Reactions of Polyarsenides with Acetylene: Synthesis and Characterization of [Cs([18]crown‐6)]₂As₇C₁₄H₁₁·6NH₃ and As₂C₆H₆

Abstract

Abstract. The reaction of Cs 3 As 7 with diphenylacetylene in the presence of [18]crown-6 in liquid ammonia results in the formation of the new compound [Cs([18]crown-6)] 2 As 7 C 14 H 11 ·6NH 3 , which crystallizes in black monoclinic crystals. It contains the first monosubstituated heptaarsenide anion with a hydrocarbon-only substituent and theoretical calculations show a significant influence of the organic substituent on the electronic structure within the cage. The (Z)-1,2-diphen-

Open Chain Polyarsenides of the Lanthanides

“…The As−As bonds within the As 4 chain range between 2.3715(13) and 2.4896(13) Å ( 1 a ) and between 2.3754(8) and 2.4891(7) Å ( 1 b ). In comparison to the starting material [(Cp′′′Co) 2 ( μ,η 2 :2 ‐As 2 ) 2 ], all bonds are significantly elongated (2.2795(5) Å) . The open side As1−As4 (3.4373(11) ( 1 a ) and 3.4385(8) Å ( 1 b )) is too long for being deliberated as a bond.…”

“…In comparison to the startingm aterial [(Cp'''Co) 2 (m,h 2:2 -As 2 ) 2 ], all bonds are significantly elongated( 2.2795 (5) ). [28] The open side As1ÀAs4 (3.4373(11) (1a)a nd 3.4385 (8) (1b)) is too long for being deliberated as ab ond. The observed AsÀAs bonds in 1a,b are in the range of those observed in As 4 (2.44 )a nd thus can be considered as single bonds.…”

Frontiers in the solution-phase chemistry of homoatomic group 15 Zintl clusters

“…10; 48) was isolated. 67 At this time, it was postulated that the hydrogen atom necessary to reduce the triple bond must be originating from the ammonia solvent, followed by As 4 elimination. Although, the reaction mechanism for these transformations…”

“…9; 49). 67 Finally, it was found that upon reaction with carbon monoxide, [P 7 ] 3− acts as a formal source of phosphide anions and afforded the phosphaethyanolate anion [PCO] − in 88% yield (if you consider P − as the limiting reagent; [P 7 ] 3− contains 3 P − units). 69 This percent conversion appears to be low but is in line with the structural description of [P 7 ] 3− discussed above.…”

A surprise landing on the terra incognita of macrocyclic dibridgehead diorganoarsines: syntheses, structures, and reactivities

“…11,12 In contrast, analogous dibridgehead diarsines As((CH 2 ) n ) 3 As ( 1 ) have remained unknown for all values of n , although systems with one or more short As(CRCR)As or AsOAs bridges have been reported. 13…”