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
dataset
posted on 2016-03-16, 00:00 authored by 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 AldridgeBy 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).
