Margaret E. Crowleya,
Christopher D. Stachurski*b,
James H. Davis Jr*a,
Matthias Zellerc,
Gabriel A. Merchanta,
E. A. Saltera,
A. Wierzbickia,
Richard A. O'Briena,
Paul C. Truloveb and
David P. Durkinb
aDepartment of Chemistry, University of South Alabama, Mobile, AL 36688, USA. E-mail: jdavis@southalabama.edu
bDepartment of Chemistry, United States Naval Academy, Annapolis, MD 21402, USA
cDepartment of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA
First published on 12th June 2025
Boron cations (boronium ions) of any charge – 1+, 2+, or 3+ – are demonstrably among the least well-known and studied family of monoboron species. Those of 3+ charge are especially few in number, and scant information is available about them. This lack of information is likely rooted in the relatively poor stability – especially towards water – of known exemplars. Now, by utilizing strongly donating 4-N,N-dialkylaminopyridines as ligands to the boron center we have succeeded in preparing salts indefinitely stable in water at pH values from 1 to 14. Further, we have acquired multinuclear NMR spectra on each of the new species and for the first time evaluated their thermal characteristics (DSC and TGA), finding that they are quite robust. In addition, the electrochemical behaviour of the new salts was evaluated using cyclic voltammetry. The structures of several of the new materials have been determined by single-crystal X-ray crystallography, and detailed computational modelling has been undertaken to provide additional insight into the experimental data.
In 1970 Bohl and Galloway isolated the parent Py4B3+ ion as an iodide salt which they reported to be exquisitely sensitive to water, rapidly decomposing upon addition to an aqueous solution of KPF6 in an attempt at anion exchange. Consequently, the sole published characterization data for it consists of elemental analysis (C, H, N, and I) of the initially isolated product.8 Contemporaneously, Ryschkewitsch and co-workers found that a derivative cation bearing four 4-methylpyridine ligands was somewhat more stable, albeit on a pH-dependent basis.9 Specifically, this cation was stable for ∼1 week in water at pH = 1, moderately stable for 24 h at pH = 7, decomposed in ∼1 h at pH = 11 and in ∼1 min at pH = 13.6. The improved stability of the latter cation versus that of Py4B3+ was attributed to the 4-methyl group increasing electron density at the pyridyl nitrogen. Against this background, and given our ongoing work with boronium ions, we were interested in attempting to further improve the aqueous stability of boronium (+3) ions so that their chemistry might be more thoroughly evaluated, including making determinations of the thermochemical and electrochemical characteristics of this cation class. It was our hypothesis that improving the stability of these cations might be accomplished by using as ligands the powerful nucleophilic N-donor DMAP (4-dimethylamino pyridine) and variants thereof (Fig. 1).10
![]() | ||
Fig. 1 Left: Basic structure of the Py4B3+ cations. Right: Structures (1–5) of the 4-alkylamino pyridine ligands of the new cations, followed by those of the Ryschkewitsch (6) and Bohl (7) cations. |
A 500 mL Erlenmeyer flask was charged with 200 mL of hot water and a magnetic stirbar. While stirring, 15.0 g (0.020 mol) of the preceding bromide salt was added. It dissolved quickly, producing a colorless solution. Separately, 20.0 g (0.062 mol) of KTf2N [potassium bis(trifluoromethanesulfonyl)imide] was likewise dissolved in hot water, and the resulting solution slowly added to that of the bromide salt. Upon mixing, a copious amount of white solid precipitated. Stirring was continued for an hour after which time the product [1(Tf2N)3] was separated by vacuum filtration, washed with water, and dried in vacuo (25.7 g, 96%). The Tf2N− salts of cations 2–5 were prepared in the same way (Scheme 1).
