Synthesis and Redox Chemistry of a Homoleptic Iron Arsenic Prismane Cluster

The redox chemistry of the homoleptic iron prismane cluster [{Cp*Fe}3(?3,?4:4:4-As6)] (A, Cp*=C5Me5) is investigated both electrochemically and synthetically. While its first oxidation leads to diamagnetic species [{Cp*Fe}3(?3,?4:4:4-As6)][X] ([1][TEF], [1][FAl], [TEF]?=[Al{OC(CF3)3}4]?, [FAl]?=[FAl{O(1-C6F5)C6F10}3]?), second yields paramagnetic [{Cp*Fe}3(?3,?4:4:4-As6)][TEF]2 ([2][TEF]2). reduction A monoanionic compound [K@[2.2.2]-cryptand][{Cp*Fe}3(?3,?4:4:4-As6)] ([K@crypt][3]), while a could only be traced spectroscopically. All compounds were comprehensively characterized, revealing structural changes accompanying described processes. findings are supported by spectroscopic as well computational studies.