Chang Yu-Lun, Lin Ya-Fan, Chuang Wan-Jung, Kao Chai-Lin, Narwane Manmath, Chen Hsing-Yin, Chiang Michael Y, Hsu Sodio C N
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan.
Dalton Trans. 2018 Apr 17;47(15):5335-5341. doi: 10.1039/c7dt03843g.
Two copper(i)-nitro complexes [Tpm3-tBuCu(NO2)] (1) and [(Ph3P)2N][Tp3-tBuCu(NO2)] (2), containing steric bulky neutral tris(3-tert-butylpyrazolyl)methane and anionic hydrotris(3-tert-butylpyrazolyl)borate ligands, have been synthesized and characterized. Complex 2 adopts a unique κ2-binding mode of Tp3-tBu around the copper(i)-nitro environment in the solid state and shows a four-coordinated tetrahedral geometry surrounded by a nitro and three pz3-tBu groups in solution. Both complexes 1 and 2 allow for the stoichiometric reduction of NO2- to NO with H+ addition. The results of this effort show that increasing steric bulk and electron donation properties on the nitrogen ancillary ligand will improve the nitrite reduction ability of the copper(i)-nitro model complexes.
已合成并表征了两种含空间位阻较大的中性三（3-叔丁基吡唑基）甲烷和阴离子氢三（3-叔丁基吡唑基）硼酸酯配体的铜（Ⅰ）-硝基配合物[Tpm3-tBuCu(NO2)]（1）和[(Ph3P)2N][Tp3-tBuCu(NO2)]（2）。配合物2在固态时在铜（Ⅰ）-硝基环境周围采用独特的Tp3-tBu的κ2-配位模式，在溶液中呈现由一个硝基和三个pz3-tBu基团包围的四配位四面体几何构型。配合物1和2都能通过添加H+将NO2-化学计量还原为NO。这项工作的结果表明，增加氮辅助配体上的空间位阻和给电子性质将提高铜（Ⅰ）-硝基模型配合物的亚硝酸盐还原能力。
