Related Experiment Video
Updated: Mar 2, 2026
Synthesis of a Borylated Ibuprofen Derivative Through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions
Published on: November 30, 2022
Silylene-Nickel Promoted Cleavage of B-O Bonds: From Catechol Borane to the Hydroborylene Ligand
Terrance J Hadlington1, Tibor Szilvási2, Matthias Driess1
1Department of Chemistry, Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
Abstract:
The first 16 valence electron [bis(NHC)](silylene)Ni0 complex 1, [(TMS L)ClSi:→Ni(NHC)2 ], bearing the acyclic amido-chlorosilylene (TMS L)ClSi: (TMS L=N(SiMe3 )Dipp; Dipp=2,6-Pri2 C6 H4 ) and two NHC ligands (N-heterocyclic carbene=:C[(Pri )NC(Me)]2 ) was synthesized in high yield and structurally characterized. Compound 1 is capable of facile dihydrogen activation under ambient conditions to give the corresponding HSi-NiH complex 2. Most notably, 1 reacts with catechol borane to afford the unprecedented hydroborylene-coordinated (chloro)(silyl)nickel(II) complex 3, {[cat(TMS L)Si](Cl)Ni←:BH(NHC)2 }, via the cleavage of two B-O bonds and simultaneous formation of two Si-O bonds. The mechanism for the formation of 3 was rationalized by means of DFT calculations, which highlight the powerful synergistic effects of the Si:→Ni moiety in the breaking of incredibly strong B-O bonds.
More Related Videos
09:37Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
10:17Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones
Published on: February 7, 2019
Related Concept Videos
02:36Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
03:08Hydroboration-Oxidation of Alkenes
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
01:29Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
02:44Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
01:14Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene