Synthesis and Oligomerization of CpM(CO)₂

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.我们展示了通式为CpM(CO)₂（其中M为铑(Rh)与铱(Ir)）的二羰基环戊二烯基金属（cyclopentadienyl metal dicarbonyl）的高效合成方法。受相对论效应影响，与铑的类似物相比，二羰基环戊二烯基铱（CpIr(CO)₂）中环戊二烯基环的¹H与¹³C信号均发生了高场位移。在脱除一氧化碳（CO）的过程中，会自发生成一种尚未见诸报道的双核配合物(CpIr)₂(μ-CO)(CO)₂，同时还会生成[CpIr(CO)]₃。通过晶体学分析，我们明确确定了这两种产物独特的分子结构：前者含1个铱-铱键，后者则含3个铱-铱键。