We report here the first purely organometallic fac‐[MnI(CO)3(bis‐MeNHC)Br] complex with unprecedented activity for the selective electrocatalytic reduction of CO2 to CO, exceeding 100 turnovers with excellent faradaic yields (η CO≈95 %) in anhydrous CH3CN. Under the same conditions, a maximum turnover frequency (TOFmax) of 2100 s−1 was measured by cyclic voltammetry, which clearly exceeds the values reported for other manganese‐based catalysts. Moreover, the addition of water leads to the highest TOFmax value (ca. 320 000 s−1) ever reported for a manganese‐based catalyst. A MnI tetracarbonyl intermediate was detected under catalytic conditions for the first time.

Registro de acceso restringido Este recurso no está disponible en acceso abierto por política de la editorial. No obstante, se puede acceder al texto completo desde la Universitat Jaume I o si el usuario cuenta con suscripción. Registre d'accés restringit Aquest recurs no està disponible en accés obert per política de l'editorial. No obstant això, es pot accedir al text complet des de la Universitat Jaume I o si l'usuari compta amb subscripció. Restricted access item This item isn't open access because of publisher's policy. The full--text version is only available from Jaume I University or if the user has a running suscription to the publisher's contents.

Treatment of pyrophoric strontium powder in tetrahydrofuran with ArOH (Ar = C6H2Buf3-2,4,6) or HNR'2 at ambient temperature affords crystalline [Sr(OAr)2(THF)4] or [Sr(NR',),(THF),]

Iron Fe(NHC)(CO)4 complexes were formed by direct reaction of Fe3(CO)12 with equimolecular amounts of NHC imidazolium halide precursors; addition of base was not needed in this reaction. When excess (9:1 ratio) 1,3-dimesitylimidazolium chloride is reacted with the iron cluster Fe3(CO)12, a mixture of Fe(IMes)(CO)4 and Fe(IMes)2(CO)3 is obtained. Single crystals of Fe(IMes)(CO)4 and crystals resulting from the cocrystallization of Fe(IMes)(CO)4 and Fe(IMes)2(CO)3 have been studied by X-ray diffraction. These iron(0) complexes were found to catalyze the reduction of benzaldehydes.