A Stable Salt of the Tris(ethene)silver Cation: Structure and Characterization of [Ag(η²‐C₂H₄)₃]⁺[Al{OC(CF₃)₃}₄]⁻

Abstract

More than 50 years after the proposal of the Dewar–Chatt–Duncanson model for the binding of olefins to transition‐metal atoms, the first structurally characterized example of a silver–C2H4 complex ([Ag(η2‐C2H4)3]+, see picture) was obtained with the help of the very weakly coordinating [Al{OC(CF3)3}4]− ion. By contrast, earlier gas‐phase investigations only suggested the existence of [Ag(η2‐C2H4)x]+ ions (x=1 and 2).

Structurally Characterized Coinage‐Metal–Ethylene Complexes

“…This scarcity is most noticeable with ethylene adducts. [8,70,[81][82][83][84][85] In fact, structurally characterized coinagemetal-ethylene complexes are not that common and get increasingly sparse as one moves down the group 11 triad towards gold. Furthermore, compounds that feature more than one ethylene moiety on Cu I , Ag I , and Au I are exceedingly rare.…”

“…Furthermore, compounds that feature more than one ethylene moiety on Cu I , Ag I , and Au I are exceedingly rare. [85][86][87][88] This is due in large part to the poor thermal stability, and/or light sensitivity, and high lability of the olefin ligand, which create difficulties during the isolation of these complexes. There are, however, some recent notable developments in the field of coinage-metal-ethylene adducts, including the first report containing structural data on a gold(I)-ethylene complex [84] and the isolation of tris-(ethylene) complexes [M(C 2 H 4 ) 3 ] + (M = Cu, Ag, Au).…”

Ring closing metathesis employing organometallic substrates and the templated synthesis of macrocycles

“…In fact, preparation of both corresponding templates, analogues of complex 19 shown in Scheme 5, for the RCM reaction was complicated by retention of a large portion (gravimetrically determined to be ∼10%) of the by-product Ag salts, formed during the pyridine complexation reaction. The silvercontaining complexes were inactive in RCM, potentially due to metathesis catalyst deactivation, competitive coordination of the olefin with Ag, [76][77][78][79] or to effective shortening of the chain by the formation of poly(ether)-Ag complexes [80,81]. Regardless, this necessitated removal of the remaining Ag salts by reaction with H 2 S to precipitate the remaining silver as AgS.…”

Homoleptische Silber(I)‐Acetylen‐Komplexe

“…In dieser Weise ermöglichen auch [Al(OR F ) 4 ] À -WCAs (OR F = Fluoralkoxid) [14][15][16][17] die Stabilisierung und vollständige Charakterisierung von Salzen einiger Gasphasenkationen, die zuvor nur durch MS-Experimente bekannt waren. [7,[18][19][20][21] [22] unbekannten Stammverbindungen aller homolep-…”

“…[29] Die Präferenz der niedrigeren Symmetrie der beobachteten + -Salzen gesehen werden. [21] Das [Ag(h 2 -C 2 H 4 ) n ] + -Ion mit n = 3 konnte in kondensierten Phasen stabilisiert werden, obwohl dies in der Gasphase bisher nicht möglich war (nur n = 1, 2).…”