Copper(I) Carboxylates of Type [('' BU3P)(m)CuO2CR] (m=1, 2, 3) - Synthesis, Properties, and their Use as CVD Precursors

Copper(I) carboxylates of type [('' Bu3P)(m)CuO2CR] (m = 1: 3a, R = Me; 3b, R = CF,: 3c. R Ph: 3d R = CH=CHlPh, m = 2: 4a, R = Me: 4b, R = CF,: 4c. R = Ph: 4d, R = CH = CHPh, m = 3: 8a. R = Me; 8b, R = CF3(;) 8c. R = CH2Ph; 8d, R = (CHOCH2)(3)H; 8e, R = 'C4H7O) are accessible by following Synthesis methodologies the reaction of [CuO2CR] (1a, R = Me; 1b, R = CF3; 1c, R = Ph; 1d, R = CH = CHPh) with m equivalents of '' Bu3P (2) (m = 1, 2, 3), or treatment of [('' Bu3P)(m) CuCl] (5a, m = 1: 5b, m = 2) with [KO2CCF3] (6). A more straight forward synthesis method for 8a - 8e is the electrolysis of copper in presence of HO2CR (7a, R = Me; 7b, R = CF3; 7c, R = CH2Ph; 7d, R = (CH2OCH2)(3)H; 7e, R = (C4H7O)-C-c) and 2. respectively. This method allows to prepare the appropriate copper(I) carboxylate complexes in virtually quantitative yield, analytically pure form, and on an industrial scale. IR spectroscopic studies revealthat the carboxylic units in 4, 5, and 8 bind in a unidentate, chelating or mu-briding fashion to copper(I) depending on m and R. The thermal properties of 4, 6. and 8 were determined by TG and DSC studies. Based on TG-MS experiments a conceivable mechanism for the thermally induced decomposition of these species is presented. presented. Hot-wall Chemical Vapor Deposition experiments (CVD) with precursor 4b showed that copper could be deposited at 480 degrees C onto a TiN-coated oxidized silicon substrate. The copper films were characterized by SEM and FDX studies. Pure layers were obtained with copper particles of size 200 - 780 nm.