Computational insights into the mechanism of iron carbonyl-catalyzed ethylene hydrosilylation or dehydrogenative silylation

Guo, Chaozhong; Liu, Xiaoyan; Jia, Jianfeng; Wu, Hai‐Shun

doi:10.1016/j.comptc.2015.07.007

Cited by 6 publications

(4 citation statements)

References 67 publications

(123 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In intermediate C , the Fe–C2 (2.019 Å), Si1–C1 (1.897 Å), and C1–C2 (1.560 Å) bond lengths change a little with respect to those (1.939, 2.022, and 1.523 Å) in TS B/C , which indicates a very late transition state. This is similar to iron carbonyl catalyzed alkene hydrosilylation . Alternatively, alkene coordination and insertion triggered by adduct B‐2 is not competitive, as shown in the Supporting Information.…”

Section: Resultssupporting

confidence: 58%

Exploring the Chemoselective Dehydrogenative Silylation and Hydrogenation of Divinyldisiloxane with Hydrosilane from DFT Computation

et al. 2018

Self Cite

View full text Add to dashboard Cite

The chemoselective dehydrogenative silylation and hydrogenation of 1,3‐divinyldisiloxane by using HSiMe3 catalyzed by CpFe(CO)2Me (Cp = η5‐cyclopentadienyl) was explored by DFT computations. The active catalyst, CpFe(CO)SiMe3, was generated from a CO‐assisted pathway and HSiMe3‐initiated acetaldehyde reductive elimination. Starting from the active catalyst, the dehydrogenative silylation step of the first vinyl group was found to be the rate‐determining step, and the subsequent chemoselective hydrogenation step of the second vinyl group was discovered to be kinetically more favored. Within the reaction, the oxygen atom of 1,3‐divinyldisiloxane was not found to play a role in competitive coordination. The computed results rationalize the experimentally observed chemoselectivity.

show abstract

Section: Resultssupporting

confidence: 58%

Exploring the Chemoselective Dehydrogenative Silylation and Hydrogenation of Divinyldisiloxane with Hydrosilane from DFT Computation

et al. 2018

Self Cite

View full text Add to dashboard Cite

show abstract

“…The NMR‐silent nature of arsine as one of the ligating centres presents some challenges in making unambiguous product assignments and to this end, the present work will be supported by density functional theory calculations. DFT‐supported assignment is well‐established in the field and has been shown to provide considerable additional insight in studies of metal complex reactivity [71–74] …”

Section: Introductionmentioning

confidence: 99%

Contrasting Photochemical and Thermal Catalysis by Ruthenium Arsine Complexes Revealed by Parahydrogen Enhanced NMR Spectroscopy

et al. 2022

View full text Add to dashboard Cite

The thermal and photochemical reactivity of Ru(CO)3(dpae) (1) and Ru(CO)2(dpae)(PPh3) (2) towards H2 and diphenylacetylene is described. These reactions are monitored by NMR spectroscopy in conjunction with the parahydrogen induced polarisation (PHIP) effect, spatially resolved chemical shift imaging and the Only Parahydrogen Spectroscopy (OPSY) signal filtering method. The results are supported by DFT. The thermal and photochemical reactions of 1 with H2 proceed by CO loss and form Ru(H)2(CO)2(dpae) (3). 1 catalyses the formation of 1,2 diphenylethane, cis‐ and trans‐stilbene, and 1,2,3,4 tetraphenylbutadiene under 325 nm irradiation at 295 K in a reaction where Ru(CO)2(dpae)(η2‐CHPh=CPhCPh=CHPh) forms. When the same reaction is monitored under thermal conditions at 333 K the η2‐diene complex is no longer detected but hydride containing Ru(CHPhCH2Ph)(H)(CO)2(dpae) and Ru(CO)2(dpae)(trans‐stilbene) are seen. For 1, the photochemical promotion of hydrogenation through 325 nm irradiation results in an approximate 5.5‐fold increase in turnover at 333 K when compared to no irradiation. In contrast, 2 reacts thermally with H2 at 295 K through PPh3 and CO loss with both Ru(H)2(CO)(dpae)(solvent) and 3 being detected. Under irradiation, CO loss dominates and two isomers of Ru(H)2(CO)(dpae)(PPh3) form. While 2 forms the same 4 organic products at 295 K and a second isomer of Ru(CHPhCH2Ph)(H)(CO)2(dpae) alongside the diene complex no photochemical promotion of hydrogenation is observed.

