A simple and efficient one-step protocol for the preparation of alkyl-substituted ammonium tetrafluoroborate and hexafluorophosphate salts

Saba, Shahrokh; Hernandez, Renee; Choy, Christine Chin; Carta, Kristine; Bennett, Yaasmin; Bondi, Steven; Kolaj, Sebastian; Bennett, Caitlin

doi:10.1016/j.jfluchem.2013.05.007

Cited by 13 publications

(9 citation statements)

References 17 publications

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“…Methanol (MeOH, Carlo Erba, analytical grade) and deuterated methanol (CD 3 OD, Eurisotop, 99.9% D) were dried over activated 4 Å molecular sieves and stored under an inert atmosphere in a sealed flask. Triethylammonium tetrafluoroborate ([Et 3 NH]BF 4 was synthesized according to the literature . The 1 H NMR spectra were recorded on a Bruker Avance III 300 or 400 MHz spectrometer at ambient temperature; chemical shifts (δ) are reported in ppm vs SiMe 4 and were determined by reference to the residual 1 H solvent peaks.…”

Section: Methodsmentioning

confidence: 99%

Reductive Termination of Cyanoisopropyl Radicals by Copper(I) Complexes and Proton Donors: Organometallic Intermediates or Coupled Proton–Electron Transfer?

et al. 2019

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Cyanoisopropyl radicals, generated thermally by the decomposition of azobis(isobutyronitrile) (AIBN), participate in reductive radical termination (RRT) under the combined effect of copper(I) complexes and proton donors (water, methanol, triethylammonium salts) in acetonitrile or benzene. The investigated copper complexes were formed in situ from [Cu I (MeCN)4] + BF4in CD3CN or Cu I Br in C6D6 using tris[2-(dimethylamino)ethyl]amine (Me6TREN), tris(2-pyridylmethyl)amine (TPMA) and 2,2'-bipyridine (BIPY) ligands. Upon keeping all other conditions constants, the impact of RRT is much greater for the Me6TREN and TPMA systems than for the BIPY system. RRT scales with the proton donor acidity (Et3NH + >> H2O > CH3OH), it is reduced by deuteration (H2O > D2O and CH3OH > CD3OD) and it is more efficient in C6D6 than in CD3CN. The collective evidence gathered in this study excludes the intervention of an outer-sphere proton-coupled electron transfer (OS-PCET), while an innersphere PCET (IS-PCET) cannot be excluded for coordinating proton donors (water and methanol). On the other hand, the strong impact of RRT for the non-coordinating Et3NH + in CD3CN results from the formation of an intermediate Cu I-radical adduct, suggested by DFT calculations to involve binding via the N atom to yield keteniminato [L/Cu-N=C=CMe2] + derivatives with only partial spin delocalization onto the Cu atom.

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Section: Methodsmentioning

confidence: 99%

Reductive Termination of Cyanoisopropyl Radicals by Copper(I) Complexes and Proton Donors: Organometallic Intermediates or Coupled Proton–Electron Transfer?

et al. 2019

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“…The phosphole ligand was synthesized according to a procedure in the literature ( 21 ). The acid Et 3 NHBF 4 was synthesized according to a modified procedure in the literature ( 39 ), where the crude product was extracted with dichloromethane to remove residual NH 4 BF 4 . All commercially available chemicals were used as received.…”

Section: Methodsmentioning

confidence: 99%

An iron-iron hydrogenase mimic with appended electron reservoir for efficient proton reduction in aqueous media

Becker

Amirjalayer

et al. 2016

Sci. Adv.

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“…Et 3 NHBF 4 was synthesized following a general procedure for preparation of alkyl-substituted ammonium tetrafluoroborate salts. [19] NH 4 BF 4 (0.521 g, 49.7 mmol, 1 equiv.) and Et 3 N (0.69 mL, 49.5 mmol, 1 equiv.)…”

Section: Synthesis Of Et 3 Nhbfmentioning

confidence: 99%

Mechanistic Elucidation of Dimer Formation and Strategies for Its Suppression in Electrochemical Reduction of Fac‐Mn(bpy)(CO)₃Br

et al. 2021

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Development of new catalytic approaches for reduction of small molecules is an aspiring technology to alleviate increasing energy demands without use of fossil fuels. One of the most promising molecular catalysts for reduction of CO 2 is fac-Mn(bpy)(CO) 3 Br (bpy = 2,2'-bipyridine). In this work, the mechanism of electrochemical reduction of this complex is elucidated using cyclic voltammetry along with digital simulations. It is revealed that the dimer complex, Mn 2 (bpy) 2 (CO) 6 , is not, as often assumed, formed by dimerization of the singly reduced manganese complex, [Mn(bpy)(CO) 3 ] * , but instead from its reduction to [Mn(bpy)(CO) 3 ] À , followed by further reaction with Mn(bpy)(CO) 3 Br (rate constant = 1.75 × 10 5 M À 1 s À 1 ). On the basis of cyclic voltammetry, infrared-spectroelectrochemistry, and 1 H NMR spectroscopy, we establish that this parent-child reaction involving Mn(bpy)(CO) 3 Br as electrophile can be diverted by adding either acids or iodomethane as substituting electrophiles. This demonstrates that [Mn(bpy)(CO) 3 ] À , which is the central catalyst for CO 2 reduction, can be formed at less extreme potentials than previously believed by suppressing the parent-child reaction.

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A simple and efficient one-step protocol for the preparation of alkyl-substituted ammonium tetrafluoroborate and hexafluorophosphate salts

Cited by 13 publications

References 17 publications

Reductive Termination of Cyanoisopropyl Radicals by Copper(I) Complexes and Proton Donors: Organometallic Intermediates or Coupled Proton–Electron Transfer?

Reductive Termination of Cyanoisopropyl Radicals by Copper(I) Complexes and Proton Donors: Organometallic Intermediates or Coupled Proton–Electron Transfer?

An iron-iron hydrogenase mimic with appended electron reservoir for efficient proton reduction in aqueous media

Mechanistic Elucidation of Dimer Formation and Strategies for Its Suppression in Electrochemical Reduction of Fac‐Mn(bpy)(CO)₃Br

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A simple and efficient one-step protocol for the preparation of alkyl-substituted ammonium tetrafluoroborate and hexafluorophosphate salts

Cited by 13 publications

References 17 publications

Reductive Termination of Cyanoisopropyl Radicals by Copper(I) Complexes and Proton Donors: Organometallic Intermediates or Coupled Proton–Electron Transfer?

Reductive Termination of Cyanoisopropyl Radicals by Copper(I) Complexes and Proton Donors: Organometallic Intermediates or Coupled Proton–Electron Transfer?

An iron-iron hydrogenase mimic with appended electron reservoir for efficient proton reduction in aqueous media

Mechanistic Elucidation of Dimer Formation and Strategies for Its Suppression in Electrochemical Reduction of Fac‐Mn(bpy)(CO)3Br

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Mechanistic Elucidation of Dimer Formation and Strategies for Its Suppression in Electrochemical Reduction of Fac‐Mn(bpy)(CO)₃Br