Construction of two novel tungsten(VI)-silver(I) mixed metal clusters controlled by bis(diphenylphosphino) methane and coordinated inorganic anions

► A novel cluster [Ag3I(dppm)2 WS4] (1) was prepared by substitution reaction, a new cluster [Ag4(SCN)2 (dppm)4 WS4]·H2O (2) was synthesized by 'one-pot' reaction. ► In synthesis of cluster 2, 1,10-phenathroline(phen) acts as catalysis. ► The coexistence of coordinated anion (SCN− or I−) and bridging dppm ligand help to form span-new frameworks in clusters 1-2 which are beyond the fourteen fundamental skeletons founded for mono-M′ clusters.