Related Experiment Video
Updated: Jun 21, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Synthesis and structure of PNP-supported iridium silyl and silylene complexes: catalytic hydrosilation of alkenes
1Department of Chemistry, University of California, Berkeley, California 94720, USA.
Abstract:
Oxidative addition of bulky primary, secondary, and tertiary silanes to PNP (PNP = [N(2-P(i)Pr(2)-4-Me-C(6)H(3))(2)](-)) iridium complexes (PNP)IrH(2) and (PNP)Ir(COE) (11) afforded iridium silyl hydride complexes (PNP)Ir(H)(SiRR'R'') (3-8). Addition of 2 equiv of PhSiH(3) or (3,5-Me(2)C(6)H(3))SiH(3) to (PNP)IrH(2) or 11 yielded disilyl complexes (PNP)Ir(SiH(2)R)(2) (R = Ph (9), 3,5-Me(2)C(6)H(3) (10)). Hydride abstraction from (PNP)Ir(H)(SiH(2)R) (R = Trip (5), Dmp (6)) by [Ph(3)C][B(C(6)F(5))(4)] afforded iridium silylene complexes [(PNP)(H)Ir=SiR(H)][B(C(6)F(5))(4)] (R = Trip (12), Dmp (13)) exhibiting downfield (29)Si NMR resonances (234 ppm (12), 226 ppm (13)) and downfield (1)H NMR resonances for the Si-H group (10.76 ppm (12), 9.76 ppm (13)). Thermally stable disubstituted silylene complexes [(PNP)(H)Ir=SiPh(2)][A] (A = (-)B(C(6)F(5))(4) (14), (-)CB(11)H(6)Br(6) (16)) were isolated via hydride abstraction from (PNP)Ir(H)(SiHPh(2)). The X-ray structure of 16 confirmed sp(2) hybridization at silicon and revealed a short Ir-Si bond of 2.210(2) A. Catalytic hydrosilation of alkenes by hydrogen-substituted silylene complexes [(PNP)(H)Ir=SiMes(H)][B(C(6)F(5))(4)] (1) and 14 exhibited anti-Markovnikov regioselectivity with an array of alkene substrates. Addition of H(3)SiMes to complex 1 afforded [(PNP)(SiH(Mes)(Hex))IrH(SiH(2)Mes)][B(C(6)F(5))(4)] (19), featuring a beta-agostic interaction demonstrated by a J(SiH) of 102 Hz for the N-SiH hydrogen. Similarly, addition of H(2)SiPh(2) to 16 afforded the structurally characterized Ir(V) disilyl complex [(PNP)(SiPh(2))Ir(SiPh(2)H)(H)(2)][CB(11)H(6)Br(6)] (20). Complex 20 was found to be catalytically active for the hydrosilation of alkenes, which is consistent with its intermediacy in the catalytic cycle.
More Related Videos
12:27Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
12:08Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes
Published on: June 24, 2022
Related Concept Videos
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Reduction of Alkenes: Catalytic Hydrogenation
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the surface of...
Alkynes 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.
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction