4.6 Article

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

Journal

CHEMCATCHEM
Volume 13, Issue 4, Pages 1152-1156

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.202001522

Keywords

Manganese; organosilyl ligand; hydrosilylation; isocyanide; 1; 1; 3; 3-tetramethyldisiloxane

Funding

  1. Kanagawa Institute of Industrial Science and Technology (KISTEC)
  2. Ministry of Education, Culture, Sports, Science and Technology, Japan [16H04120, 20H02751]
  3. Grants-in-Aid for Scientific Research [20H02751, 16H04120] Funding Source: KAKEN

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The article discusses a method of catalytic hydrosilylation using manganese complexes, with improved catalytic efficiency achieved by modifying the structure of the complex and combining it with isocyanide.
The coordinatively unsaturated manganase(II) bis(supersilyl) complex Mn[Si(SiMe3)(3)](2)(THF)(2) (2) was synthesized in one step via the reaction of MnBr2 with two equivalents of KSi(SiMe3)(3) in THF. Complex 2 acts as an effective precatalyst for the catalytic hydrosilylation of aldehydes and ketones with 1,1,3,3-tetramethyldisiloxane (TMDS). The catalytic efficiency can be improved by combining 2 and adamantyl isocyanide (CNAd). The stoichiometric reaction of 2 and two equivalents of CNAd led to the isolation of Mn[Si(SiMe3)(3)](2)(CNAd)(2) (3) in high yield. Complex 3 shows superior catalytic performance than 2 in the hydrosilylation of relatively unreactive ketones.

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