Manganese carbonyl compounds as hydrosilation catalysts for organoiron acyl complexes

Manganese‐Catalyzed Hydrosilylation Reactions

“…Since the first example reported by Yates in 1982, a variety of manganese complexes have been developed for hydrosilylation reactions. In the 1990s, manganese carbonyl acyl catalysts were widely utilized in the works reported by the group of Cutler, and exhibited high reactivities in the hydrosilylation of ketones, esters, and organoiron complexes . In addition, many manganese catalysts covered in this review, including carbonyl–Mn complexes, half‐sandwich manganese complexes, Salen–Mn complexes, bis‐NHC–Mn complexes, pincer manganese complexes, as well as manganese–amide complexes, also presented their features on carbonyl hydrosilylation reactions.…”

“…In the 1990s, the Cutler group achieved a real breakthrough in the Mn‐catalyzed hydrosilylation of carbonyls, including ketones, esters, and transition‐metal acyl complexes. Specifically, they reported the hydrosilylation of organoiron acyl complexes 1 catalyzed by [(CO) 5 MnC(O)R] ( 2 ; R=Me or Ph) in 1991 (Scheme a) . Moreover, this strategy was extended to the hydrosilylation of methoxycarbonyl complexes 3 under the catalysis of [(PPh 3 )(CO) 4 MnC(O)Me] ( 4 ) to afford η 4 ‐cyclopentadiene complex 5 and methoxysilane 6 (Scheme b) .…”

“…Specifically,t hey reported the hydrosilylation of organoiron acyl complexes 1 catalyzed by [(CO) 5 MnC(O)R] (2;R = Me or Ph) in 1991( Scheme 2a). [11] Moreover,t his strategy was extended to the hydrosilylation of methoxycarbonyl complexes 3 under the catalysis of [(PPh 3 )(CO) 4 MnC(O)Me] (4)t oa fford h 4 -cyclopentadiene complex 5 and methoxysilane 6 (Scheme 2b). [12] Interestingly,t he cyclopentadienyl (Cp) ligand of iron was reduced by meanso fa nexo-hydridet ransfer, which was supported by deuterium-labeling experiments.…”

“…In the 1990s, manganese carbonyl acyl catalysts were widely utilized in the works reported by the group of Cutler, and exhibited high reactivities in the hydrosilylationo f ketones, [14] esters, [15] and organoiron complexes. [11][12][13] In addition, many manganese catalysts covered in this review,i ncluding carbonyl-Mn complexes, half-sandwich manganese complexes, [16,18] Salen-Mn complexes, [17] bis-NHC-Mn complexes, [20] pincerm anganese complexes, [21][22][23] as well as manganeseamide complexes, [26] also presented their features on carbonyl hydrosilylation reactions. Of particular note is that the catalytic system reported by Trovitchh ad the highest TOF (4950 min À1 ) among all the base-metal catalysts, [21d] which might provide potentialf or large-scale applications of manganese catalysts in the hydrosilylation industry.…”

Comparing Well-Defined Manganese, Iron, Cobalt, and Nickel Ketone Hydrosilylation Catalysts

“…11 Moreover, this complex has been found to mediate the hydrosilylation of transition-metal acyl complexes. [12][13][14] In 1999, Chung and co-workers reported that (η 5 -C 10 H 9 )Mn(CO) 3 catalyzes the ambient-temperature hydrosilylation of ketones when employing Ph 2 SiH 2 as the reductant. 15 Soon after, this investigation was extended to the utilization of the naphthalene-supported complex, [(η 6 -C 10 H 8 )Mn(CO) 3 ][BF 4 ], which was found to exhibit improved, yet limited, TOF for ketone reduction of up to 99 h -1 .…”