A β-diketiminate manganese catalyst for alkene hydrosilylation: substrate scope, silicone preparation, and mechanistic insight

Abstract

A (BDI)Mn catalyst has been found to hydrosilylate olefins and the observed selectivity can be attributed to alkene insertion.

Silica‐Supported MnII Sites as Efficient Catalysts for Carbonyl Hydroboration, Hydrosilylation, and Transesterification

“…To further investigate the nature of 1@SiO 2 – 400 , EPR measurements were performed. At room temperature, 1 display a wide spectrum in the 50–650 mT range with g =2.16 for the principle line (Figure S7, Supporting Information), which is consistent with previously reported compounds . Upon grafting, the spectrum shows differences in structure of the bands, and the g factor of 1@SiO 2 is 2.02 (Figure S8).…”

“…At room temperature, 1 display aw ide spectrumi nt he 50-650 mT range with g = 2.16 for the principle line ( Figure S7, Supporting Information), which is consistent with previously reportedc ompounds. [22] Upon grafting, the spectrums hows differences in structure of the bands, and the g factor of 1@SiO 2 is 2.02 ( Figure S8). The EPR spectrumo f 1@SiO 2-400 shows substantial differences;one considerably narrower signal with the g = 2.01 is observed ( Figure S9) which may suggest that 1@SiO 2-400 does not maintain the dimeric structure upon thermal treatment.…”

Recent Advances in Catalytic Hydrosilylations: Developments beyond Traditional Platinum Catalysts

“…Furthermore, b-diketiminate-based catalysts,s uch as the dimeric b-diketiminate manganese hydride (Mn-1)a nd the dimeric b-diketiminatomagnesium hydride (Mg-1)i nF igure 3, were also developed for anti-Markovnikov alkene hydrosilylation. [54,55] Using Mn-1 as catalyst, aliphatic alkenes underwent anti-Markovnikov hydrosilylation to afford (E)-bvinylsilanes with 37-99 %c onversion, while the hydrosilylation of styrenes afforded a-vinylsilanes with 19-99 %c onversion through Markovnikov hydrosilylation.…”

Reduction of carbonyl compounds via hydrosilylation catalyzed by well-defined PNP-Mn(I) hydride complexes

“…An attractive alternative to that is the use of hydrogen donors such as silanes [19,20]. Since the first report on manganese-catalyzed hydrosilylation reactions by Yates and coworkers in 1982 [21], several protocols for the hydrosilylation of polarized double bonds such as ketones [22][23][24][25][26][27], esters [28,29], amides [30][31][32] and acids [33] as well as alkenes [34][35][36] and alkynes [37] were developed.…”