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Phosphite copper(I) trifluoroacetates [((RO)(3)P)(m)CuO2CCF3] (m=1, 2, 3): synthesis, solid state structures and their potential use as CVD precursors

: Mothes, R.; Rüffer, T.; Shen, Y.Z.; Jakob, A.; Walfort, B.; Petzold, H.; Schulz, S.E.; Ecke, R.; Gessner, T.; Lang, H.


Dalton transactions 39 (2010), Nr.46, S.11235-11247
ISSN: 1477-9226
ISSN: 2209-2386
ISSN: 1477-9234
Fraunhofer ENAS ()

Metal-organics [((RO)(3)P)(m)CuO2CCF3] (R = CH3: 11a, m = 1; 11b, m = 2; 11c, m = 3. R = CH2CH3: 12a, m = 1; 12b, m = 2; 12c, m = 3. R = CH2CF3: 13a, m = 1; 13b, m = 2; 13c, m = 3) are either accessible by the reaction of [((RO)(3)P)(m)CuCl] (R = CH3: 5a, m = 1; 5b, m = 2; 5c, m = 3. R = CH2CH3: 6a, m = 1; 6b, m = 2; 6c, m = 3) with [KO2CCF3] (7), or treatment of [Cu2O] (8) with HO2CCF3 (9) and P(OR)(3) (2, R = CH3; 3, R = CH2CH3; 4, R = CH2CF3). P-31{H-1} NMR spectra [((CH3O)(3)P)(m)CuO2CCF3] (m = 1, 1.5, 2, 2.5, 3, 3.5, and 4) have been studied at 25 and -80 degrees C showing phosphite ligand exchange in solution. The molecular structures of 11a and 13a-13c in the solid state are reported. Complexes 11a and 13a are tetramers featuring mu-eta(2)(1 kappa O:2 kappa O')- and mu(3)-eta(2)(1 kappa O:2kO':3 kappa O')-(11a) or mu(3)-eta(2)(1kO:2kO':3kO')-bonded O2CCF3 ligands (13a) with the Cu(I) ions being part of CuPO2 and CuPO3 units (11a), while in 13a solely a CuPO3 moiety is present. Skeletal isomerism of 11a vs. 13a is discussed. Compound 13b is dimeric ({CuP2O2}(2)) with pseudo-tetrahedral Cu environments and mu-eta(2)(1 kappa O:2 kappa O')O2CCF3 functionalities. In monomeric 13c the O2CCF3 ligand is eta(1)(kappa O)-bonded to a tetra-coordinated Cu(I) ion. The thermal solid state properties of 11, 12 and 13 were studied by Thermo Gravimetry (TG). These complexes decompose by phosphite elimination, decarboxylation and dealkylation. Hot-wall Chemical Vapour Deposition (CVD) experiments were carried out at 380 degrees C using 11c as precursor for the deposition of copper onto pieces of TiN-coated oxidized silicon substrates. Copper layers of high purity were obtained with grain sizes between 200-1200 nm.