Larsen Emil Mickey Hilligsøe, Brock-Nannestad Theis, Skibsted Jørgen, Reinholdt Anders, Bendix Jesper
Department of Chemistry, University of Copenhagen Universitetsparken 5 DK-2100 Copenhagen Denmark
Department of Chemistry and Interdisciplinary Nanoscience Center (iNANO), Aarhus University Langelandsgade 140 DK-8000 Aarhus C Denmark.
Chem Sci. 2024 Sep 30;15(43):18067-75. doi: 10.1039/d4sc04843a.
Herein, the first example of a homoleptic Ag complex stabilized by a monodentate N-donor ligand is presented. Na[SO] oxidizes the linear Ag complex, Na[Ag(succ)] (1), to form a square planar argentate(iii) ion, [Ag(succ)], which crystallizes with a polymeric chain-structure, M[Ag(succ)] (2), when treated with alkali metal sulfate MSO (M = K, Rb, Cs). A mixed-valent Robin-Day class I system, [(HO)Ag][Ag(succ)] (2), forms in the absence of K/Rb/Cs ion. Diamagnetic 2 displays a succinimide C[double bond, length as m-dash]O stretching frequency at higher energy than does the isoelectronic Pd complex, [(HO)Na][Pd(succ)] (3). Moreover, 2 displays UV-vis absorptions that are more intense and occur at lower energy than those in 3. The electron-deficient nature of 2 is further evident from its ability to oxidize water to O. From Ag magic-angle spinning NMR studies, a highly deshielded Ag environment in 2 (2080 ppm) relative to the Ag starting material 1 (492 ppm) is observed.
在此，展示了由单齿氮供体配体稳定的同配体银配合物的首个实例。Na[SO]将线性银配合物Na[Ag(succ)] (1)氧化，形成平面正方形的银(III)离子[Ag(succ)]，当用碱金属硫酸盐MSO (M = K、Rb、Cs)处理时，其以聚合链结构M[Ag(succ)] (2)结晶。在不存在K/Rb/Cs离子的情况下形成了混合价态的罗宾 - 戴I类体系[(HO)Ag][Ag(succ)] (2)。抗磁性的2显示出琥珀酰亚胺C[双键，长度为中划线]O伸缩频率，其能量高于等电子的钯配合物[(HO)Na][Pd(succ)] (3)。此外，2的紫外 - 可见吸收比3中的更强且出现在更低能量处。2的缺电子性质从其将水氧化为O的能力中进一步显现出来。通过银魔角旋转核磁共振研究，观察到相对于银起始原料1 (492 ppm)，2中银的环境高度去屏蔽(2080 ppm)。
