Review. Solvothermal Synthesis and Structure of Chalcogenidoarsenate Anions

Abstract

A rich variety of chalcogenidoarsenate anions and ligands have been prepared under mild solvothermal conditions in strongly polarizing solvents such as water, methanol and amines in the temperature range 100 -200 • C. This review covers synthetic and structural aspects of such species As x E y z− with particular emphasis being placed on the trends and differences observed for E = S, Se, Te and on developments within the past decade. These include the preparation of quaternary Main Group element chalcogenidoarsenates(III) such as Cs 3 AsGeSe 5 and polymeric selenidoarsenates(II, III) such as Cs 2 As 4 Se 6 . A currently expanding area of interest involves the employment of transition metal-polyamine or -polyimine fragments such as {Mn(tren)} 2+ or {Mn(terpy)} 2+ as structuredirecting agents. The metal atoms of such cations can be connected to the terminal chalcogen atoms of oligomeric or polymeric anions As x E y z− to prevent their further condensation or can be directly incorporated into anionic or neutral networks when at least two free coordination sites are available in the fragment. This strategy has led to the characterization of novel ligands including cyclo-

Infinite Anionic Chains Formed by Alternating Bidentately Acting [SbS4]3- Anions and [Mn(dien)]2+ Complexes in the Compound [Mn(dien)2][Mn(dien)SbS4]2

“…Further analysis has shown that the compound crystallizes monoclinically in space group P2 1 , and that the crystal is non-merohedrically twinned with a 2-fold axis as the twin element (BASF parameter: 0.5249(1)). In this space group no disorder is present, and the absolute structure can easily be determined and is in agreement with the selected setting; x (Flack) parameter: 0.06 (2).…”

Synthesis, crystal structures, and optical properties of NaCdPnS3 (Pn=As, Sb)

“…Unlike its heavier homologues Sb and Bi, trivalent arsenic exhibits a remarkable reluctance to adopt hypervalent coordination polyhedra in its chalcogenido anions [11,12]. The most prominent anions are the pyramidal [As III Q 3 ] 3− and tetrahedral [As V Q 4 ] 3− anions, observed in ternary or quaternary compounds [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30].…”

Synthesis and Crystal Structure of K3AsSe4 and K4As2Se5 Containing [AsSe4]3- Anions and a Novel [As2Se5]4- Isomer Featuring an As–As Bond

“…Over the past few years, the mild solvothermal technique has proved to open convenient synthetic routes to chalcogenidoarsenates which are often inaccessible via the traditional solution approach [4]. Focusing on selenoarsenates, a wide variety of isolated [As x Se y ] n− anions have been reported with diverse connectivity patterns of arsenic and selenium atoms as well as with various formal oxidation states of arsenic [4]. These anions include the selenium-rich species [AsSe 3 ] 3− [5,6], [AsSe 4 ] 3− [7 -10], [AsSe 6 ] − [11,12] [26], the structures of which are of cluster or cage type.…”

“…We also studied the reactions of group 15 elements with the higher chalcogens in superheated ethylenediamine aiming at the synthesis of heteroatomic Zintl clusters using potassium carbonate as mineralizer. In the present contribution we report the synthesis and crystal structure of the two novel selenoarsenates K 3 AsSe 4 (Fig. 1) that are surrounded by potassium cations.…”