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Mono- and bimetallic silver(I) complexes with bridging and terminal-bound organic chelating ligands

The synthesis of the mononuclear and homobimetallic silver(I) complexes [P(C6H4CH2NMe2-2) 3]AgL2 [L2=acetylacetonate, acac (5a); tropolonate, trop (5b); 3-hydroxy-2-methyl-γ-pyranoate, pyro (5c)], [P(C6H4CH2NMe2-2) 3]AgOC(O)Me (8) and [P(C6H4CH 2NMe2-2)3]Ag-L4-Ag[P(C 6H4CH2NMe2-2)3] [L 4=2,5-dihydroxy-p-benzochinoate, benz (6a); 1,4-dihydroxy- anthrachinoate, anthra (6b)] can be achieved by the reaction of the silver(I) salts [AgL2] [L2=acac (3a), trop (3b), pyro (3c)], [Ag2L4] [L4=benz (3d), anthra (3e)] or [AgCO2Me] (7) with P(C6H4CH2NMe 2-2)3 (4) in a 1:1 or 1:2 molar ratio. The respective silver(I) salts 3a-3e are accessible by treatment of [AgNO3] (1) with HL2 or H2L4 (2a-2d), respectively. In 5a-5c, 6a and 6b the silver atom possesses a pseudotetrahedral environment caused by the chelate-bound ligands acac, trop, pyro, benz or anthra and the bidentate coordinated phosphane 4. In homobimetallic 6a and 6b the appropriate transition metals are spanned by the benz or anthra units, respectively. While in 5a-5c, 6a and 6b the silver metal possesses the coordination number 4, in 8 a T-shaped arrangement is set-up with a linear P-Ag-O unit. The chemical and physical behaviour of complexes 5a-5c, 6a, 6b and 8 is reported. Spectroscopic studies reveal that on the NMR time-scale the phosphane group with its Me 2NCH2 built-in arms is dynamic.

Mono- and Bimetallic Copper(I)- and Silver(I)-Phosphane Complexes with β-Diketonate Units

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.