show abstract

“…Another good example involves the use of strong π-acids such as CO as the ligand . Several iron and cobalt carbonyls have been reported as catalysts for hydrosilylation of alkenes.…”

Section: Introductionmentioning

confidence: 99%

“…A previous report indicated possible involvement of “Fe(0)(CNR) 2 ” and “Co(I)(CNR) 3 ” species in the reaction mechanisms . In the literature, , Fe(CO) 5 and Co 2 (CO) 8 are conventional base metal catalysts for alkene hydrosilylation and dehydrogenative silylation, and Fe(CO) 3 , R 3 SiCo(CO) 3 , and HCo(CO) 3 have been discussed as plausible catalytic intermediates. Analogous electronic structures of CNR with CO provide possible hydrosilylation mechanisms involving “Fe(0)(CNR) 3 ” and “Co(I)(CNR) 3 ” species.…”

Section: Introductionmentioning

confidence: 99%

Cobalt(0) and Iron(0) Isocyanides as Catalysts for Alkene Hydrosilylation with Hydrosiloxanes

Sanagawa

Nagashima

2018

Organometallics

View full text Add to dashboard Cite

Iron and cobalt isocyanides, Fe(CNR) 5 (1) and Co 2 (CNR) 8 (2), where R = t-butyl ( t Bu), adamantyl (Ad), and mesityl (Mes), were prepared by reduction of FeBr 2 or CoI 2 in the presence of CNR by C 8 K or silica-Na. These complexes were subjected to catalytic hydrosilylation of alkenes with hydrosiloxanes, and the results are compared with those obtained by previously reported Fe(OPiv) 2 /CNAd or Co-(OPiv) 2 /CNAd catalyst systems. Hydrosilylation of allylic ethers with 1,1,1,3,3-pentamethyldisiloxane (PMDS) catalyzed by 1 and the reaction of several alkenes with PMDS or 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD′M) catalyzed by 2 exhibited greater catalytic activity than that observed for the Fe(OPiv) 2 or Co(OPiv) 2 /CNR catalyst system. Complexes 1 and 2 were effective for catalytic chemical modification of silicone fluids containing Si−H groups and for two-component silicone curing. In all cases, selectivity of the reaction in terms of formation of the desired product by hydrosilylation and of byproducts due to dehydrogenative silylation did not differ between the metal isocyanide complexes and the corresponding M(OPiv) 2 /CNR catalyst system. Catalytically active species generated from 1, 2, and the M(OPiv) 2 /CNR catalyst system were also investigated.

show abstract

Computational insights into the mechanism of iron carbonyl-catalyzed ethylene hydrosilylation or dehydrogenative silylation

Cited by 6 publications

References 67 publications

Exploring the Chemoselective Dehydrogenative Silylation and Hydrogenation of Divinyldisiloxane with Hydrosilane from DFT Computation

Exploring the Chemoselective Dehydrogenative Silylation and Hydrogenation of Divinyldisiloxane with Hydrosilane from DFT Computation

Contrasting Photochemical and Thermal Catalysis by Ruthenium Arsine Complexes Revealed by Parahydrogen Enhanced NMR Spectroscopy

Cobalt(0) and Iron(0) Isocyanides as Catalysts for Alkene Hydrosilylation with Hydrosiloxanes

Contact Info

Product

Resources

About