We report here the first purely organometallic fac‐[Mn^I(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 (TOF_max) 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 TOF_max value (ca. 320 000 s⁻¹) ever reported for a manganese‐based catalyst. A Mn^I tetracarbonyl intermediate was detected under catalytic conditions for the first time.

Treatment of pyrophoric strontium powder in tetrahydrofuran with ArOH (Ar = C₆H₂Bu^t ₃-2,4,6) or HNR′₂ at ambient temperature affords crystalline [Sr(OAr)₂(THF)₄] or [Sr(NR′₂)₂(THF)₂]3, respectively, and 3 with 1,4-dioxane yields crystalline [{trans-Sr(NR′₂)₂(µ-1,4-dioxane)}∞]4; co-condensation of calcium vapour and RBr in THF at 77 K affords [CaR₂(THF)₃]5, which with 1,4-dioxane gives [CaR₂(1,4-dioxane)₂]6; X-ray structures reveal the alkaline earth metal environment to be square-planar for 4[Sr-N 2.449(7), Sr-O 2.533(9)Å] but tetrahedral for 6[Ca-C 2.483(5), Ca-O 2.373(4)Å] with dioxane as a bridging bidentate 4 or monodentate 6 ligand.

The high valent molybdenum-dioxo complex [MoO₂Cl₂] catalyzes the addition of dimethylphenylsilane to aldehydes and ketones to afford the corresponding dimethylphenylsilyl ethers in quantitative yield.