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Issue 6, 2014
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Multi-nuclear silver(I) and copper(I) complexes: a novel bonding mode for bispyridylpyrrolides

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Abstract

Reaction of deprotonated 2,5-bis(2′-pyridyl)pyrrole (HPDPH) with AgOTf (where OTf = triflato) in THF readily yields a yellow triangular Ag3 complex [(PDPH)Ag]3 (1), of which the av. Ag⋯Ag distance is 2.902 Å. A mixture of HPDPH and AgOTf reacts with PPh3 to afford a linear Ag3 complex [Ag{(PDPH)Ag(PPh3)}2](OTf) (2·OTf), whereas it reacts with diethyl phosphite in the presence of Li[N(SiMe3)2] to yield a di-nuclear complex Li2[(PDPH)Ag2{P(O)(OEt)2}2](OTf) (Li2·3·OTf). In 2, the terminal Ag atoms are three coordinate containing one phosphorous atom from PPh3 and two nitrogen atoms of the PDPH ligand. The center Ag atom is only two coordinate, binding to the residued pyridyl N atom of the PDPH ligand. In 3, two silver atoms are bridged by one PDPH ligand. Treatment of PDPH with CuCl in the presence of NaH afforded a heterobimetallic copper–sodium complex [Cu(PDPH)2Na(thf)2] (4). The PDPH ligand in 1–4 is nonplanar, with torsion angles between pyridine and pyrrole rings in the range of 15.8–38.3°. The argentophilic interactions, π⋯π stacking, and weak interaction of Ag⋯C(aromatic) are observed in these complexes. Interestingly, treatment of the analogous 2,5-bis(6′-bromo-2′-pyridyl)pyrrole (HPDPBr) with AgOTf affords a di-nuclear complex [(HPDPBr)Ag]2(OTf)2 (5·(OTf)2). Its HPDPBr ligands coordinate to Ag atoms in a head-to-head fashion, and two protonated pyrrole linkages reside in the anti-parallel direction and are non-coordinating. Short Ag⋯Br distances of 3.255–3.390 Å are observed.

Graphical abstract: Multi-nuclear silver(i) and copper(i) complexes: a novel bonding mode for bispyridylpyrrolides

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Publication details

The article was received on 07 Oct 2013, accepted on 13 Nov 2013 and first published on 15 Nov 2013


Article type: Paper
DOI: 10.1039/C3DT52794H
Citation: Dalton Trans., 2014,43, 2458-2464
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    Multi-nuclear silver(I) and copper(I) complexes: a novel bonding mode for bispyridylpyrrolides

    X. Hu, Y. Liang, C. Li and X. Yi, Dalton Trans., 2014, 43, 2458
    DOI: 10.1039/C3DT52794H

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