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This study develops mechanistic understanding of the factors which control the phase in syntheses of copper selenide nanocrystals by investigating how the chemistry of the dodecylselenol reactant is altered by the ligand and solvent environment. 1 H NMR and 77 Se NMR were used to study how commonly used solvents (octadecene and dioctylether) and ligands (oleylamine, oleic acid, stearylamine, stearic acid and trioctyl phosphine) change the nature of the dodecylselenol reactant at 25 °C, 155 °C and 220 °C. Unsaturations were prone to selenol additons, carboxylates underwent selenoesterification, amines caused the release of H 2 Se gas, and the phosphine formed phosphine selenide. Adventitious water caused oxidation to didodecyldiselenide. NMR studies were correlated with the phases that resulted in syntheses of nanocrystalline copper selenides, in which berzalianite, umangite or a metastable hexagonal phase were produced as identified by X-ray diffraction, depending on the ligand and solvent environemnts. Formation of the rare hexagonal Cu 2− x Se phase could be assigned to cases that included DD 2 Se 2 as a reactive intermediate, or strong L-type ligation of amines which was dependant on alkyl chain length.