Cluster core growth upon the decarbonylation of cyclopentadienyl-iron-dicarbonyl ferrocenyltelluride CpFe(CO)2TeFc: Fe1Te1 to Fe3Te3

CpFe(CO)2TePh → [CpFe(CO)TePh]2 → [CpFe(μ-TeFc)]3(μ-CO)(CO) is an illustrative example of the increasing nuclearity in Fe1 → Fe2 → Fe3 row, upon the stepwise electron-compensating decarbonylation of iron-carbonyl complexes. Introduction of electron rich and bulky ferrocenyl moiety instead of Ph in [CpFe(CO)TePh]2 provide deeper photochemical decarbonylation, resulting unusual [CpFe(μ-TeFc)]3(μ-CO)(CO) cluster and two new redox-active sites in the, otherwise, relatively redox inert molecule of trans-[CpFe(CO)TePh]2. [Display omitted] Formal substitution of aryl group on to the ferrocenyl in [CpFe(CO)(μ-TeR)]2 (R = Ar, Fc) complex dramatically changes its Fe2Te2 core structure and chemical properties. Introduction of electron-rich and bulky ferrocenyl moiety instead of Ph in [CpFe(CO)TePh]2 provide flattening of Fe2Te2 core in [CpFe(CO)(μ-TeFc)]2 (1), further photochemical decarbonylation resulting unusual [(CpFe)3(μ-TeFc)3(μ-CO)(CO)] cluster (2). The electrochemical oxidation of 1 shows two reversible one-electron oxidation waves attributed to oxidation of Fe2Te2 core. Chemical oxidation of 1 is accompanied by isomerization of its core and results in dicationic salt cis-[CpFe(CO)(μ-TeFc)]2 (PF6)2 (3). This study also provides an illustrative example of the increasing nuclearity in Fe1 → Fe2 → Fe3 row, upon the stepwise electron-compensating decarbonylation of iron-carbonyl complexes and (apart from this) insight into the distribution of toluene molecules inclusion inside the channels of crystals of compound 2.