Photolytic or Oxidative Fragmentation of Trityl Diazeniumdiolate (O 2 N 2 CPh 3 – ): Evidence for Both C–N and N–N Bond Cleavage
Photolytic or Oxidative Fragmentation of Trityl Diazeniumdiolate (O 2 N 2 CPh 3 – ): Evidence for Both C–N and N–N Bond Cleavage
复制标题
三苯甲基二氮烯鎓二醇 (O 2 N 2 CPh 3 – ) 的光解或氧化断裂：C–N 和 N–N 键断裂的证据
DOI：
10.1021/acs.inorgchem.2c01809
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发表时间：
2022
影响因子：
4.6
通讯作者：
Hayton, Trevor W.
中科院分区：
文献类型：
--
作者：
Baeza Cinco, Miguel Á.;Kräh, Sabrina;Guzman, Camilo F.;Wu, Guang;Hayton, Trevor W.
将[K（18-冠-6）（THF）2][CPh 3]（THF =四氢呋喃; Ph =苯基）暴露于一氧化氮（NO）气氛中以优异的产率干净地生成[K（18-冠-6）][O2 N2 CPh 3]（1）。[ZnCl_2（THF）_2]与3当量的1反应得到C-二醇二氮烯配合物[K（18-冠-6）][Zn（O_2N_2CPh_3）_3]（2）。化合物1和2的结构均经1H和13 C {1H} NMR表征，其结构经X射线单晶衍射确证。用371 nm的光使2光解，生成三种含三苯甲基的产物，即Ph 3CH、9-苯基芴和Ph 3CN（H）OCPh 3（3）。此外，我们检测到一氧化二氮（N2 O），以及少量的NO在反应混合物中。相反，用1.2当量的[Ag（MeCN）4][PF 6]氧化2导致形成O（CPh 3）2作为主要的含三苯甲基的产物;在反应混合物中也检测到N2 O，但在这种情况下没有明显形成NO。这些断裂产物的观察表明，[O2 N2 CPh 3]−配体对C-N键和N-N键的断裂都很敏感。此外，不同的产物分布表明[O2 N2 CPh 3]−对不同的裂解模式敏感。
Exposure of [K(18-crown-6)(THF)2][CPh3] (THF = tetrahydrofuran; Ph = phenyl) to an atmosphere of nitric oxide (NO) cleanly generates [K(18-crown-6)][O2N2CPh3] (1) in excellent yields. A subsequent reaction of [ZnCl2(THF)2] with 3 equiv of1affords theC-diazeniumdiolate complex [K(18-crown-6)][Zn(O2N2CPh3)3] (2). Both1and2were characterized by1H and13C{1H} NMR spectroscopy, and their structures were confirmed by X-ray crystallography. Photolysis of2using 371 nm light resulted in the formation of three trityl-containing products, namely, Ph3CH, 9-phenylfluorene, and Ph3CN(H)OCPh3(3). In addition, we detected nitrous oxide (N2O), as well as small amounts of NO in the reaction mixture. In contrast, oxidation of2with 1.2 equiv of [Ag(MeCN)4][PF6] resulted in the formation of O(CPh3)2as the major trityl-containing product; N2O was also detected in the reaction mixture, but NO was not apparently formed in this case. The observation of these fragmentation products indicates that the [O2N2CPh3]−ligand is susceptible to both C–N bond and N–N bond cleavage. Moreover, the different product distributions suggest that [O2N2CPh3]−is susceptible to different modes of fragmentation.