title: 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.
abstract: 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.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford , South Parks Road, Oxford, OX1 3QR, U.K.
authors.forename: Andrey V
authors.initials: AV
authors.lastname: Protchenko
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford , South Parks Road, Oxford, OX1 3QR, U.K.
authors.forename: Joshua I
authors.initials: JI
authors.lastname: Bates
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford , South Parks Road, Oxford, OX1 3QR, U.K.
authors.forename: Liban M A
authors.initials: LM
authors.lastname: Saleh
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford , South Parks Road, Oxford, OX1 3QR, U.K.
authors.forename: Matthew P
authors.initials: MP
authors.lastname: Blake
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford , South Parks Road, Oxford, OX1 3QR, U.K.
authors.forename: Andrew D
authors.initials: AD
authors.lastname: Schwarz
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford , South Parks Road, Oxford, OX1 3QR, U.K.
authors.forename: Eugene L
authors.initials: EL
authors.lastname: Kolychev
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford , South Parks Road, Oxford, OX1 3QR, U.K.
authors.forename: Amber L
authors.initials: AL
authors.lastname: Thompson
authors.affiliation: School of Chemistry, Monash University , PO Box 23, Melbourne, VIC 3800, Australia.
authors.forename: Cameron
authors.initials: C
authors.lastname: Jones
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford , South Parks Road, Oxford, OX1 3QR, U.K.
authors.forename: Philip
authors.initials: P
authors.lastname: Mountford
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford , South Parks Road, Oxford, OX1 3QR, U.K.
authors.forename: Simon
authors.initials: S
authors.lastname: Aldridge