Neutral Chalcogenide Tungsten Cluster with Tris(2‐Cyanoethyl)phosphine

Abstract

Despite the great prospects for the use of octahedral metal cluster complexes in various fields, chalcogenide tungsten compounds with functional organic ligands have practically not been studied. In this work, we present the synthesis and detailed characterization of a tungsten cluster with tris(2cyanoethyl)phosphine [{W 6 S 8 }(P(C 2 H 4 CN) 3 ) 6 ]. The compound [a] A.

Water-Soluble Chalcogenide W6-Clusters: On the Way to Biomedical Applications

“…The compound H 6 - 1 was prepared according to the modified method published for the cluster with phosphine P(C 2 H 4 CN) 3 as a ligand, namely [{W 6 S 8 }(P(C 2 H 4 CN) 3 ) 6 ] [ 43 ]. Briefly, the reaction mixture of (Bu 4 N) 2 [{W 6 I 8 }I 6 ]/NaHS/ t BuOK/PPh 2 CH 2 CH 2 COOH in a molar ratio of 1:16:8:16 in dry DMF was heated in a sealed glass tube at 100 °C for 4 days, resulting in the complete substitution of inner and terminal iodine ligands with a good yield (69%).…”

“…They are more hydrolytically stable than tungsten halides, and no examples of their photosensitizing properties are known to date. However, the pool of such clusters is not large enough due to the synthetic problems: only 36 individual cluster complexes (31 for Q = S, 2 for Q = Se, and 3 for Q = Te) with different organic or inorganic terminal ligands were described [ 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 ]. Moreover, only one of the known W 6 Q 8 -clusters is soluble in water, namely [{W 6 S 8 }(CN) 6 ] 6− [ 38 ].…”

Selective Oxidation of Inner Pnictogenide Ligands in Mixed-Ligand Rhenium Cubane-Type Cluster Complexes

“…However, the inner ligands affect the electronic structure and physical properties of cluster compounds to a much greater extent than the apical ligands. As typical examples of such an influence, chalcogenide and halide clusters of molybdenum and tungsten with the {M 6 Q 8 } (Q = S, Se) or {M 6 X 8 } (X = Cl, Br, I) cluster cores, chalcohalide rhenium clusters with {Re 6 Q 8– n X n } cores, and 12-nuclear clusters with {Re 12 CS 14 (Q/X) 3 } cores should be mentioned. These compounds exhibit very different optical, chemical, and electrochemical properties, depending on the composition of the inner ligand environment.…”