Charge-compensated nido-carborane derivatives in the synthesis of iron(II) bis(dicarbollide) complexes

Dalton Transactions. 2024. Vol. 53. No. 7. P. 3363–3376.

Stogniy M., Anufriev S., Bogdanova E., Gorodetskaya N., Anisimov A., Sivaev I.

A series of stable iron(II) bis(dicarbollide) derivatives [8,8’-(RNHC(Et)vHN)2-3,3’-Fe(1,2-C2B9H10)2] (R = Pr, R = Ph, (CH2)2OH, (CH2)3OH, (CH2)2NMe2) was prepared starting from FeCl2 or [FeCl2(dppe)] and the corresponding nido-carboranyl amidines [10-RNHC(Et)vHN-7,8-C2B9H11]. In a similar way, the reactions of the oxonium derivatives of nido-carborane with FeCl2 in tetrahydrofuran in the presence of t-BuOK lead to the corresponding stable oxonium derivatives iron(II) bis(dicarbollide) [8,8’-(RR’O)2-3,3’-Fe(1,2-C2B9H10)2] (RR’ = (CH2)4, (CH2)2O(CH2)2, (CH2)5; R = R’ = Et), which can be alternatively prepared by the reaction of the parent iron(II) bis(dicarbollide) with  tetrahydrofuran or 1,4-dioxane in the presence of Me2SO4. The cyclic voltammetry studies of the synthesized iron(II) bis(dicarbollide) derivatives revealed that the introduction of amidinium and oxonium substituents leads to a significant increase in the Fe2+/Fe3+ redox potential relative to the parent iron(II) bis(dicarbollide). The redox potentials of the oxonium derivatives are close to the redox potential of ferrocene and somewhat lower than redox potentials of
sulfonium and phosphonium derivatives of iron(II) bis(dicarbollide).

Keywords: synthesis, electrochemistry, metallacarboranes, single crystal X-ray diffraction