The decomposition of copper formate clusters is investigated in the gas phase by infrared multiple photon dissociation of Cu(II)_n(HCO₂)_2n+1⁻, n≤8. In combination with quantum chemical calculations and reactivity measurements using oxygen, elementary steps of the decomposition of copper formate are characterized, which play a key role during calcination as well as for the function of copper hydride based catalysts. The decomposition of larger clusters (n>2) takes place exclusively by the sequential loss of neutral copper formate units Cu(II)(HCO₂)₂ or Cu(II)₂(HCO₂)₄, leading to clusters with n=1 or n=2. Only for these small clusters, redox reactions are observed as discussed in detail previously, including the formation of formic acid or loss of hydrogen atoms, leading to a variety of Cu(I) complexes. The stoichiometric monovalent copper formate clusters Cu(I)_m(HCO₂)_m+1⁻, (m=1,2) decompose exclusively by decarboxylation, leading towards copper hydrides in oxidation state +I. Copper oxide centers are obtained via reactions of molecular oxygen with copper hydride centers, species containing carbon dioxide radical anions as ligands or a Cu(0) center. However, stoichiometric copper(I) and copper(II) formate Cu(I)(HCO₂)₂⁻ and Cu(II)(HCO₂)₃⁻, respectively, is unreactive towards oxygen.

中文翻译：

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分解铜甲酸盐簇：洞悉煅烧和二氧化碳活化的基本步骤。

甲酸铜簇的分解在气相中的Cu红外线多个光子解离（II）研究_Ñ（HCO ₂）_{2 Ñ 1} ^- ，Ñ ≤8。与量子化学计算和使用氧气的反应性测量相结合，表征了甲酸铜分解的基本步骤，这些步骤在煅烧以及氢化铜基催化剂的功能中起着关键作用。较大簇（n > 2）的分解仅通过中性甲酸铜单元Cu（II）（HCO ₂）₂或Cu（II）₂（HCO ₂）₄，得到n = 1或n = 2的簇。仅对于这些小簇，如先前详细讨论的那样观察到了氧化还原反应，包括甲酸的形成或氢原子的损失，从而导致各种Cu（I）络合物。化学计量的一价甲酸铜簇簇Cu（I）_m（HCO ₂）_{m +1} ^-，（m =1,2）仅通过脱羧而分解，从而生成氧化态+ I的氢化铜。氧化铜中心是通过分子氧与氢化铜中心，含有二氧化碳自由基阴离子作为配体的物种或Cu（0）中心反应而获得的。然而，化学计量铜（I）和铜（II），甲酸铜（I）（HCO ₂）₂ ^-和Cu（II）（HCO ₂）₃ ^-分别是对氧不反应。