Me3SiCtriple bond; length of mdashC–CMedouble bond; length as m-dashCH2 copper(I) β-diketonates: Synthesis, solid state structure, and low-temperature chemical vapour deposition

The ene-yne copper(I) β-diketonates [(η2-TMSMB)Cu(β-diketonate)] (β-diketonate = acetylacetonate/acac, 5; = 1,3-di-tert-butylacetonate/dbac, 6; = 1,1,1,5,5,5-hexafluoroacetylacetonate/hfac, 7; TMSMB = 4-TriMethylSilyl-2-Methyl-But-1-ene-3-yne, Me3SiCtriple bond; length of mdashC–CMedouble bond; length as m-dashCH2) are accessible by the reaction of [(η2-TMSMB)Cu(μ-Cl)]2 (3) with [Na(β-diketonate)] (β-diketonate = acac, 4a; = dbac, 4b; = hfac, 4c) in a 1:2 molar ratio. Complexes 6 and 7 are also formed, when Cu2O (8) is reacted with H-hfac (9a) or H-dbac (9b), respectively. The solid state structure of 7 is reported. The copper(I) ion possesses a planar environment caused by the η2-coordinated TMSMB ligand and the chelate-bound hfac group, while the CMedouble bond; length as m-dashCH2 entity stays free. The thermal properties of 5–7 were determined by applying ThermoGravimetry (TG) and Differential Scanning Calorimetry (DSC). All complexes decompose in a two-step process beginning at ca. 85 °C. Elimination of TMSMB produces [Cu(β-diketonate)] which disproportionates to give [Cu(β-diketonate)2] and elemental copper. Preliminary hot-wall Chemical Vapour Deposition experiments (CVD) were carried out with 7. Copper films were deposited onto TiN-coated oxidised silicon wafers at a precursor vaporisation temperature of 50 °C and a deposition temperature of 145 °C. The films were characterised by SEM and EDX.