Publisher: American Chemical Society (ACS)

Issue: 13

License: http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html

Publication date(s): 2016/04/06 (print) 2016/03/28 (online)

Pages: 4555-4564

Volume: 138 Issue: 13

Journal: Journal of the American Chemical Society

Link: https://pubs.acs.org/doi/pdf/10.1021/jacs.6b00710

URL: http://dx.doi.org/10.1021/jacs.6b00710

By employing strongly σ-donating boryl ancillary ligands, the oxidative addition of H2 to a single site SnII 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).