Stabilization of Tetrahedral P₄ and As₄ Molecules as Guests in Polymeric and Spherical Environments

Abstract

As you like it: [Ag(η2‐As4)2]+[pftb]− can be used to store yellow arsenic (As4). From it, As4 can be easily released to give concentrated, light‐stable solutions. These As4 solutions, and those of white phosphorus (P4), allowed molecular As4 and P4 to be encapsulated inside giant, spherical aggregates and polymeric matrices, enabling the first determination of their EE (E=P, As) bond lengths by diffraction methods.

Crystal structure of a giant supramolecule encapsulating o-carborane

“…At the same time each fragment 1 is coordinated to five Cu atoms in an η 1 , η 1 , η 1 , η 1 , η 1 , η 5 -P 5 mode. The bond distances (Table 2) are close to those found in other pentaphosphaferrocene-based supramolecules [6][7][8][9][10][11][12][13][14][15]. The outer diameter of the supramolecules 2 and 3 is close to 23 Å.…”

“…Our investigations during the last 10 years show that the reaction between pentaphosphaferrocenes, [Cp R Fe(η 5 -P 5 )] (Cp R = η 5 -C 5 Me 5 , η 5 -C 5 Me 4 Et, η 5 -C 5 (CH 2 Ph)) and copper(I) halides results in two general types of products, coordination polymers and oligomeric supramolecules [6][7][8][9][10][11][12][13][14][15]. We found that the coordination of CuX (X = Cl, Br, I) building blocks to phosphorus atoms of [Cp*Fe(η 5 -P 5 )] (1, Cp* = η 5 -C 5 Me 5 ) results in the formation of giant spheres with large inner cavities.…”

“…These supramolecules can act as molecular containers for fullerene C 60 [9], transition metal π-complexes [8,11,12], and can, e.g., stabilize the paramagnetic [CpCr(η 5 -As 5 )] complex that does not exist outside its host molecule at all [12]. Even so unprecedented guest molecules as P 4 and As 4 could be introduced [13].…”

Facile storage and release of white phosphorus and yellow arsenic

“…Here, P 4 was synthesized from red phosphorus and trapped by gas phase diffusion. Furthermore, we succeeded in the encapsulation and stabilization of intact tetrahedral E 4 molecules (E = P, As) in polymeric and spherical aggregates constructed by copper halides and [Cp*Fe(η 5 -P 5 )] (Cp* = η 5 -C 5 Me 5 ) 10 . Even if the corresponding crystals are air and light-stable, they are insoluble in common solvents and the group 15 tetrahedra are not releasable without the decomposition of the complexes.…”

Cyclo‐P4‐Bausteine – Verwirklichung nichtklassischer Fulleren‐Analogie und weiterer Topologien

“…[9] Durch vorsichtiges Überschichten einer Lçsung von CuI in CH 3 .B ei der Bildung von 4,a ls jedoch ein anderes Solvatomorph (4a), entstehen auch braune Nadeln des früher beschriebenen 2D-Koordinationspolymers [{Cp*Fe(h 5 -P 5 )}(CuI)] n . [10] Offensichtlich verhindert die Anwesenheit von [Cp*Fe(h 5 -P 5 )] im Reaktionsgemisch die zunächst einsetzende Bildung von 3 und begünstigt die Bildung von 4.…”