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Issue 27, 2012
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Formation of N-heterocyclic diphosphine ligands from Ag(I)-assisted condensation reactions between bdppeda and formaldehyde and their binuclear silver(I) complexes

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Abstract

The reaction of [Ag(MeCN)4]ClO4 with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda) in CH2Cl2/MeOH afforded an unexpected cationic binuclear complex [Ag2(L1)2(η,η-μ-ClO4)2](ClO4)2 (L1 = N,N′-bis(diphenylphosphanylmethyl)-3H-4,5-dihydroimidazole-1-ium) (1). Compound 1 was also prepared in high yield from reactions of [Ag(MeCN)4]ClO4 with N,N′-bis(diphenylphosphanylmethyl)ethylenediamine (bdppeda) in the presence of formaldehyde (HCHO) or formic acid (HCOOH). Analogous reactions of AgCl with bdppeda and HCHO resulted in the formation a neutral binuclear complex [Ag2(L2)2(μ-Cl)2] (L2 = N,N-bis(diphenylphosphanylmethyl)-tetrahydroimidazole) (2). Treatment of 1 with concentrated HCl gave rise to a partially anion-exchanged product [Ag2(L1)2(μ-Cl)2](ClO4)2 (3). Compounds 1 and 3 have a similar cationic binuclear structure, in which a [Ag2(η,η-μ-ClO4)2] or [Ag2(μ-Cl)2] ring is sandwiched by two in situ-formed cationic L1 ligands. The L1 ligand may be generated by the Ag(I)-assisted condensation reaction between bdppeda and HCHO or HCOOH. Compound 2 holds a neutral binuclear structure, in which a [Ag2(μ-Cl)2] ring is connected by two in situ-formed L2 ligands from its top and bottom sites. The neutral ligand L2 may be produced from another Ag(I)-assisted condensation reaction between bdppeda and HCHO. The in situ formation of the L1 and L2 ligands provides a new route to the N-heterocyclic diphosphine ligands, and an interesting insight into the coordination chemistry of their metal complexes.

Graphical abstract: Formation of N-heterocyclic diphosphine ligands from Ag(i)-assisted condensation reactions between bdppeda and formaldehyde and their binuclear silver(i) complexes

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Publication details

The article was received on 19 Apr 2012, accepted on 23 May 2012 and first published on 23 May 2012


Article type: Paper
DOI: 10.1039/C2DT30860F
Citation: Dalton Trans., 2012,41, 8447-8454
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    Formation of N-heterocyclic diphosphine ligands from Ag(I)-assisted condensation reactions between bdppeda and formaldehyde and their binuclear silver(I) complexes

    S. Sun, Z. Ren, J. Yang, R. He, F. Wang, X. Wu, W. Gong, H. Li and J. Lang, Dalton Trans., 2012, 41, 8447
    DOI: 10.1039/C2DT30860F

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