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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Multi-nuclear silver(I) and copper(I) complexes: a novel bonding mode for bispyridylpyrrolides
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Multi-nuclear silver(I) and copper(I) complexes: a novel bonding mode for bispyridylpyrrolides

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摘要

Reaction of deprotonated 2,5-bis(2'-pyridyl)pyrrole (HPDP_H) with AgOTf (where OTf~- = triflato) in THF readily yields a yellow triangular Ag_3 complex (PDP_H)Agl_3 (1), of which the av. Ag...Ag distance is 2.902 ?. A mixture of HPDP_H and AgOTf reacts with PPh_3 to afford a linear Ag_3 complex Ag{(PDP_H)Ag(PPh_3)}_2~- (OTf) (2?OTf), whereas it reacts with diethyl phosphite in the presence of LiN(SiMe_3)_2 to yield a dinuclear complex Li_2(PDP_H)Ag_2{P(O)(OEt)_2}_2(OTf) (Li_2?3?OTf). In 2, the terminal Ag atoms are three coordinate containing one phosphorous atom from PPh_3 and two nitrogen atoms of the PDP_H ligand. The center Ag atom is only two coordinate, binding to the residued pyridyl N atom of the PDP_H ligand. In 3, two silver atoms are bridged by one PDP_H ligand. Treatment of PDP_H with CuCl in the presence of NaH afforded a heterobimetallic copper-sodium complex Cu(PDP_H)_2Na(thf)_2 (4). The PDP_H 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 (HPDP_(Br)) with AgOTf affords a di-nuclear complex (HPDP_(Br))Ag_2(OTf)_2 (5?(OTf)_2). Its HPDP_(Br) 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 ? are observed.

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