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(MeOC<

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).

Silver Dimer, Tetramer, Polymer, and Network Structures with the Stannylene Stanna-closo-dodecaborate

“…These very short Ag−Ag interatomic distances are shorter than the comparable distance in the phosphine adduct [{Ag(SnB 11 H 11 )PPh 3 } 2 ] 2− [2.7160(4) Å] and the Ag−Ag distance in metallic silver [2.89 Å] . Furthermore, the found Ag−Ag contacts belong to the group of the shortest values known in the literature. − In [{Ag(SnB 11 H 11 )PEt 3 } 3 ] 3− we found, with 2.6326(10) Å, an example with a shorter Ag−Ag distance, and in diaryltriazene- and amidinate-bridged dimers the Ag−Ag bond length is only a little bit longer. − In the complexes 5 − 7 an interesting distortion in the solid state was detected: the plane through the nitrogen atoms is not perpendicular to the plane through the tin and silver atoms (Figure ). Probably due to packing forces, the angle between the best planes through the nitrogen atoms and the four Sn and Ag atoms ranges from 65° to 76°.…”

Synthesis and Structures of Dinuclear Copper(I) and Silver(I) 1, 3‐Bis[(2‐chloro)benzene]triazenide Complexes

“…The molecular structure of the complexes [Cu 2 (L) 2 ], and [Ag 2 (L) 2 ] are depicted in Figure 1 and Figure 2. The copper and silver complexes [Cu 2 (L) 2 ] and [Ag 2 (L) 2 ] are isotypic, and share many of the gross structural features of previously structurally characterized Cu I , and Ag I di‐metallic systems17–20 (Table 3), consisting of two central metal atoms bridged by two triazenide ligands in an μ,η 1 ,η 1 ‐fashion, with approximately linear two coordinate arrangements [N(1)–Cu(1)–N(3#1): 171.00(7)° and N(1)–Ag(1)–N(3#1): 166.64(7)°, respectively], with the deviation caused by the metal atoms moving away from each other. The N–N–N angle in [Ag 2 (L) 2 ]is 117.47(18)°, larger than that observed in [Cu 2 (L) 2 ] [115.43(16)°], due to different sizes for silver and copper atoms.…”

Synthesis, characterization and electrocatalytic performance of a dinuclear triazenidosilver(I) complex for hydrogen production

“…[Ag 2 (L) 2 ] consists of two silver centers bridged by two triazenido ligands in a μ,η 1 ,η 1 fashion, with two approximately linear coordinate geometries (N(12)–Ag(3)–N(2 i ), 165.35(11)°; N(2)–Ag(3 i )–N(12 i ), 165.35(11)°) with the deviation caused by silver atoms being displaced away from each other. The AgN bond distances in [Ag 2 (L) 2 ] are in the range 2.149(3)–2.163(3) Å, and the AgAg distance is 2.7424(7) Å, which is longer than those of reported dinuclear silver(I) complexes [Ag 2 (μ‐Ph‐NNN‐Ph) 2 ] (2.669(1) Å), [Ag 2 {μ‐MeOC 6 H 4 ‐NNN‐C 6 H 4 OMe} (2.680(2) Å) and [Ag 2 {μ‐ o ‐C 6 H 4 (Cl)‐NNN‐ o ‐C 6 H 4 ‐(Cl)} 2 ] (2.7208(5) Å) …”