Parr Joseph M, White Andrew J P, Crimmin Mark R
Molecular Sciences Research Hub, Department of Chemistry, Imperial College London, 82 Wood Lane, White City, Shepherds Bush London W12 0BZ UK
Chem Sci. 2022 May 16;13(22):6592-6598. doi: 10.1039/d2sc02063g. eCollection 2022 Jun 7.
Herein we report the first comprehensive series of crystallographically characterised transition metal formyl complexes. In these complexes, the formyl ligand is trapped as part of a chelating structure between a transition metal (Cr, Mn, Fe, Co, Rh, W, and Ir) and a magnesium (Mg) cation. Calculations suggest that this bonding mode results in significant oxycarbene-character of the formyl ligand. Further reaction of a heterometallic Cr-Mg formyl complex results in a rare example of C-C coupling and formation of an ethenediolate complex. DFT calculations support a key role for the formyl-intermediate in ethenediolate formation. These results show that well-defined transition metal formyl complexes are potential intermediates in the homologation of carbon monoxide.
在此，我们报道了首个经晶体学表征的过渡金属甲酰基配合物的全面系列。在这些配合物中，甲酰基配体作为螯合结构的一部分被困在过渡金属（铬、锰、铁、钴、铑、钨和铱）与镁（Mg）阳离子之间。计算表明，这种键合模式导致甲酰基配体具有显著的氧卡宾特征。异金属铬 - 镁甲酰基配合物的进一步反应产生了一个罕见的碳 - 碳偶联实例，并形成了乙烯二醇酸酯配合物。密度泛函理论计算支持甲酰基中间体在乙烯二醇酸酯形成中的关键作用。这些结果表明，定义明确的过渡金属甲酰基配合物是一氧化碳同系化反应中的潜在中间体。
