Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14850 (USA).
Department of Chemistry, Center for Advanced Scientific Computing and Modeling (CASCaM), University of North Texas, Box 305070, Denton, TX 76203-5070 (USA).
Angew Chem Int Ed Engl. 2015 Nov 23;54(48):14407-11. doi: 10.1002/anie.201507463. Epub 2015 Oct 6.
The impact of redox non-innocence (RNI) on chemical reactivity is a forefront theme in coordination chemistry. A diamide diimine ligand, {-CH=N(1,2-C6H4)NH(2,6-iPr2C6H3)}2 (n = 0 to -4), (dadi)(n), chelates Cr and Fe to give [(dadi)M] ([1Cr(thf)] and [1Fe]). Calculations show [1Cr(thf)] (and [1Cr]) to have a d(4) Cr configuration antiferromagnetically coupled to (dadi)(2-)*, and [1Fe] to be S = 2. Treatment with RN3 provides products where RN is formally inserted into the C-C bond of the diimine or into a C-H bond of the diimine. Calculations on the process support a mechanism in which a transient imide (imidyl) aziridinates the diimine, which subsequently ring opens.
氧化还原非中性（RNI）对化学反应性的影响是配位化学的前沿主题。一种二酰胺二亚胺配体，{-CH=N(1,2-C6H4)NH(2,6-iPr2C6H3)}2 (n = 0 至-4)，(dadi)(n)，螯合 Cr 和 Fe 以得到[(dadi)M] ([1Cr(thf)] 和[1Fe])。计算表明[1Cr(thf)]（和[1Cr]）具有反铁磁耦合到(dadi)(2-)*的 d(4)Cr 构型，而[1Fe]为 S = 2。用 RN3 处理提供了 RN 形式插入二亚胺的 C-C 键或插入二亚胺的 C-H 键的产物。该过程的计算支持一种机制，其中瞬态亚胺（亚氨）将二亚胺氮丙啶化，随后环打开。
