Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and, Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, P. R. China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai, 200032, P. R. China.
Chemistry. 2022 Dec 1;28(67):e202202803. doi: 10.1002/chem.202202803. Epub 2022 Nov 14.
By applying the potassium salts of cyclopentadienyl-phosphine ligands LK to CoCl , the corresponding cobalt chlorides (1, LCo Cl) were prepared. By reducing complexes 1 with KHBEt under a N atmosphere, bridging end-on complexes, LCo -N -Co L (2 a and 2 b), were successfully obtained. N -labeled [ N ]-2 a was prepared under N / N exchange in THF solution. LCo -N -Co L complex 2 a could react with P molecules to release N and generate a Co-P -Co moiety 4. Further reduction of complex 2 b led to cleavage of a P-C bond in the cyclopentadienyl-phosphine ligand to provide novel μ-PCy -bridged Co -N complex 5. DFT calculations confirmed the experimental observations.
将环戊二烯基膦配体 LK 的钾盐应用于 CoCl ,得到相应的氯化钴(1,LCoCl)。通过在 N 气氛下用 KHBEt 还原配合物 1,成功地获得了桥接端到端配合物 LCo-N-CoL(2a 和 2b)。在 THF 溶液中的 N/N 交换下制备了 N 标记的[N]-2a。LCo-N-CoL 配合物 2a 可以与 P 分子反应释放 N 并生成 Co-P-Co 部分 4。进一步还原配合物 2b 导致环戊二烯基膦配体中的 P-C 键断裂,提供了新型的 μ-PCy-桥连 Co-N 配合物 5。DFT 计算证实了实验观察结果。