Alkene metathesis with directly fluorinated alkenes is challenging, limiting its application in the burgeoning field of fluoro‐organic chemistry. A new nickel tris(phosphite) fluoro(trifluoromethyl)carbene complex ([P3Ni]=CFCF3) reacts with CF2=CF2(TFE) or CF2=CH2(VDF) to yield both metallacyclobutane and perfluorocarbene metathesis products, [P3Ni]=CF2and CR2=CFCF3(R=F, H). The reaction of [P3Ni]=CFCF3with trifluoroethylene also yields metathesis products, [P3Ni]=CF2and
Stereoretention in styrene heterodimerisation promoted by one-electron oxidants
Radical cations generated from the oxidation of CC π-bonds are synthetically useful reactive intermediates for C–C and C–X bond formation. Radical cation formation, induced by sub-stoichiometric amounts of external oxidant, are important intermediates in the Woodward–Hoffmann thermally disallowed [2 + 2] cycloaddition of electron-rich alkenes. Using density functional theory (DFT), we report the detailed mechanisms underlying the intermolecular heterodimerisation of anethole and β-methylstyrene to give unsymmetrical, tetra-substituted cyclobutanes. Reactions between trans -alkenes favour the all-trans adduct, resulting from a kinetic preference for anti -addition reinforced by reversibility at ambient temperatures since this is also the thermodynamic product; on the other hand, reactions between a trans -alkene and a cis -alkene favour syn -addition, while exocyclic rotation in the acyclic radical cation intermediate is also possible since C–C forming barriers are higher. Computations are consistent with the experimental observation that hexafluoroisopropanol ( HFIP ) is a better solvent than acetonitrile, in part due to its ability to stabilise the reduced form of the hypervalent iodine initiator by hydrogen bonding, but also through the stabilisation of radical cationic intermediates along the reaction coordinate.
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- Award ID(s):
- 1955876
- NSF-PAR ID:
- 10316174
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 11
- Issue:
- 34
- ISSN:
- 2041-6520
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract cis /trans ‐CFCF3=CFH. However, unlike reactions with TFE and VDF, this reaction forms metallacyclopropanes and fluoronickel alkenyl species, resulting presumably from instability of the expected metallacyclobutanes. DFT calculations and experimental evidence established that the observed metallacyclobutanes arenot intermediates in the formation of the observed metathesis products, thus highlighting a novel variant of the Chauvin mechanism enabled by the disparate four‐coordinate transition states. -
null (Ed.)Bio-derived isobutanol has been approved as a gasoline additive in the US, but our understanding of its combustion chemistry still has significant uncertainties. Detailed quantum calculations could improve model accuracy leading to better estimation of isobutanol's combustion properties and its environmental impacts. This work examines 47 molecules and 38 reactions involved in the first oxygen addition to isobutanol's three alkyl radicals located α, β, and γ to the hydroxide. Quantum calculations are mostly done at CCSD(T)-F12/cc-pVTZ-F12//B3LYP/CBSB7, with 1-D hindered rotor corrections obtained at B3LYP/6-31G(d). The resulting potential energy surfaces are the most comprehensive isobutanol peroxy networks published to date. Canonical transition state theory and a 1-D microcanonical master equation are used to derive high-pressure-limit and pressure-dependent rate coefficients, respectively. At all conditions studied, the recombination of γ-isobutanol radical with O 2 forms HO 2 + isobutanal. The recombination of β-isobutanol radical with O 2 forms a stabilized hydroperoxy alkyl radical below 400 K, water + an alkoxy radical at higher temperatures, and HO 2 + an alkene above 1200 K. The recombination of β-isobutanol radical with O 2 results in a mixture of products between 700–1100 K, forming acetone + formaldehyde + OH at lower temperatures and forming HO 2 + alkenes at higher temperatures. The barrier heights, high-pressure-limit rates, and pressure-dependent kinetics generally agree with the results from previous quantum chemistry calculations. Six reaction rates in this work deviate by over three orders of magnitude from kinetics in detailed models of isobutanol combustion, suggesting the rates calculated here can help improve modeling of isobutanol combustion and its environmental fate.more » « less
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The reaction of the D1-silylidyne radical (SiD; X 2 Π) with phosphine (PH 3 ; X 1 A 1 ) was conducted in a crossed molecular beams machine under single collision conditions. Merging of the experimental results with ab initio electronic structure and statistical Rice–Ramsperger–Kassel–Marcus (RRKM) calculations indicates that the reaction is initiated by the barrierless formation of a van der Waals complex (i0) as well as intermediate (i1) formed via the barrierless addition of the SiD radical with its silicon atom to the non-bonding electron pair of phosphorus of the phosphine. Hydrogen shifts from the phosphorous atom to the adjacent silicon atom yield intermediates i2a, i2b, i3; unimolecular decomposition of these intermediates leads eventually to the formation of trans / cis -phosphinidenesilyl (HSiPH, p2/p4) and phosphinosilylidyne (SiPH 2 , p3) via hydrogen deuteride (HD) loss (experiment: 80 ± 11%, RRKM: 68.7%) and d - trans / cis -phosphinidenesilyl (DSiPH, p2′/p4′) plus molecular hydrogen (H 2 ) (experiment: 20 ± 7%, RRKM: 31.3%) through indirect scattering dynamics via tight exit transition states. Overall, the study reveals branching ratios of p2/p4/p2′/p4′ ( trans / cis HSiPH/DSiPH) to p3 (SiPH 2 ) of close to 4 : 1. The present study sheds light on the complex reaction dynamics of the silicon and phosphorous systems involving multiple atomic hydrogen migrations and tight exit transition states, thus opening up a versatile path to access the previously elusive phosphinidenesilyl and phosphinosilylidyne doublet radicals, which represent potential targets of future astronomical searches toward cold molecular clouds (TMC-1), star forming regions (Sgr(B2)), and circumstellar envelopes of carbon rich stars (IRC + 10216).more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0sc03059g
