Synthese von zweikernigen Triazenido- und Pentaazadienidokomplexen des einwertigen Silbers. Kristallstruktur von [Ag(MeOC6H4N3C6H4OM e)]2· 2/3 Py, [Ag(MeOC6H4N5C6H4OMe)]2 und [Ag(EtOC6H4N5C6H4OEt)]2 · Py / Dimeric Triazenido and Pentaazadienido Complexes of Monovalent Silver. Synthesis and Structure of [Ag(MeOC6H4N3C6H4OM e)]2· 2/3 Pyridine, [Ag(MeOC6H4N5C6H4OMe)]2 und [Ag(EtOC6H4N5C6H4OEt)]2 · Pyridine

Abstract

[Ag(MeOC6H4N3C6H4OMe)]2 (1) is formed in THF from AgNO3 , and the triazenide anion, as obtained from the corresponding triazene and Na. 1 crystallizes from pyridine in the form of orange-yellow , air stable crystals with the com position 1·2/3 C5H5N: space group P 1̅ with a = 1468.0(5), b = 1514.1(6), c - 1316.1(3) pm, a = 113.45(3)°, β = 1 1 4 .8 1 (2 )°, γ = 66.78(3)°, Z - 3. The triazenide ion functions as a bridging ligand forming planar (AgN3)2 heterocycles. The unit cell contains two symmetry-independent dinuclear complexes, one of which is centrosymmetrical. The short Ag -Ag distances of 268.0 and 269.8 pm suggest Ag -Ag bonding. The pentaazadienido complexes Ag(RN5R) with R = p -MeO - C6H4 (2), p -EtO - C6H4 (3), p-Cl -C6H4 (4), p -F -C6H4 (5), are obtained from saturated solutions of the pentaazadiene in conc. NH3 and AgNO3 , as explosive, red precipitates which are stable in air. Crystals of 2 and 3 · C5H5N are obtained from pyridine. 2 crystallizes in the monoclinic space group P21/c: a - 583.7(6), b = 1705.1(9), c = 1489.6(9) pm. β = 96.2(1)°, Z = 2; 3 · C5H5N is triclinic (space group P 1̅) with a = 1160.4(4). b = 1671.0(6), c = 509.0(1) pm. a = 97.51(2)°, β = 97.36(2)°, γ = 81.51(3)°, Z = 1. The complexes 2 and 3 are dinuclear with the pentaazadienide ion as a (N1)-η1,(N5)-η1 bridging ligand in 2 and a (N1)-η1, (N3)-η1 bridging ligand in 3. The bridging mode in 3 results in a short Ag -Ag contact of 283.44 pm. The Ag -N distances range from 210.8 to 215.7 pm in 1 and from 215.0 to 220 pm in (2) and (3).