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

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...

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Bibliographic Details
Published in:ChemCatChem 2021-02, Vol.13 (4), p.1152-1156
Main Authors: Saito, Kyoka, Ito, Tatsuyoshi, Arata, Shogo, Sunada, Yusuke
Format: Article
Language:English
Subjects:
1,1,3,3-tetramethyldisiloxane
Aldehydes
Equivalence
Hydrosilylation
isocyanide
Ketones
Manganese
organosilyl ligand
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Summary: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. Powerful Mn‐disilyl complexes: The four‐coordinated manganese(II)‐disilyl complex Mn[Si(SiMe3)3]2(THF)2 (2) acts as a good precatalyst for the hydrosilylation of aldehydes and ketones with 1,1,3,3‐tetramethyldisiloxane (TMDS). The addition of adamantyl isocyanide to 2 led to an improvement of the catalyst efficiency, and to the isolation of Mn[Si(SiMe3)3]2(CNAd)2 (3).
ISSN:1867-3880
1867-3899
DOI:10.1002/cctc.202001522