Abstract

We showcase efficient synthetic protocols of cyclopentadienyl metal dicarbonyl, CpM(CO)2 (M = Rh and Ir). Reflecting the relativistic effect, the 1H and 13C signals of the Cp ring in CpIr(CO)2 were upfield shifted when compared with the Rh analogue. A missing dinuclear complex, (CpIr)2(μ-CO)(CO)2, was spontaneously generated together with [CpIr(CO)]3 by the loss of CO. The crystallographic analyses unambiguously determined their unique structures with one and three Ir–Ir bonds, respectively.

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