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Group 11 complexes with the bis(3,5-dimethylpyrazol-1-yl)methane ligand. How secondary bonds can influence the coordination environment of Ag(I): the role of coordinated water in [Ag2(µ-L)2(OH2)2](OTf)2

AuthorsCalhorda, Maria José; Costa, Paulo J.; Crespo, Olga ; Gimeno, M. Concepción ; Jones, Peter G.; Laguna, Antonio ; Naranjo, Mar; Quintal, Susana; Yu-Jun, Shi; Villacampa, M. Dolores
Issue Date2006
PublisherRoyal Society of Chemistry
CitationDalton Transactions (34): 4104-4113 (2006)
AbstractThe complexation properties of the ligand bis(3,5-dimethylpyrazol-1-yl)methane ( L) towards group 11 metals have been studied. The reaction in a 1 : 1 molar ratio with [Cu(NCMe)4]PF6 or Ag(OTf) complexes gives the mononuclear [CuL(NCMe)]PF6 ( 1), with crystallographic mirror symmetry, or dinuclear [Ag2(µ-L)2](OTf)2 ( 2) (OTf = trifluoromethanesulfonate) in which the ligand bridges both silver centres, an unprecedented mode of coordination for this type of ligands. Compound 2 crystallizes with two water molecules and forms a supramolecular structure through classical hydrogen bonding. The reaction in a 2 : 1 ratio affords in both cases the four-coordinated derivatives [ML2]X (M = Cu, X = PF6 ( 3); Ag, X = OTf ( 4)). The treatment of [Ag(OTf)(PPh3)] with the ligand L gives [AgL(PPh3)]OTf ( 5). The gold(I) derivative [Au2(C6F5)2(µ-L)] ( 6) has also been obtained by reaction of L with two equivalents of [Au(C6F5)(tht)]. These complexes present a luminescent behaviour at low temperature; the emissions being mainly intraligand but enhanced after coordination of the metal. Compounds 1–4 have been characterized by X-ray crystallography. DFT studies showed that, in the silver complex 2, coordination of H2O to Ag in the binuclear complex is favoured by formation of a hydrogen-bonding network, involving the triflato anion, and releasing enough energy to allow distortion of the Ag2 framework.
Description10 pages, 9 tables, 9 figures, 1 scheme.
Publisher version (URL)http://dx.doi.org/10.1039/b605034d
Appears in Collections:(ICMA) Artículos
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