Chen Ming, Zhang Zhaoyin, Liu Jun, Li Gongyu, Zhao Lili, Mo Zhenbo
State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin, 300071, China.
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing, 211816, China.
Angew Chem Int Ed Engl. 2023 Nov 27;62(48):e202312837. doi: 10.1002/anie.202312837. Epub 2023 Oct 27.
Due to their limited capacity for π-backdonation, isolation of π-complexes of main-group elements remains a great challenge. We report herein the synthesis of a homoleptic diphosphene lead complex (2) from the degradation of P with a bis(germylene)-stabilized Pb(0) complex. Structural and computational studies showed that 2 possesses significant π bonding interactions between Pb atom and diphosphene ligands, which is reminiscent of transition-metal diphosphene complexes. Consistent with its unique electronic structure, complex 2 can deliver Pb(0) atoms to perform redox reaction with an iminoquinone to produce a cyclic plumbylene (4) and perform 2,5-dimethyl-3,4-dimethylimidazol-1-ylidene (IMe Me ) induced phosphorus cation abstraction to give an anionic PbP complex (6).
由于主族元素的π-反馈能力有限，分离主族元素的π-配合物仍然是一个巨大的挑战。我们在此报告了一种由双（亚锗烯）稳定的Pb(0)配合物降解P合成的均配双膦铅配合物（2）。结构和计算研究表明，2在Pb原子和双膦配体之间具有显著的π键相互作用，这让人联想到过渡金属双膦配合物。与其独特的电子结构一致，配合物2可以提供Pb(0)原子与亚胺醌进行氧化还原反应生成环状铅烯（4），并进行2,5-二甲基-3,4-二甲基咪唑-1-亚基（IMe Me ）诱导的磷阳离子抽取反应，得到阴离子PbP配合物（6）。
