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.