Iron(II) Catalyzed Activation of SiN and SiO Bonds Using Hydroboranes

Mirela A. Johnson, Danila Gasperini, Andrew K. King, Sakshi Mohan, Adam N. Barrett, Samantha Lau, Mary F. Mahon, Yann Sarazin, Sara Kyne, Ruth Webster

Research output: Contribution to journalReview articlepeer-review


We report the activation and functionalization of Si–N bonds with pinacol borane catalyzed by a three-coordinate iron(II) β-diketiminate complex. The reactions proceed via the mild activation of silazanes to yield useful hydrosilanes and aminoboranes. The reaction is studied by kinetic analysis, along with a detailed investigation of decomposition pathways using catecholborane as an analogue of the pinacol borane used in catalysis. We have extended the methodology to develop a polycarbosilazane depolymerization strategy, which generates hydrosilane quantitatively along with complete conversion to the Bpin-protected diamine. The analogous Si–O bond cleavage can also be achieved with heating, using silyl ether starting materials to generate hydrosilane and alkoxyborane products. Depolymerization of poly(silyl ether)s using our strategy successfully converts the polymer to 90% Bpin-protected alcohols.
Original languageEnglish
Pages (from-to)3013–3024
Number of pages12
Issue number20
Early online date4 Oct 2023
Publication statusPublished - 23 Oct 2023

Bibliographical note

The University of Bath (M.A.F.-J., A.K.K., A.N.B.) and EPSRC (D.G., S.L., R.L.W.) are thanked for funding. Merck is thanked for the supply of Durazane polymers. Dr. John Lowe, Dr. Catherine Lyall, Dr. Martin Levere, and Dr. Kathryn Proctor are thanked for their assistance with the analysis.


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