Enabling and probing oxidative addition and reductive elimination at a group 14 metal center: cleavage and functionalization of E-H bonds by a bis(boryl)stannylene

Journal article

By employing strongly σ-donating boryl ancillary ligands, the oxidative addition of H2 to a single site Sn(II) system has been achieved for the first time, generating (boryl)2SnH2. Similar chemistry can also be achieved for protic and hydridic E-H bonds (N-H/O-H, Si-H/B-H, respectively). In the case of ammonia (and water, albeit more slowly), E-H oxidative addition can be shown to be followed by reductive elimination to give an N- (or O-)borylated product. Thus, in stoichiometric fashion, redox-based bond cleavage/formation is demonstrated for a single main group metal center at room temperature. From a mechanistic viewpoint, a two-step coordination/proton transfer process for N-H activation is shown to be viable through the isolation of species of the types Sn(boryl)2·NH3 and [Sn(boryl)2(NH2)](-) and their onward conversion to the formal oxidative addition product Sn(boryl)2(H)(NH2).

Authors: Protchenko, A; Bates, J; Saleh, L; Blake, M; Schwarz, A

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Chemical Society
• Journal: Journal of the American Chemical Society
• Volume: 138
• Issue: 13
• Pages: 4555-4564
• Publication date: 2016-04-01
• Acceptance date: 2016-01-20
• DOI: 10.1021/jacs.6b00710
• EISSN: 1520-5126
• ISSN: 0002-7863
• Language: English
• Keywords: SBTMR