NO and N 2 O Release from the Trityl Diazeniumdiolate Complexes [M(O 2 N 2 CPh 3 ) 3 ] − (M = Fe, Co)
NO and N 2 O Release from the Trityl Diazeniumdiolate Complexes [M(O 2 N 2 CPh 3 ) 3 ] − (M = Fe, Co)
复制标题
三苯甲基二氮烯鎓二醇络合物释放 NO 和 N 2 O [M(O 2 N 2 CPh 3 ) 3 ] — (M = Fe, Co)
DOI：
10.1021/acs.inorgchem.2c04088
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发表时间：
2023
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.;Chakraborty, Arunavo;Guzman, Camilo F.;Kräh, Sabrina;Wu, Guang;Hayton, Trevor W.
MBr2 与 3 当量的 [K(18-crown-6)][O2N2CPh3] 反应生成三苯甲基二氮烯二醇配合物 [K(18-crown-6)][M(O2N2CPh3)3] (M = Co,2; Fe,3)，收率良好。使用371 nm光照射2和3分别导致NO形成，产率为10%和1%（假设每个复合物最多产生6当量的NO来计算）。 N2O也在2的光解过程中形成，产率63%，而3的光解导致N2O以及Ph3CN(H)OCPh3的形成，产率分别为37%和5%。这些产物表明二醇二氮烯鎓通过 C-N 和 N-N 键断裂途径发生断裂。相反，用 1.2 当量的 [Ag(MeCN)4][PF6] 氧化络合物 2 和 3 导致 N2O 形成，但没有 NO 形成，表明在这些条件下二醇二氮烯鎓断裂仅通过 C-N 键断裂发生。虽然 NO 的光解产率不大，但与之前报道的 Zn 同系物相比，它们增加了 10 至 100 倍，这表明氧化还原活性金属中心的存在有利于三苯甲基二醇二氮烯鎓裂解时形成 NO。
Reaction of MBr2with 3 equiv of [K(18-crown-6)][O2N2CPh3] generates the trityl diazeniumdiolate complexes [K(18-crown-6)][M(O2N2CPh3)3] (M = Co,2; Fe,3) in good yields. Irradiation of2and3using 371 nm light led to NO formation in 10 and 1% yields (calculated assuming a maximum of 6 equiv of NO produced per complex), respectively. N2O was also formed during the photolysis of2, in 63% yield, whereas photolysis of3led to the formation of N2O, as well as Ph3CN(H)OCPh3, in 37 and 5% yields, respectively. These products are indicative of diazeniumdiolate fragmentation via both C–N and N–N bond cleavage pathways. In contrast, oxidation of complexes2and3with 1.2 equiv of [Ag(MeCN)4][PF6] led to N2O formation but no NO formation, suggesting that diazeniumdiolate fragmentation occurs exclusively via C–N bond cleavage under these conditions. While the photolytic yields of NO are modest, they represent a 10- to 100-fold increase compared to the previously reported Zn congener, suggesting that the presence of a redox-active metal center favors NO formation upon trityl diazeniumdiolate fragmentation.