Synthesis and Reactivity of a Transient, Terminal Nitrido Complex of Rhodium
Synthesis and Reactivity of a Transient, Terminal Nitrido Complex of Rhodium
复制标题
DOI：
10.1021/ja409764j
复制
发表时间：
2013-11-27
影响因子：
15
通讯作者：
Schneider, Sven
中科院分区：
文献类型：
--
作者：
Scheibel, Markus G.;Wu, Yanlin;Schneider, Sven
用Rh(N-3){N(CHCHPtBu2)(2)}照射Rh(II)叠氮络合物，可以对报道的第一个末端含氮配体的Rh(N-3)[N(CHCHPtBu2)(2)}]进行光谱表征。密度泛函理论计算表明，氮化罗络合物[Rh(N){N(CHCHPtBu2)(2)}]的未配对电子位于与氮基有关的反键Rh-N pi*键中，从而导致了主要的N-自由基特征，从而为其瞬变性质和观察到的氮化物与氮氮的偶联提供了理论基础。
Irradiation of rhodium(II) azido complex [Rh(N-3){N(CHCHPtBu2)(2)}] allowed for the spectroscopic characterization of the first reported rhodium complex with a terminal nitrido ligand. DFT computations reveal that the unpaired electron of rhodium(IV) nitride complex [Rh(N){N(CHCHPtBu2)(2)}] is located in an antibonding Rh-N pi* bond involving the nitrido moiety, thus resulting in predominant N-radical character, in turn providing a rationale for its transient nature and observed nitride coupling to dinitrogen.