Search

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. more...

Copper(I) carboxylates of type [(nBu3P)mCuO2CR] (m = 1: 3a, R = Me; 3b, R = CF3; 3c, R = Ph; 3d, R = CH=CHPh. m = 2: 4a, R = Me; 4b, R = CF3; 4c, R = Ph; 4d, R = CH=CHPh. m = 3: 8a, R = Me; 8b, R = CF3; 8c, R = CH2Ph; 8d, R = (CH2OCH2)3H; 8e, R = cC4H7O) 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 nBu3P (2) (m = 1, 2, 3), or treatment of [(nBu3P)mCuCl] (5a, m = 1; 5b, m = 2) with [KO2CCF3] (6). A more straightforward 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)3H; 7e, R = cC4H7O) 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 reveal that the carboxylic units in 4, 5, and 8 bind in a unidentate, chelating or μ-bridging 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. Hot-wall Chemical Vapor Deposition experiments (CVD) with precursor 4b showed that copper could be deposited at 480 °C onto a TiN-coated oxidized silicon substrate. The copper films were characterized by SEM and EDX studies. Pure layers were obtained with copper particles of size 200 – 780 nm. more...

Die Reaktion von [(η2-Me3SiC≡CSiMe3)CuBr]2 (1) mit zwei Aquivalenten an [M(O∩O)] [M = Na, Ag; O∩O = Acetylacetonat, acac, 2a/ 3a; = 1, 1, 1, 5, 5, 5-Hexafluoroacetylacetonat, hfac, 2b/ 3b; = 2, 2, 6, 6-Tetramethyl-3, 5-heptandionat, tehe, 2c/ 3c; = 1, 3-Diphenyl-1, 3-propandionat, dipa, 2d/ 3d; = 2-Methyl-4-pyronat, mepy, 2e/ 3e; = Troponolat, trop, 2f/ 3f) fuhrt zu [(η2-Me3SiC≡CSiMe3)Cu(O∩O)] (4a, acac; 4b, hfac; 4c, tehe; 4d, dipa; 4e, mepy; 4f, trop), welche durch Umsetzung mit PR3 (R = C6H4CH2NMe2-2)3 (5) unter Verdrangung von Me3SiC≡CSiMe3 die Phosphan-Kupfer(I)-β-Diketonato-Komplexe [(R3P)Cu(O∩O)] (O∩O = acac, 6a; = hfac, 6b; = tehe, 6c; = dipa, 6d; = mepy , 6e; = trop, 6f) ] ergeben. Die Komplexe 6a — 6f werden auch gebildet, wenn man 5 mit aquimolaren Mengen an CuCl (7) und dann mit Na(O∩O) (2) zur Reaktion bringt. Verwendet man an Stelle von 2 bzw. 3 das Silbersalz Ag2(O2∩O2) (O2∩O2 = 1, 4-Benzochinoat, benz, 9a; = 1, 4-Anthrachinoat, anth, 9b), so werden homobimetallische Komplexe des Typs [(R3P)CuO2∩O2Cu(PR3)] (O2∩O2 = benz, 10a; = anth, 10b) erhalten, in denen zwei Kupfer(I)-Phosphan-Bausteine uber π-konjugierte organische O2∩O2-Brucken miteinander verknupft sind. Die Reaktion von 3 mit 5 im Verhaltnis von 1:1 ergibt die entsprechenden phosphanstabilisierten Silber(I)-Komplexe [(R3P)Ag(O∩O)] (O∩O = acac, 11a; = mepy , 11b; = trop, 11c)]. Bringt man dagegen 5 mit 0.5 Teilen an Ag2(O2∩O2) (9) zur Umsetzung, so sind die zu 10 isostrukturellen zweikernigen Komplexe [(R3P) AgO2∩O2Ag(PR3)] (O2∩O2 = benz, 12a; = anth, 12b) zuganglich. Wahrend die Kupfer(I)-Komplexe 6 und 10 in Losung und im Festkorper bestandig sind, beobachtet man fur die isostrukturellen Silber(I)-Spezies 11 und 12, das sie sich unter Einwirkung von Licht unter Abscheidung von elementarem Silber zersetzen. Die Verwendung von 4a und 6c als Ausgangsverbindungen zur Abscheidung von Kupferfilmen auf TiN-beschichteten SiO2-Wafern durch die chemische Gasphasenabscheidung wird vorgestellt. Die Kristallstruktur von 6f wird beschrieben. Einkerniges 