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

• Published in: Inorganica Chimica Acta Vol. 350; pp. 114 - 120
• Main Authors: Leschke, M, Melter, M, Lang, H
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 04.07.2003
• Subjects: Carboxylate; Chelate; Chinoate; Phosphane; Silver(I); β-Diketonate; Silver(I); β-Diketonate; Carboxylate; Chinoate; Phosphane; Chelate
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(02)01500-1

The synthesis of the mononuclear and homobimetallic silver(I) complexes [P(C 6H 4CH 2NMe 2-2) 3]AgL 2 [L 2=acetylacetonate, acac ( 5a); tropolonate, trop ( 5b); 3-hydroxy-2-methyl-γ-pyranoate, pyro ( 5c)], [P(C 6H 4CH 2NMe 2-2) 3]AgOC(O)Me ( 8) and [P(C 6H 4CH 2NMe 2-2) 3]AgL 4Ag[P(C 6H 4CH 2NMe 2-2) 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 [AgL 2] [L 2=acac ( 3a), trop ( 3b), pyro ( 3c)], [Ag 2L 4] [L 4=benz ( 3d), anthra ( 3e)] or [AgCO 2Me] ( 7) with P(C 6H 4CH 2NMe 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 [AgNO 3] ( 1) with HL 2 or H 2L 4 ( 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 2NCH 2 built-in arms is dynamic. The synthesis of a series of mono- and bimetallic phosphane-stabilised silver(I) transition metal complexes with teminal-bound and bridging organic ligands, such as carboxylates and β-diketonates and derivatives thereof is reported. The two silver(I) ions in the respective homobimetallic species are spanned by a benzochinoate or anthrachinoate unit, respectively. In the [P(C 6H 4CH 2NMe 2-2) 3]AgOC(O)Me carboxylate complex a T-shaped arrangement with a linear PAgO unit is characteristic.