Expanding molecular transition metal cubane clusters of the form [M4(μ3)-O)4]12+: syntheses, spectroscopic and structural characterizations of molecules M4(μ3-O)4(O2P(Bn)2)4(O4), M = V(V) and W(V).

Oxidizing the trimer V(3)(μ(3)-O)(O(2))(μ(2)-O(2)P(Bn)(2))(6)(H(2)O) in the presence of excess (t)BuOOH results in V(4)(μ(3)-O)(4)(μ(2)-O(2)P(Bn)(2))(4)(O(4)) and heating W(CO)(6) and bis(benzyl)phosphinic acid in 1:1 EtOH/THF at 120 °C produces W(4)(μ(3)-O)(4)(μ(2)-O(2)P(Bn)(2))(4)(O(4)). This journal is © The Royal Society of Chemistry 2011