D2O solutions were prepared having pH (pD) values ranging monotonically from 7 to 14. The bromide salt of the parent DMAP boronium, 1, was dissolved in these solutions and 1H-, 13C- and 10B-NMR spectra were acquired (T = 20 °C) five minutes after dissolution, after one week, after two weeks, and finally after four months (note: the Tf2N− salt of the cation is water-insoluble; hence, to gauge the cation's stability towards water, the soluble bromide salt was used). The outcome was clear. The spectra of 1 were unchanged at pHs 1–13 (acidic pH range experiments below) over any length of time; some evidence of decomposition (extra peaks) was observed at pH = 14 after four months. We then undertook a similar study on 2, (selected as a representative of those salts bearing more lipophilic R2N− groups). The spectra of 2 showed no changes at benchmark pH values of 1, 7, or 13 after five minutes, after one week, or after four months. However, (apparent) decomposition products were visible even after one week at pH = 14.
We also considered that using these N,N-dialkylamino pyridine ligands might create a sensitivity on the part of the boroniums towards acidic media due to the lone electron pair on the dialkylamine groups. We note that protonation of the Me2N− group of a DMAP ligand coordinated to a molybdenum atom through the pyridyl nitrogen has been reported by Harman et al.11 Further, Forsythe and co-workers have shown that DMAP protonated at the pyridine nitrogen can be further protonated at the Me2N group in acidic media.12 Consequently, we thought it wise to extend our pH studies into the acidic domain. Accordingly, the bromide salts of 1 and 2 were dissolved in D2O having pH (pD) values varying monotonically from 1–7, with 1H-, 13C-, and 10B-NMR spectra acquired on each after five minutes, one week, two weeks, and four months. Here again, no changes were observed for either boronium at any of those pH values over any of those periods of time, indicating that the cations remained stable in the acidic pH domain as well. Indeed, the wholesale lack of any chemical shift changes also suggests that no protonation at the R2N− substituents occurs in these ions, in contrast to the Harman and Forsythe cases (vide supra). We posit that the coordination of the present ligands to the B (+3) center is sufficiently depleting of electron density on the R2N− nitrogen atoms to render them inert to protonation. Globally, these NMR studies provide clear evidence that at ambient temperature, boronium cations 1 and 2 – and by extension, we posit, 3–5 as well – are highly resistant to hydrolysis under conditions ranging from very acidic to very basic. This is in sharp contrast to previous reports detailing the aqueous stability of (Py)4B3+ (the Bohl cation) and (Pic)4B3+ (Pic = picoline, 4-methylpyridine, the Ryschkewitsch cation). Indeed, given the very well-known propensity for molecular monoboron compounds to react with water to form boric acid ( = −1093 kJ mol−1), this degree of pH-independent stability towards water is impressive.
Seeking to gain insight into origins of the enhanced stability of cations 1–5, computational studies were also carried out. The cation geometries were optimized, and atomic natural bond order (NBO) partial charges of the new species were assigned using Gaussian 16.13 All structures were optimized under S4 symmetry using the wB97XD density functional method and the 6-31g(d) basis set, followed by evaluation of frequencies, then reoptimized using the cc-pvtz basis set. Subsequently, electrostatic potential maps were generated by Spartan'24 from single-point calculations.14 The partial charges on the B and N atoms in each cation are presented in Table 1. Additional computational details and coordinates of optimized structures are available in the ESI.†
As is apparent from this data, the presence of a dialkylamine group in the pyridine 4-position enhances the partial negative charge on the pyridinyl nitrogen in 1–5 relative to those in cations 6 and 7. In turn, the p-methyl group on cation 6 enhances the negative charge on the pyridinyl nitrogen versus that on cation 7, as posited by Ryschkewitsch. But notably the 6 vs. 7 negative-charge difference of 0.007 is dwarfed by that of 0.043 which exists between that of the average value of cations 1–5 versus cation 7. This substantiates our hypothesis that introducing an R2N− substituent in the 4-position of pyridine would result in ligands better able to stabilize the high charge on a boronium (+3) center. Indeed, the computed negative charge on the pyridyl Ns progressively becomes more negative as the putative donor strength in the 4-position of the pyridine ring increases, and by the same token the positive charge on the boron decreases as the donor strength increases. These general trends can be visually appreciated by comparing the electrostatic potential maps for cations 1, 6, and 7 (Fig. 2). Consistent with the foregoing, the computed (Table 1) N–B bond distances in 1–5 are shorter than those in 6 and 7, suggesting stronger bonds between those atoms in the new set of cations.
