LCM, CNRS, Ecole polytechnique, Route de Saclay, 91128 Palaiseau Cedex, France.
Dalton Trans. 2018 Jul 17;47(28):9226-9230. doi: 10.1039/c8dt02196a.
The divalent samarium triflate salt does not react with CO2 or water, but does react with traces of O2 or N2O to form a tetrameric bis-oxo samarium motif. The reaction with O2 is a 4e- reductive cleavage where the electrons are coming from four different samarium centers. This highlights a rare synergistic effect for cleaving O2, which has no precedent in divalent lanthanide complexes. Additionally, the addition of CO2 to the tetrameric bis-oxo intermediate leads to the formation of a tetrameric bis-carbonate samarium triflate. Thus, the concomitant reaction of CO2 with traces of O2 leads to the same bis-carbonate tetrameric assembly.
二价钐三氟甲磺酸盐水合物不与 CO2 或水反应，但与痕量的 O2 或 N2O 反应，形成四聚体双-氧代钐基元。与 O2 的反应是一个 4e-还原裂解，电子来自四个不同的钐中心。这突出了一种罕见的协同效应，用于裂解 O2，在二价镧系元素配合物中没有先例。此外，将 CO2 添加到四聚体双-氧代中间体中，导致形成四聚体双碳酸根合三氟甲磺酸钐。因此，痕量 CO2 与 O2 的伴随反应导致相同的双碳酸根四聚体组装。
