Nguyen Thuy-Ai D, Cook Andrew W, Wu Guang, Hayton Trevor W
Department of Chemistry and Biochemistry, University of California , Santa Barbara, California 93106, United States.
Inorg Chem. 2017 Jul 17;56(14):8390-8396. doi: 10.1021/acs.inorgchem.7b01062. Epub 2017 Jun 28.
We report a critical re-evaluation of the synthesis and characterization of Cu(MPP). This product was reportedly formed by the reaction of Cu(NO) with 2-mercapto-5-n-propylpyrimidine (HMPP) and NaBH, in ethanol, in the presence of [N(CH)][Br]. In our hands, we found no experimental evidence to support the existence of Cu(MPP) in the reaction mixture. Instead, we demonstrate that the material isolated from this reaction is a complex mixture containing [N(CH)], Br, NO, and 2-mercapto-5-n-propyl-1,6-dihydropyrimidine (HMPP*), along with the Cu(I) coordination polymer, [Cu(MPP)]. To support our conclusions, we have independently synthesized HMPP* and [Cu(MPP)], as well as the related Cu(I) coordination complexes, [Cu(HMPP*)] and [Cu(MPP*)]. All new materials were characterized by NMR spectroscopy and mass spectrometry, while HMPP*, [Cu(HMPP*)] (n = 4), and [Cu(MPP)] (n = 6) were also characterized by X-ray crystallography.
我们报告了对Cu(MPP)合成与表征的关键重新评估。据报道，该产物是由Cu(NO)与2-巯基-5-正丙基嘧啶（HMPP）以及NaBH在乙醇中，于[N(CH)][Br]存在下反应形成的。在我们的实验中，未发现支持反应混合物中存在Cu(MPP)的实验证据。相反，我们证明从该反应中分离出的物质是一种复杂混合物，包含[N(CH)]、Br、NO以及2-巯基-5-正丙基-1,6-二氢嘧啶（HMPP*），还有Cu(I)配位聚合物[Cu(MPP)]。为支持我们的结论，我们独立合成了HMPP和[Cu(MPP)]，以及相关的Cu(I)配位配合物[Cu(HMPP)]和[Cu(MPP*)]。所有新材料均通过核磁共振光谱和质谱进行表征，而HMPP*、[Cu(HMPP*)]（n = 4）和[Cu(MPP)]（n = 6）还通过X射线晶体学进行了表征。
