Studies on solid state reactions of coordination compounds. LXIII. Solid state synthesis of a series of tetranuclear Mo(W)—Ag mixed‐metal clusters. Crystal structures of [( n ‐Bu) 4 N] 3 [MoOS 3 Ag 3 Br 4 ] and [( n ‐Bu) 4 N] 3 [WS 4 Ag 3 Cl 4 ]

A series of tetranuclear Mo(W)‐Ag mixed‐metal clusters have been synthesized by making use of the solid state reactions of [NH 4 ] 2 [MYS 3 ](M= Mo, W; Y= O, S), AgX(X= Cl, Br, I) and ( n ‐Bu) 4 NX' (X' =Cl, Br), two of which [( n ‐Bu) 4 N] 3 [MoOS 3 Ag 3 Br 4 ] (1) and [( n ‐Bu) 4 N] 3 [WS 4 Ag 3 Cl 4 ] ( 2 ) have been structurally characterized by X‐ray analysis. The crystal data: 1 , cubic, P 4 3 m , αequals;12.093(4) Å, Z =1, R =0.076; 2 , cubic, P 4 3 m , αequals;12.059(2) Å, Z =1, R =0.075. The cluster anion core [Ag 3 MS 3 X'] of the two compounds can be viewed as a cube in which the four metal atoms and the four non‐metal atoms are statistically distributed, respectively. Substitution reaction with PPh 3 ligand is also discussed for this type of tetranuclear clusters.