Transition Metal/Lanthanide-Nitrogen Double Bonds Co-stabilized in a Carbon Cage  

作　　者：Zhanxin Jiang Ziqi Hu Yang-Rong Yao Wenhao Xiang Xinyi Han Jinpeng Xin Huaimin Jin Shangfeng Yang 

机构地区：[1]Key Laboratory of Precision and Intelligent Chemistry,Collaborative Innovation Center of Chemistry for Energy Materials(iChEM),Department of Materials Science and Engineering,University of Science and Technology of China,Hefei 230026,China

出　　处：《Precision Chemistry》2024年第5期193-199,共7页精准化学（英文）

基　　金：National Natural Science Foundation of China(51925206,U1932214,52302052,22301288);Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450301);Anhui Provincial Natural Science Foundation(2308085MB33,2308085MB31);Fundamental Research Funds for the Central Universities(20720220009,WK2060000051);National Synchrotron Radiation Laboratory(KY2060000240).

摘　　要：Metal−nitrogen double bonds have been commonly reported for conventional metal complexes,but the coexistence of both transition metal−nitrogen and lanthanide−nitrogen double bonds bridged by nitrogen within one compound has never been reported.Herein,by encapsulating a ternary transition metallanthanide heteronuclear dimetallic nitride into a C_(84) fullerene cage,transition metal−nitrogen and lanthanide-nitrogen double bonds are costabilized simultaneously within the as-formed clusterfullerene TiCeN@C_(1)(12)-C_(84),which is a representative heteronuclear dimetallic nitride clusterfullerene.Its molecular structure was unambiguously determined by single-crystal X-ray diffraction,revealing a slightly bentμ2-bridged nitride cluster with short Ti−N(1.761Å)and Ce−N(2.109Å)bond lengths,which are comparable to the corresponding Ti=N and Ce=N double bonds of reported metal complexes and consistent with the theoretically predicted values,confirming their coexistence within TiCeN@C_(1)(12)-C_(84).Density functional theory(DFT)calculations unveil three-center two-electron(3c-2e)bonds delocalized over the entire TiCeN cluster,which are responsible for costabilization of Ti�N and Ce�N double bonds.An electronic configuration of Ti4+Ce^(3+)N^(3−)@C_(84)^(4−)is proposed featuring an intramolecular four-electron transfer,drastically different from the analogous actinide dimetallic nitride clusterfullerene(U_(2))^(9+)N^(3−)@C_(80)^(6−)and trimetallic nitride clusterfullerene(Sc_(2))^(6+)Ti^(3+)^(N3−)@C_(80)^(6−),indicating the peculiarity of 4-fold negatively charged fullerene cage in stabilizing the heteronuclear dimetallic nitride cluster.

关 键 词：FULLERENE METALLOFULLERENE transitionmetal LANTHANIDE metal−nitrogen multiplebond 

分 类 号：O62[理学—有机化学]