Disilver(I) Coordination Complexes: Synthesis, Reaction Chemistry, and Their Potential Use in CVD and Spin-Coating Processes for Silver Deposition

Jakob A, Rüffer T, Schmidt H, et al. Disilver(I) Coordination Complexes: Synthesis, Reaction Chemistry, and Their Potential Use in CVD and Spin-Coating Processes for Silver Deposition. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. 2010;2010(19):2975-2986.The synthesis of complexes [Ag2X] [X = O2CCO2 (3a), C4O4 (3b), O2CCH2CO2 (3c), O2C(CH2)2CO2 (3d), cis-O2CCH=CHCO2 (3e), trans-O2CCH=CHCO2 (3f), para-O2CC6H4CO2 (3g)] and [(R3P)mAgXAg(PR3)m] [R = Ph, X = C4O4, m = 2 (10a), m = 3 (10b); R = nBu, X = O2CCH2CO2, m = 2 (10c), m = 3 (10d); X = O2C(CH2)2CO2, m = 1 (10e), m = 2 (10f), m = 3 (10g); X = cis-O2CCH=CHCO2, m = 1 (10h), m = 2 (10i), m = 3 (10j); X = trans-O2CCH=CHCO2, m = 1 (10k), m = 2 (10l), m = 3 (10m); X = para-O2CC6H4CO2, m = 2 (10n)] is reported. Compoundds 3a–3g are accessible by the reaction of [AgNO3] (1) with H2X (2a–2g), while 10a–10n can be prepared by treatment of 3a–3g with PR3 (9a, R = Ph; 9b, R = nBu) in the ratios of 1:2, 1:4, or 1:6. When [{Ag(bipym)(NO3)·H2O}n] (6) (bipym = bipyrimidine) reacts with (HNEt3)2(O2CCO2) (7), [{Ag(bipym)Ag(O2CCO2)·4H2O}n] (5) and [{(bipym)(Ag(O2CCO2H))2}n] (8) are formed. The molecular structures for 5, 6, and 8 in the solid state are reported. For 5, the formation of a 3D network is characteristic, in which 1D chains of {Ag(bipym)Ag(O2CCO2)}n interact with each other through π–π interactions between the bipym ligands to extend in one direction, while H2O molecules act as connectivities thorugh the intermolecular H-bridge formation to extend in the other direction. Polymeric 6 consists of 2D layers formed by individual 1D chains of {Ag(bipym)Ag(bipym)}n with π–π interactions between the bipym ligands. In 8, {(HO2CCO2)Ag(bipym)Ag(O2CCO2H)} units undergo intermolecular H-bridge formation to create 2D layers, π–π interactions between individual bipym ligands produce a 3D network. The use of 10d as a CVD precursor in the deposition of Ag on glass by using a direct liquid injection system is discussed. The Ag films show a rough appearance and contain C impurities. The use of 10e and 10f as spin-coating precursors for the deposition of Ag on TiN-coated oxidized Si wafers is reported