Colorless, X-ray quality single crystals of the Tf2N− salts of cations 1, 2, 3 and 5 were obtained by recrystallization of the initial solid products from hot methanol or acetone-methanol mixtures, allowing us to acquire structures (Fig. 3 and Table 1) that enabled us to compare the B–N bond distances in the present boroniums with that in the (4-MePy)4B3+ (Ryschkewitsch) cation; note that years after the original Ryschkewitsch work, Vargas-Baca, Cowley, and co-workers successfully crystallized and obtained an X-ray structure on the bromide salt of the latter.15 In contrast, no comparison to the Bohl cation is possible since there is no published X-ray structure of any salt containing it.8 It also bears mention that while the Tf2N− salt of cation 4 produced visually satisfactory crystals, they yielded hopelessly disordered structures even after multiple recrystallizations from different solvent media.
As shown in Table 1, the B–N bond distances in 1, 2, 3, and 5 are the same within experimental error, consistent with the five DMAP-family ligands having similar electron-donating strength to the boronium center. Further, these distances are significantly shorter than that between N and B in the Ryschkewitsch cation 6, validating the computational results (vide supra), and suggesting a weaker B–N bond in the latter. This is consistent with the longstanding understanding that amine groups are more “electron donating” (better ortho–para directors) than are alkyl groups. In accord with the foregoing, the C(3)–N(2) distances in 1, 2, 3, and 5 are such as to suggest that the capacity of their 4-amino groups to ‘push’ electron density into the pyridines were fundamentally the same. Again, complimenting these data are the computed charges (Table 1) for the boron and pyridine N atoms in boroniums 1–7. Note that the charges on the pyridine Ns in 1–4 are quite close, and that of 5 relatively close as well, but there is a sharp drop-off for those in 6 and 7. Even more significant, the positive charges on the Bs of 1–5 are close, but there is a noticeable increase for those in 6 and 7, the Ryschkewitsch and Bohl cations, respectively.
Thermal properties of the suite of the Tf2N− salts of cations 1–5 were measured using both TGA and DSC. Temperatures (T5) were measured in duplicate to ensure consistency (Fig. S1†). Remarkably, the boronium (+3) cations exhibit thermal stabilities (Table 2) up to 278 °C, nearly 50 °C higher than boronium salts in which the cation contains at least one trialkylamine moiety. The salt of cation 5 exhibits the highest thermal stability (336 °C), on par with some of the highest reported thermal stabilities for both past reported boronium salts and other onium salts such as imidazolium, phosphonium, and pyrrolidinium cations.16–22 We speculate that the increase in T5 from cations 1–4 to cation 5 may indicate that the very large bulk of the latter leads to a delay in the onset of whatever mechanism is operative in its thermal decomposition.23,24
Thermal characteristics | ||
---|---|---|
Cation | T5 (oC) | Tm (oC) |
1 | 291 ± 2 | 202 |
2 | 295 ± 3 | 149 |
3 | 278 ± 10 | — |
4 | 280 ± 2 | — |
5 | 336 ± 4 | 89 |
In addition to thermal stability, the phase behavior of salts such as the present boroniums is of interest to better understand how the charge distribution and chemical nature of the cation influence the overall properties of the material. The high charge on each cation, and consequentially higher number of associated anions, leads to salts with melting temperatures well above room temperature for the Tf2N− salts of 1–5; this differs significantly from the characteristics of several known boronium (+1) Tf2N salts which are ionic liquids (having sub-100 °C Tm). Across the board with 1–5, no phase transitions at low temperatures (i.e., glass transitions) were observed. On the heating curves, the Tf2N− salts of 1, 2, and 5 all exhibit clean melting behavior, at 202, 149, and 89 °C, respectively (Fig. S2†). We note that the Tm of 5(Tf2N)3 makes it ‘classifiable’ as an ionic liquid by the frequently used (but arbitrary) metric of being <100 °C.24 In addition to an initial solid–liquid transition, cation 5 exhibits a second endothermic peak at 198 °C, which appears to be an example of a high temperature liquid–liquid transition.25 Salts 3 and 4 also undergo endothermic transitions at elevated temperatures, though broader peaks are seen compared to those of 1, 2, and 5 (Fig. S2†). While less well-defined, two endothermic peaks can be distinguished from the heating curve of 3, much like 5, suggesting similar thermal behavior for the two samples.
