Open AccessEnabling 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
Author(s) -
Andrey V. Protchenko,
Joshua I. Bates,
Liban M. A. Saleh,
Matthew P. Blake,
Andrew D. Schwarz,
Eugene L. Kolychev,
Amber L. Thompson,
Cameron Jones,
Philip Mountford,
Simon Aldridge
Publication year - 2016
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.6b00710
Subject(s) - chemistry , oxidative addition , reductive elimination , stoichiometry , metal , bond cleavage , medicinal chemistry , cleavage (geology) , center (category theory) , oxidative phosphorylation , redox , ammonia , stereochemistry , crystallography , inorganic chemistry , organic chemistry , catalysis , biochemistry , geotechnical engineering , fracture (geology) , engineering
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).