A Manganese N‐Heterocyclic Carbene Catalyst for Reduction of Sulfoxides with Silanes

Abstract

The first reduction of sulfoxides catalysed by a well‐defined manganese complex is described. A variety of sulfoxides are reduced to the corresponding sulfides in high yields using phenylsilane, diphenylsilane, and the economically feasible 1,1,3,3‐tetramethyldisiloxane (TMDS) as reducing agents in the presence of a Mn‐NHC complex. The reaction is performed under air and without the need of any additive. The involvement of radicals in the catalytic reaction is probed by spin‐trap experiments.

Four‐Coordinated Manganese(II) Disilyl Complexes for the Hydrosilylation of Aldehydes and Ketones with 1,1,3,3‐Tetramethyldisiloxane

“…In contrast, manganese catalysts that enable the hydrosilylation of carbonyl compounds with TMDS have not yet been reported. Recently, the catalyst reported by Royo was shown to promote the reduction of the O=S bond of various sulfoxides with TMDS [10] . However, the use of TMDS was not effective in the related catalytic hydrosilylation of esters, giving only <2 % of the targeted products [8a] .…”

Recent progress on NHC-stabilized early transition metal (group 3–7) complexes: Synthesis and applications

“…151 Further synthesis of silica-supported tungsten oxo alkylidene complex 158 allowed an unprecedented activity and stability in in propene self-metathesis catalysis (over 161 Noteworthy, manganese complex 164 is also active in the reduction of sulfoxide to sulfide with silane as reducing agents. 162 It also displayed high activity for the selective N-alkylation of anilines with alcohols such as example that in eq. 1 of Scheme 45, or for the a-alkylation of ketones with alcohols such as eq.…”

Click-Derived Triazoles and Triazolylidenes of Manganese for Electrocatalytic Reduction of CO2

“…In this work, keeping up with our interest in Mn-NHC complexes for catalysis [23][24][25][26][27] and in particular for CO 2 reduction [21], we have developed a new family of Mn(I) tricarbonyl complexes with chelating ligands containing combinations of the mesoionic triazolylidene (MIC), triazole, and pyridine ligands and explored their activity in the CO 2electrocatalytic reduction. We became interested in exploring the impact of the presence of triazolylidene, triazole, and pyridine fragments in the coordination sphere of Mn.…”