Phosphor-Chalkogen-Moleküle als Komplexliganden - Reaktionen mit NbCl5

Ring‐shaped [(TiCl2)(1,3‐P2S8)]2 Molecules Containing Uncommon [P2S8]2– Anions

“…These have different phosphorus and sulfur atoms within the cages which can act as possible coordination sites, and α-P 4 S 7 and P 4 S 10 furthermore exhibit terminal sulfur atoms as possible coordination sites. These cages should be able to act as Lewis-bases similar as found for other metal halides (see for example [7][8][9][10]). Herein we present [(TiCl 2 )(1,3-P 2 S 8 )] 2 which was obtained en route from TiCl 4 and P 4 S 10 in CS 2 at room temperature.…”

Adduct Compounds (MCl5)2(β-P4Ch4) with M = Nb, Ta and Ch = S, Se

“…The mechanism of this adduct formation is still unknown [9]. In the case of the niobium-containing adducts, presumably the reduction of the metal from Nb(V) to Nb(IV) and an oxidative chlorination of phosphorus are involved (see also ref.…”

“…Direct Methods revealed the positions of the atoms which were then subsequently refined including anisotropic displacement parameters for all atoms [19] (Tables 2 -4). A re-determination of the crystal structure of (NbCl 5 ) 2 (β -P 4 S 4 ) [9] was also performed for a better comparability of the data (see below).…”

“…[9], was looked at more closely. First results of these investigations -the formation and crystal structures of (TaCl 5 ) 2 (β -P 4 S 4 ), (TaCl 5 ) 2 (β -P 4 -Se 4 ) and (NbCl 5 ) 2 (β -P 4 Se 4 ), which are isotypic with (NbCl 5 ) 2 (β -P 4 S 4 ) [9] -are reported here. The characterization of adduct compounds of sulfur-rich cages with MCl 5 (M = Nb, Ta) is described in ref.…”

“…There is experimental evidence that these molecules either decompose upon heating or even in solution (β -P 4 S 4 ) [2] or polymerize forming chains of catenated molecules (β -P 4 Se 4 ) [3 -5]. However, these β -P 4 Ch 4 phosphorus chalcogenide cages can be found in several quaternary adduct compounds, such as (CuI) 3 (β -P 4 Se 4 ) [6], (CuI) 3 (β -P 4 S 4 ) [7], (CuBr) 3 (β -P 4 Se 4 ) [8], and (NbCl 5 ) 2 (β -P 4 S 4 ) [9], where metal atoms are coordinated to phosphorus atoms of the cages.…”