Synthesis and characterization of bis(alkylammonium) tetrasulfidometalates

Abstract

The synthesis and characterization of the bis(alkylammonium) tetrasulfidometalates, (EtNH 3 ) 2 [MS 4 ] (M¼ W 1, Mo 2), [BuNH 3 ] 2 [MS 4 ] (M¼ W 3; Mo 4) and (Et-enH 2 )[WS 4 ] 1-en (Et-en ¼ N-ethylethane-1,2-diamine), are reported. Compound 1 crystallizes in the centrosymmetric orthorhombic space group Pnma and its structure consists of discrete slightly distorted tetrahedral [WS 4 ] 2À of m symmetry, separated by two crystallographically independent (EtNH 3 ) þ ions located on mirror planes. The carbons of one ethylammonium are disordered. Compound 1-en crystallizes in the centrosymmetric orthorhombic space group Pbca with all atoms situated in general positions. Its structure consists of discrete (Et-enH 2 ) 2þ and a slightly distorted tetrahedral [WS 4 ] 2À with the cations and anions linked by several weak hydrogen bonds.

Synthesis, Structure, and Photochemistry of an Organic Heptamolybdate‐Monomolybdate

“…A systematic study of the alklylammonium heptamolybdates has not been developed except the early work of Yamase [7i] and Roman et al [7h] In our ongoing research program, we have employed organic amines as structure-directing agents and have developed a very rich structural chemistry of organic tetrasulfidomolybdates [MoS 4 ] 2-and the corresponding tetrasulfidotungstates [WS 4 ] 2-. [9] In addition to a general basepromoted cation-exchange reaction for the facile synthesis of group VI tetrasulfidometalates that contain organic ammonium cations, we have shown that the reaction of MoO 3 with aqueous alkylamine followed by treatment with H 2 S gas can be employed for the synthesis of organic [MoS 4 ] 2-compounds. [9a-9g] During the course of our study of alkylammonium tetrasulfidomolybdates, [9a-9d] Figure S1 in the Supporting Information).…”

Oxygen out, sulfur in: The alkali metal sulfidotungstates K2[WS4] and novel Na2[WS4] ⋅ 4 H2O

“…The earliest works comprise structure elucidation of ammonium sulfidotungstate, [2] followed by the derivatives of the larger alkali metals rubidium, [3] cesium [4] and two closely related modifications of Cu 2 [WS 4 ] [5] as coinage metal representatives. Furthermore, a verified plethora of alkylated and arylated ammonium salts according to (R 1-4 NH 3-0 ) 2 [WS 4 ] (e. g. R = ethyl, butyl, [6] methylbenzyl, [7] etc.) are known as well as sulfidotungstates with mono-and divalent organic cations have been investigated by the group of Srinivasan (e. g. bis(piperazine-1ium) tetrasulfidotungstate, piperazine-diium tetrasulfidotungstate, etc.).…”

Synthesis, properties and supramolecular structure of piperazinediium thiosulfate monohydrate+

“…[4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Hydrated salts of organic amines exhibit interesting structural features such as a bilayer in 2-aminoanilinium perchlorate monohydrate, 12 sulfate anion helices in ophenylenediammonium sulfate sesquihydrate, 13 a onedimensional polymeric chain of water in [(3-aba) (dabcoH)(H 2 O) 2 ] (3-aba = 3-aminobenzoate; dabco = 1,4-diazabicyclo [2,2,2]octane), 14 a water bridged cyclic dibromide unit in (dbtmen)Br 2 •2H 2 O (dbtmen = N,N′dibenzyl-N,N,N′,N′-tetramethylethylenediammonium), 15 a spiral-like anionic water chain containing a water dimer in (dbtmen)Cl 2 •3H 2 O 16 , water pipe held up by a polyoxometalate supported transition metal complex 17 and linear water dimer in an alkaline earth 4nitrobenzoate. 18 In our research, we have investigated the supramolecular structure of compounds containing tetrahedral anions like tetrasulfidotungstate [19][20][21][22] [WS 4 ] 2− , tetrasulfidomolybdate [23][24][25] [MoS 4 ] 2− , monooxidotrisulfidotungstate 26 [WOS 3 ] 2− , etc. charge balanced by organic ammonium cations.…”