680602-14-6Relevant articles and documents
Mono- and Bimetallic Copper(I)- and Silver(I)-Phosphane Complexes with β-Diketonate Units
Lang,Leschke,Melter,Walfort,Koehler,Schulz,Gessner
, p. 2371 - 2380 (2008/10/09)
The reaction of [(η2-Me3SiC≡CSiMe 3)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-Me3- SiC≡CSiMe3)Cu(O∩O)] (4a, acac; 4b, hfac; 4c, tehe; 4d, dipa; 4e, mepy; 4f, trop), which further reacts with PR3 (R = C6H4CH2NMe 2-2)3 (5) to give the phosphane copper(I) ss-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) (O 2∩O2 = 1,4-benzochinoate, benz, 9a; = 1,4-anthrachinoate, anth, 9b) instead of 2 or 3, than homobimetallic complexes of type [(R3P)CuO2∩O2. Cu(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. Te 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∩O 2Ag2(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∩O 2) (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 PI 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) A 3, 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 CuPNCH2C 2/Phenyl ycle is found and the troponolate ligand is symmetrical chelate-bound via both oxygen atoms to the copper(I) ion.
