In addition, exemplary calculations on the complexation energies and Gibbs energies were conducted for complexes 18-20, 25, and 26a, hypothetical complexes (entries 2, 6, and 7), and entries 9 and 10, without a crystal structure. The obtained energies should give information on the theoretical spontaneity of the respective complex formation step. For this purpose, the reaction of the ligand in the bridging conformation with the respective metal precursor was considered (see Supporting Information for further information, pages 33-38). The obtained energies support the experimental results; all formed complexes 18-20, 25, and 26 have negative theoretical complexation and Gibbs energies. A complexation of 5a with silver acetate is not expected due to the positive free Gibbs energy of the reaction (Table , entry 2), whereas the exergonic reaction to the other silver complexes 18, 19, and 25, summarized in Table , can occur. The strongly negative free energy of the silver nitrate complexation (18, entry 1) might be related to simplifying the three-dimensional crystal lattice to a separated Ag + and NO3 -pair within the single-molecule modeling approach. A slight tendency toward the bridging conformation of the heteroleptic silver triazolylquinoxaline-phosphine complexation can be derived from entries 5 and 6 as well as 9 and 10. The observed complexation mode seems to be mostly favored due to the higher stability of the final complex (see section above), not only due to the energetically slightly favored formation. For the copper complex 26, the formation of the experimentally observed chelate complex is predicted to be slightly energetically favored compared to the bridging complexation (entries 7 and 8). .12 1 Polymeric complex structure simplified for calculation as a tetramer with three silver atoms and four additional ammonia atoms to account for the next quinoxaline units.