Cyclic voltammetry (CV) was performed on cation 1 to determine a baseline electrochemical behavior for a boronium (+3) salt, something which to our knowledge has not previously been reported. Although our earlier studies on boronium salts focused on innately liquid materials, i.e., ionic liquids, the high Tm values of the boronium (+3) salts prevented their direct study as neat electrolytes; accordingly, solutions in acetonitrile were used to investigate their electrochemical behavior, particularly with respect to electrochemical degradation or the buildup of solid–electrolyte interface (SEI) layers.26,27
Sweeping negative from the open circuit potential (OCP) in the presence of cation 1 reveals three clearly separated, irreversible reductions at −2.19 V, −2.55 V, and −2.87 V (vs. Fc/Fc+) (Fig. 4). In context, we were surprised by these values since two other boronium cations of lesser positive charge (8 (ref. 28) and 9,29 Fig. 5) which are also supported by pyridine-derivative ligands, are reduced at lower potentials (−1.62 and −0.673/−1.003 V, respectively). Intuitively, we expected the more positively charged material to reduce more readily.
![]() | ||
Fig. 4 Cyclic voltammogram of the Tf2N− salt of 1. Scans were conducted at 50 mV s−1 from Vocp, first negative, then positive. The three sequential one-electron reduction steps are clearly apparent. |
Further by way of context, the structurally similar tetraphenylphosphonium (PPh4+) monocation exhibits a single reduction potential of −3.25 V (vs. Fc/Fc+). Clearly multiple factors, including the formal charge on the cation and the electronic nature of the ligands can contribute to the vastly different reduction potentials between these cations despite similarities in structure.30
On the return sweep in the CV of 1(Tf2N)3, a single oxidation was seen at 1.8 V (vs. Fc/Fc+) which is consistent with studies on neat boronium electrolytes with Tf2N− anions. The presence of this peak, which is dependent on initial sweeps beyond the cathodic limit of the cell, is believed to be the oxidation of the surface–electrolyte interface (SEI) layer which assembles at the onset of cation degradation.26,27,31,32 Continuous sweeping of the electrode reveals reduced cathodic activity, likely due to surface passivation from SEI accumulation, while the intensity and position of the oxidative peak remains consistent. In addition, the Tf2N− salts of 2 and 3 were also tested for electrochemical activity in acetonitrile (Fig. S3†). Unlike the Tf2N− salt of cation 1, both compounds exhibited broad, single step reductions when sweeping from OCP to negative potentials.33 The oxidation peak observed on return sweeps was also present, though significantly altered in shape from what was observed for cation 1. The difference in behavior between these samples suggest potentially different decomposition pathways as the test cell approaches either the cathodic or anodic limiting potential, warranting further studies on the reductive products of any future boronium (+3) salts as well.31
Footnote |
† Electronic supplementary information (ESI) available. CCDC 2394932–2394934 and 2394936. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d5ra02301g |
This journal is © The Royal Society of Chemistry 2025 |