Ni(CO)₄, CO, and other products. The chemistry of these metal clusters with an active alumina surface strongly parallels the reactions with aluminum bromide.