New Compounds. A New Acetylene Silver Nitrate Complex

Abstract

New Compounds 2745 added. The mixture was heated for fifteen minutes on a steam-bath and then diluted with 300 ml. of water. The precipitation and purification of the base was as described in method A.

Argentophilic Interactions

“…[214] If only arene units are available for silver coordination in addition to the terminal alkynyl groups, and if there is a deficit in anion coordination, then the silver atoms entertain h 2 -bonding to the edges of phenyl rings to assist in their coordinative saturation. [203] Butterfly-type Ag 4 units have also been detected in the supramolecular aggregates produced from 4-pyridylethyne and CF 3 COOAg (1:6) or AgNO 3 (2:4) with structural patterns as shown in 65. The compounds are strongly luminescent in the solid state (l em = 564 and 610/556 and 620, l ex= 362/380 nm, respectively).…”

“…In early structural work is had already been demonstrated that in crystals of the classical example (Ag 2 C 2 )(AgNO 3 ) 6 the C 2 dumbbell is surrounded by a rhombohedral Ag 8 cage ([C 2 @Ag 8 ] 6+ , 62 a). [203] In (Ag 2 C 2 )(AgNO 3 ) 5 , isolated from the same lot of crystals, the C 2 unit is accommodated in a trigonal prism monocapped at a square face or at a trigonal face ([C 2 @Ag 7 ] 5+ , 62 b, 62 c). [194,204] Dissolving Ag 2 C 2 in a concentrated aqueous solution of AgF produces a complex of the composition Ag 2 C 2 ·8 AgF in which the C 2 dumbbells are located in the center of a capped square antiprism (62 d) with one external silver atom on the fourfold axis (described as [{C 2 @Ag 9 }Ag] 8+ .…”

Argentophile Wechselwirkungen

“…Darüber hinaus sind die Ketten wohl über eine Side-on-p-Koordination der Acetyleneinheiten an Metallatome und über argentophile Wechselwirkungen verknüpft. 1946 wurde beobachtet, [203] dass der Niederschlag in einer wässrigen Lçsung, die einen Überschuss an AgNO 3 enthält, unter Bildung eines "Doppelsalzes" (Ag 2 C 2 )(AgNO 3 ) 6 leicht lçslich ist, und in der Folge wurden verschiedene andere Produkte dieses Typs mit Silbersalzen mit anderen Anionen als Nitrat gefunden. Diese Befunde belegen, dass das [CC] 2À -Dianion eine starke Affinität zu Silberkationen hat, und in späteren Untersuchungen wurde gezeigt, dass seine mehrfache Versilberung zu einer faszinierenden Vielfalt an C 2 -zentrierten Silberclustern führt, die mit Formeln wie [C 2 @Ag n ] (nÀ2)+ (n = 6-10) beschrieben werden.…”

Crystallographic data for silver acetylide

“…6AgNO 3. The 1 : 1 complex can also be made by reaction of the 1:6 complex with water (Shaw & Fisher, 1946).…”