Phosphane Copper(I) Dicarboxylates: Synthesis and Their Potential Use as Precursors for the Spin‐coating Process in the Deposition of Copper 

Abstract

Dicopper dicarboxylates [(R3P)mCuXCu(PR3)m] (5a, X = O2CCO2, R = Ph, m = 2; 5b, X = O2CCO2, R = nBu, m = 3) were prepared by treatment of [Cu2O] (1a) with HO2CCO2H (2a) in presence of PR3 (4a, R = Ph; 4b, R = nBu). A further synthesis approach to mono‐ and dicopper dicarboxylates is given using an electrolysis cell equipped with Cu electrodes and charged with acids H2X and phosphanes R3P. Without addition of a base mononuclear [(nBu3P)mCuXH] (6a, m = 3, XH = O2CCO2H, 6b, m = 3, XH = O2CCH2CO2H, 6c, m = 3, XH = O2CCH2CH2CO2H, 6d, m = 2, XH = O2C‐2‐C5H4N‐6‐CO2H) was formed, whereas in presence of NEt3 (3), the dicopper systems [(R3P)mCuXCu(PR3)m] (5a, X = O2CCO2, R = Ph, m = 2; 5b, X = O2CCO2, R = nBu, m = 3; 5c, X = O2CCH2CO2, R = nBu, m = 3; 5d, X = O2CCH2CH2CO2, R = nBu, m = 3; 5e, X = O2C‐2‐C5H4N‐6‐CO2, R = nBu, m = 3) were produced. When 6a reacted with [(tmeda)Zn(nBu)2] (7), trimetallic [(tmeda)Zn((nBu3P)3CuO2CCO2)2] (8) was accessible. In this heterobimetallic complex the Zn(tmeda) unit spans two CuO2CCO2 entities. The molecular structures of 5a, 6a and 6d in the solid state were determined by single X‐ray structure analysis. Complexes 5a and 6a are monomers, whereas 6d creates in the solid state a linear open chain coordination polymer by hydrogen bridge formation. Characteristic for 6d is the somewhat distorted trigonal bipyrimidal arrangement around the copper atom with the nBu3P ligands in axial and the C5H3NCO2H oxygen and nitrogen atoms in equatorial positions. In 5a the oxalate connectivity binds in a μ‐1,2,3,4 fashion being part of a planar Cu2(oxalate) core. TG studies of several mono‐ and dicopper dicarboxylates were carried out. Release of the PR3 ligands is recognized and the remaining Cu‐(di)carboxylate unit decomposes to afford elemental copper and CO2. The deposition of copper onto pieces of PVD‐Cu oxidized silicon wafers by applying the spin‐coating process and using 5c and 5d as precursors is discussed.

Copper(II) Schiff base complexes and their mixed thin layers with ZnO nanoparticles

“…The layers were then heated up to 450 • C, and the result of this process was the conversion of complexes to CuO by decomposition. 20 In this case, SEM results showed incomplete homogeneous layers and defects in the surface structure. This was explained by the different film thicknesses obtained during the spin coating process, which upon heating produced defects due to unequal evaporation leading to partially cracked copper oxide films.…”

“…The layers were amorphous, but small crystallites appeared in some places due to incomplete solidification of the complex solution during the spin coating process, as previously reported. 20,54 In the case of Cu(en(pyca) 2 )Cl 2 ] (1a)/Si and [Cu(en(dmbaH) 2 )Cl 2 ] (3a)/Si materials, the whole silicon surface was covered regularly with copper complexes (900, 1100 and 2000 rpm/min (1a)/Si and 1000, 1100 and 2000 rpm/min (3a)/Si). The EDS results confirmed the presence of copper (0.45% -900 rpm, 0.71% -1000 rpm and 0.47% -1100 rpm) in all (1a)/Si layers.…”

Copper(I) oxalate complexes: Synthesis, structures and surprises

“…The reaction mixture was immediately filtered hot through a 0. (8). In an oven-dried 10 mL round-bottom flask, 0.091 g anhydrous oxalic acid (1 mmol) was dissolved in 5 mL degassed pyridine (py) with stirring.…”

“…However, as is frequently the case in these older papers and patents, the characterization data presented were very meager. Another early example of a copper(I) oxalate complex was a dinuclear triphenylphosphine complex reported by Gimeno et al [7], structurally characterized later by the Lang group [8], which also reported a few other copper(I) oxalate phosphine complexes in the same paper. Lang et al also reported a copper(I) oxalate complex with a bis(trimethylsilylpentadienyl)titanium bis(trimethylsilylacetylide) tweezer ligand, but the complex was not structurally characterized [9].…”

μ-Oxalato-bis[bis(triphenylphosphine)copper(I)] dichloromethane disolvate. Corrigendum

“…However, the authors were unaware of a previous report (Jakob et al, 2010) on the structure of (PPh 3 ) 2 Cu(C 2 O 4 )-Cu(PPh 3 ) 2 with a different number of dichloromethane solvent molecules. The authors sincerely regret this unintentional oversight.…”