State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. China.
LPCNO, CNRS & INSA, Université Paul Sabatier, 135 Avenue de Rangueil, 31077 Toulouse, France.
J Am Chem Soc. 2021 Feb 24;143(7):2705-2709. doi: 10.1021/jacs.1c00148. Epub 2021 Feb 11.
The first isolation and structural characterization of a rare-earth metal-terminal imido complex were reported in 2010, but a rare-earth metal-terminal phosphinidene complex is still absent, to date. Herein, we report the synthesis and structure of the first example of a rare-earth-terminal phosphinidene complex, namely the scandium boronylphosphinidene complex. Single-crystal X-ray diffraction shows that the complex has a much shorter Sc-P bond length as compared to that in a related scandium boronylphosphido complex, 2.381(1) Å vs 2.564(1) Å. DFT calculations indicate the presence of a strong Sc-P π interaction in this complex, which is in striking contrast to the weak interaction found in the phosphido complex. A preliminary reactivity study demonstrates that the scandium-terminal boronylphosphinidene complex behaves as a nucleophilic phosphinidene complex.
2010 年首次报道了稀土金属端亚氨基配合物的分离和结构特征，但迄今为止，尚未有稀土金属端膦烯配合物的报道。在此，我们报告了首例稀土端膦烯配合物，即钪硼基膦烯配合物的合成与结构。单晶 X 射线衍射表明，与相关的钪硼基膦化物配合物相比，该配合物中的 Sc-P 键要短得多，为 2.381(1)Å 对 2.564(1)Å。DFT 计算表明，该配合物中存在强烈的 Sc-Pπ 相互作用，这与膦化物配合物中发现的弱相互作用形成鲜明对比。初步反应性研究表明，钪端硼基膦烯配合物表现为亲核膦烯配合物。
