A Highly Active Manganese Precatalyst for the Hydrosilylation of Ketones and Esters
作者:Tufan K. Mukhopadhyay、Marco Flores、Thomas L. Groy、Ryan J. Trovitch
DOI:10.1021/ja4116346
日期:2014.1.22
The reduction of ((PDI)-P-Ph2PPr)MnCl2 allowed the preparation of the formally zerovalent complex, ((PDI)-P-Ph2PPr)Mn, which features a pentadentate bis(imino)pyridine chelate. This complex is a highly active precatalyst for the hydrosilylation of ketones, exhibiting TOFs of up to 76,800 h(-1) in the absence of solvent. Loadings as low as 0.01 mol % were employed, and ((PDI)-P-Ph2PPr)Mn was found to mediate the atom-efficient utilization of Si-H bonds to form quaternary silane products. ((PDI)-P-Ph2PPr)Mn was also shown to catalyze the dihydrosilylation of esters following cleavage of the substrate acyl C-O bond. Electronic structure investigation of ((PDI)-P-Ph2PPr)Mn revealed that this complex possesses an unpaired electron on the metal center, rendering it likely that catalysis takes place following electron transfer to the incoming carbonyl substituent.
URTANE, I. P.;ZELCHAN, G. I.;LUKEVICS, E., Z. ANORG. UND ALLG. CHEM., 1985, 520, N 1, 179-195
作者:URTANE, I. P.、ZELCHAN, G. I.、LUKEVICS, E.
DOI:——
日期:——
Trialkoxysilane Exchange: Scope, Mechanism, Cryptates and pH‐Response
作者:Selina Hollstein、Philipp Erdmann、Andreas Ulmer、Henrik Löw、Lutz Greb、Max von Delius
DOI:10.1002/anie.202304083
日期:2023.6.26
The exchange reaction of trialkoxysilanes with alcohols typically requires very harsh conditions and has therefore not been used for the self-assembly of host-guest systems. In this work, unexpected solvent and salt effects are described, rationalized and exploited for the synthesis of degradable supramolecular hosts.