Phosphane- and phosphite-silver(I) phenolates: Synthesis, characterization and their use as CVD precursors

The silver(I) salts [AgOR] (3a, R = C9H6N; 3b, R = C6H4-2-CHO, 3c, R = C6H4-2-Cl; 3d, R = C6H4-2-CN; 3e, R = C6H4-2-NO2) are accessible by the stoichiometric reaction of [AgNO3] (1) with HOR (2a, R = C9H6N; 2b, R = C6H4-2-CHO; 2c, R = C6H4-2-Cl; 2d, R = C6H4-2-CN; 2e, R = C6H4-2-NO2) in presence of NEt3. Treatment of 3a–3e with PnBu3 (4), P(OMe)3 (5a) or P(OCH2CF3)3 (5b) in the ratios of 1:1 and 1:2, respectively, produced complexes [LmAgOR] (L = PnBu3, m = 1: 6a, R = C9H6N; 6b, R = C6H4-2-CHO; 6c, R = C6H4-2-Cl; 6d, R = C6H4-2-CN; 6e, R = C6H4-2-NO2. m = 2: 7a, R = C9H4; 7b, R = C6H4-2-CHO; 7c, R = C6H4-2-Cl; 7d, R = C6H4-2-CN; 7e, R = C6H4-2-NO2. L = P(OMe)3, m = 1: 8a, R = C6H4-2-CHO; 8b, R = C6H4-2-NO2. m = 2: 9, R = C6H4-2-NO2. L = P(OCH2CF3)3, m = 1: 10, R = C6H4-2-NO2). Based on TGA, temperature-programmed and in situ molecular beam mass spectrometry metal–organic 7e was applied as CVD precursor in the deposition of silver onto glass substrates. The resulting silver films were characterized by XRD. The SEM image of a film grown from 7e at 350 °C showed a homogeneous surface with grain sizes of 40 nm. The molecular structures of 8b and 10 in the solid state were determined. They are isostructural and are cubane-like structured. Low-temperature 31P{1H} NMR studies showed that the title complexes are dynamic in solution and exchange at room temperature their ligands.