This article reviews the chemistry of nickel and palladium complexes with terminally bound hydroxide and alkoxide ligands. The research carried out in our group is discussed in the context of the general literature. It is shown that suitable methods of synthesis, combined with the choice of adequate ligands allow the isolation of a range of stable complexes. This has enabled a detailed investigation of the chemical reactivity of the M−O bonds, once believed to be intrinsically weak. The elucidation of trends in thermodynamic stability and kinetic lability is the key for a better understanding of the reactivity of this class of compounds, that combines basic and nucleophilic properties with typical organometallic patterns, like β‐hydrogen elimination. Based on reversible acid‐base exchange and CO₂ insertion reactions, we discuss how the polarity of the M‐OR bonds influence their relative stability, their hydrolytic sensitivity and their tendency to react with electrophiles.

中文翻译：

---

具有反应性σ-金属-氧共价键的镍和钯配合物

本文介绍了具有末端结合的氢氧化物和醇盐配体的镍和钯配合物的化学性质。我们小组进行的研究是在一般文献的背景下进行的。结果表明，合适的合成方法与适当配体的选择相结合，可以分离出一系列稳定的复合物。一旦被认为本质上是弱的，这使得能够对M-O键的化学反应性进行详细的研究。阐明热力学稳定性和动力学不稳定性的趋势是更好地了解此类化合物反应性的关键，该类化合物将基本和亲核性质与典型的有机金属图案（如β-氢消除）结合在一起。基于可逆的酸碱交换和CO ₂ 在插入反应中，我们讨论了M-OR键的极性如何影响其相对稳定性，水解敏感性以及与亲电试剂反应的趋势。