Several copper(I) iminopyrrolidinates have been evaluated by thermogravimetric analysis (TGA) and solution based (1)H NMR studies to determine their thermal stability and decomposition mechanisms. Iminopyrrolidinates were used as a ligand for copper(I) to block previously identified decomposition routes of carbodiimide deinsertion and β-hydrogen abstraction. The compounds copper(I) isopropyl-iminopyrrolidinate (1) and copper(I) tert-butyl-iminopyrrolidinate (2) were synthesized for this study, and compared to the previously reported copper(I) tert-butyl-imino-2,2-dimethylpyrrolidinate (3) and the copper(I) guanidinate [Me(2)NC((i)PrN)(2)Cu](2) (4). Compounds 1 and 2 were found to be volatile yet susceptible to decomposition during TGA. At 165 °C in C(6)D(6), they had half-lives of 181.7 h and 23.7 h, respectively. The main thermolysis product of 1 and 2 was their respective protonated iminopyrrolidine ligand. β-Hydrogen abstraction was proposed for the mechanism of thermal decomposition. Since compound 3 showed no thermolysis at 165 °C, it was further studied by chemisorption on high surface area silica. It was found to eliminate an isobutene upon chemisoption at 275 °C. Annealing the sample at 350 °C showed further evidence of the decomposition of the surface species, likely eliminating ethene, and producing a surface bound methylene diamine.