Jena Rashmi, Benner Florian, Delano Francis, Holmes Daniel, McCracken John, Demir Selvan, Odom Aaron L
Michigan State University, Department of Chemistry 578 S. Shaw Ln East Lansing MI USA 48824
Chem Sci. 2023 Mar 21;14(16):4257-4264. doi: 10.1039/d3sc00171g. eCollection 2023 Apr 26.
A room temperature stable complex formulated as Y(NHAr*) has been prepared, where Ar* = 2,6-(2,4,6-(Pr)CH)CH, by KC reduction of ClY(NHAr*). Based on EPR evidence, Y(NHAr*) is an example of a d Y(ii) complex with significant delocalization of the unpaired electron density from the metal to the ligand. The isolation of molecular divalent metal complexes is challenging for rare earth elements such as yttrium. In fact, stabilization of the divalent state requires judicious ligand design that allows the metal center to be coordinatively saturated. Divalent rare earth elements tend to be reactive towards various substrates. Interestingly, Y(NHAr*) reacts as a radical donor towards BuNC to generate an unusual yttrium isocyanide complex, CNY(NHAr*), based on spectroscopic evidence and single-crystal X-ray diffraction data.
通过用钾还原ClY(NHAr*),制备了一种室温稳定的配合物,其化学式为Y(NHAr*),其中Ar* = 2,6-(2,4,6-(Pr)CH)CH。基于电子顺磁共振(EPR)证据,Y(NHAr*)是一种d Y(ii)配合物的实例,其未成对电子密度从金属到配体有显著的离域。对于钇等稀土元素而言,分离分子二价金属配合物具有挑战性。事实上,稳定二价态需要精心设计配体,使金属中心达到配位饱和。二价稀土元素往往对各种底物具有反应性。有趣的是,根据光谱证据和单晶X射线衍射数据,Y(NHAr*)作为自由基供体与丁腈反应,生成一种不寻常的异氰酸钇配合物CNY(NHAr*)。