6f kristallisiert zusammen mit [(R3P)CuCl] (8) (Verhaltnis 6f : 8 = 85 : 15) in der triklinen Raumgruppe P1¯ mit den Zellparametern a = 8.962(2), b = 10.753(3), c = 17.037(5)A, α = 78.29(2), β = 77.12(2), γ = 81.220(10), V = 1557.3(7)A3, Z = 2 mit 4703 beobachteten unabhangigen Reflexen (R1 = 0.0661). Das Kupfer(I)-Ion in 6f weist die Koordinationszahl 4 auf. Es liegt eine wannenformige Konformation fur die sechsgliedrigen CuPNCH2C2/Phenyl-Ringe vor und der Troponolat-Ligand bindet uber beide Sauerstoffatome symmetrisch an das Kupfer(I)-Ion. Mono- and Bimetallic Copper(I)- and Silver(I)-Phosphane Complexes with β-Diketonate Units The reaction of [(η2-Me3SiC≡CSiMe3)CuBr]2 (1) with two equivalents of [M(O∩O)] [M = Na, Ag; O∩O = acetylacetonate, acac, 2a/ 3a; = 1, 1, 1, 5, 5, 5-hexafluoroacetylacetonate, hfac, 2b/ 3b; = 2, 2, 6, 6-tetramethyl-3, 5-heptanedionate, tehe, 2c/ 3c; = 1, 3-diphenyl-1, 3-propandonate, dipa, 2d/ 3d; = 2-methyl-4-pyronate, mepy, 2e/ 3e; = troponolate, trop, 2f/ 3f) affords [(η2-Me3SiC≡CSiMe3)Cu(O∩O)] (4a, acac; 4b, hfac; 4c, tehe; 4d, dipa; 4e, mepy; 4f, trop), which further reacts with PR3 (R = C6H4CH2NMe2-2)3 (5) to give the phosphane copper(I) β-diketonato complexes [(R3P)Cu(O∩O)] (O∩O = acac, 6a; = hfac, 6b; = tehe, 6c; = dipa, 6d; = mepy , 6e; = trop, 6f) ] via replacement of Me3SiC≡CSiMe3. Complexes 6a — 6f are also formed, when 5 is reacted with equimolare amounts of CuCl (7) and than with Na(O∩O) (2). Using the silver salt Ag2(O2∩O2) (O2∩O2 = 1, 4-benzochinoate, benz, 9a; = 1, 4-anthrachinoate, anth, 9b) instead of 2 or 3, than homobimetallic complexes of type [(R3P)CuO2∩O2Cu(PR3)] (O2∩O2 = benz, 10a; = anth, 10b) are accessible in which two copper(I) phosphane building blocks are spanned by the π-conjugated organic bridging unit O2∩O2. The reaction of 3 with 5 in the ratio of 1:1 produces the phosphane-stabilized silver(I) complexes [(R3P)Ag(O∩O)] (O∩O = acac, 11a; = mepy , 11b; = trop, 11c)]. Homobimetallic [(R3P) AgO2∩O2Ag2(PR3)] (O2∩O2 = benz, 12a; = anth, 12b), which is isostructural to 10, is accessible by treatment of 5 with 0.5 equivalent of Ag2(O2∩O2) (9). While the respective copper(I) complexes 6 and 10 are stable in solution and in the solid-state, it appeared that the appropriate silver(I) complexes 11 and 12 decompose upon precipitation of silver on their exposure to light. The application of 4a and 6c as precursors in the CVD process (CVD = Chemical Vapour Deposition) for the deposition of copper films on TiN-coated SiO2 wafers is discussed. The solid-state structure of 6f is reported. Mononuclear 6f crystallizes together with [(R3P)CuCl] (8) (ratio 6f : 8 = 85 : 15) in the triclinic space group P1¯ with the cell parameters a = 8.962(2), b = 10.753(3), c = 17.037(5)A, α = 78.29(2), β = 77.12(2), γ = 81.220(10), V = 1557.3(7)A3, Z = 2 with 4703 observed unique reflections (R1 = 0.0661). The copper(I) ion in 6f possesses the coordination number 4. A boat-like conformation for the six-membered CuPNCH2C2/Phenyl cycle is found and the troponolate ligand is symmetrical chelate-bound via both oxygen atoms to the copper(I) ion. more...