Comparison of Isoelectronic Heterometallic and Homometallic Binuclear Cyclopentadienylmetal Carbonyls: The Iron–Nickel vs. the Dicobalt Systems

The heterometallic binuclear cyclopentadienylironnickel carbonyl compounds Cp2FeNi(CO)n (n =3 , 2, 1; Cp =η 5 -C5H5) have been studied by density functional theory (BP86) for comparison with the isoelectronic homometallic dicobalt derivatives Cp2Co2(CO)n. The FeNi tricarbonyl is shown to be the doubly bridged isomer Cp2Fe(CO)Ni(µ-CO)2 with an Fe– Ni distance of 2.455 A (BP86), in accord with experiment and in contrast to Cp2Co2(CO)3 where singly and triply bridged but not doubly bridged isomers are found. The dicarbonyl compounds Cp2FeNi(µ-CO)2 and Cp2Co2(µ-CO)2 both have analogous doubly bridged structures with M=M distances around 2.35 A, suggesting formal M=M double bonds. The monocarbonyl compounds have analogous singly bridged axial structures Cp2FeNi(µ-CO) and Cp2Co2(µ-CO) with

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