The effectiveness of a primary aliphatic amino group as an internal Lewis base on the formation of a boron–oxygen–carbon linkage: a computational study

Bhat, Krishna L.; Braz, Valerie A.; Laverty, Erin; Bock, Charles W.

doi:10.1016/j.theochem.2004.07.036

Cited by 17 publications

(34 citation statements)

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“…o -(pyrrolidinylmethyl)phenylboronic acid) structures reported by Anslyn 32 was ~2.7 Å, whereas results at the MP2 and PBE1PBE methods of this study predict much shorter distances, 1.768–1.860 Å, see Table 1S and 2S) indicative of a boron-nitrogen dative bond; this difficultly with describing intramolecular N→B bonding in boronic acids appears to be symptomatic of B3LYP methodology. 29,34–39 On the other hand, there are some areas of agreement with our calculations and those of Anslyn and coworkers 32 e.g. the boronate ester (formed from the reaction of an o -( N,N -dialkylaminomethyl)arylboronic acid ( i.e.…”

Section: Resultssupporting

confidence: 89%

“…In view of the role that diffuse functions play in the MP2 thermochemistry of 10 – 23 noted above (see Table 1A), we decided to re-optimize these structures employing the more economical DFT methodology using the PBE1PBE functional with the larger 6–311++G( d,p ) and aug-cc-pVDZ basis sets which explicitly include diffuse functions. 29,34–35,39 Interestingly, overlaying the MP2/cc-pVDZ, PBE1PBE/6–311++G( d,p ), and PBE1PBE/aug-cc-pVDZ optimized structures showed no significant variation in the geometry as a result of altering the computational methodology from MP2 to PBE1PBE and increasing the size of the basis set, see Figure 1S in the Supplementary Materials. Furthermore, the trends observed for the PBE1PBE reaction energetics are generally in accord to those seen at the various MP2 levels we employed, compare Tables 1A and 1B, although some details are different.…”

Section: Resultsmentioning

confidence: 99%

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A Computational Investigation of the Nitrogen−Boron Interaction in o-(N,N-Dialkylaminomethyl)arylboronate Systems

et al. 2010

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o-(N,N-Dialkylaminomethyl)arylboronate systems are an important class of compounds in diol-sensor development. We report results from a computational investigation of fourteen o-(N,N-dialkylaminomethyl)arylboronates using second-order Møller-Plesset (MP2) perturbation theory. Geometry optimizations were performed at the MP2/cc-pVDZ level and followed by single-point calculations at the MP2/aug-cc-pVDZ(cc-pVTZ) levels. These results are compared to those from density functional theory (DFT) at the PBE1PBE(PBE1PBE-D)/6-311++G(d,p)(aug-cc-pVDZ) levels, as well as to experiment. Results from continuum PCM and CPCM solvation models were employed to assess the effects of a bulk aqueous environment. Although the behaviour of o-(N,N-dialkylaminomethyl) free acid and ester proved to be complicated, we were able to extract some important trends from our calculations: 1) for the free acids the intramolecular hydrogen-bonded B-O-H⋯N seven-membered ring conformers 12 and 16 are found to be slightly lower in energy than the dative-bonded N→B five-membered ring conformers 10 and 14 while conformers 13 and 17, with no direct boron-nitrogen interaction, are significantly higher in energy than 12 and 16; 2) for the esters where no intramolecular B-O-H⋯N bonded form is possible, the N→B conformers 18 and 21 are significantly lower in energy than the no-interaction forms 20 and 23; 3) H2O insertion reactions into the N→B structures 10, 14, 18, and 21 leading to the seven-membered intermolecular hydrogen-bonded B⋯OH2⋯N ring structures 11, 15, 19, and 22 are all energetically favorable.

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 99%

A Computational Investigation of the Nitrogen−Boron Interaction in o-(N,N-Dialkylaminomethyl)arylboronate Systems

et al. 2010

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“…Whilst speculative, this structural interpretation of the interaction between boronic acid and the proximal tertiary amine through a bound protic solvent molecule (solvent insertion into the N -B bond) corresponds well with contemporary computational and potentiometric titration data, in which the formation of intramolecular seven-membered rings should not be ignored [31,36,72,73]. The values for the bond length (from the X-ray crystal structure) and for the bond strength (from the potentiometric titrations) are those that would be expected for a hydrogen bonding interaction manifested through a bound solvent molecule at the boron centre.…”

Section: Methodssupporting

confidence: 71%

Saccharide-Selective Boronic Acid Based Photoinduced Electron Transfer (PET) Fluorescent Sensors

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Creative Chemical Sensor Systems

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“…It should be noted that other problems have surfaced concerning the capability of the B3LYP functional with split-valence basis sets for describing various aspects of boron chemistry, most notably dative bonding issues 68,116,–121 .…”

Section: Discussionmentioning

confidence: 99%

Thermodynamics of Boroxine Formation from the Aliphatic Boronic Acid Monomers R–B(OH)₂ (R = H, H₃C, H₂N, HO, and F): A Computational Investigation

et al. 2011

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Boroxines are the 6-membered cyclotrimeric dehydration products of organoboronic acids: 3 R– B(OH)2 → R3B3O3 + 3 H2O, and in recent years have emerged as a useful class of organoboron molecules with applications in organic synthesis both as reagents and catalysts, as structural components in boronic acid derived pharmaceutical agents, as anion acceptors and electrolyte additives for battery materials [AL Korich and PM Iovine, Dalton Trans. 39 (2010) 1423–1431]. Second-order Møller-Plesset perturbation theory, in conjunction with the Dunning-Woon correlation-consistent cc-pVDZ, aug-cc-pVDZ, cc-pVTZ, and aug-cc-pVTZ basis sets, was used to investigate the structures and relative energies of the endo-exo, anti, and syn conformers of the aliphatic boronic acids R–B(OH)2 (R = H, H3C, H2N, HO, and F), as well as the thermodynamics of their boroxine formation; single-point calculations at the MP2/aug-cc-pVQZ, MP2/aug-cc-pV5Z, and CCSD(T)/aug-cc-pVTZ level using the MP2/aug-cc-pVTZ optimized geometries were also performed in selected cases. The endo-exo conformer was generally lowest in energy in vacuo, as well as in PCM and CPCM models of aqueous and carbon tetrachloride media. The values of ΔnormalH2980 for boroxine formation via dehydration from the endo-exo conformers of these aliphatic boronic acids ranged from −2.9 for (H2N)3B3O3 to +12.2 kcal/mol for H3B3O3 at the MP2/aug-cc-pVTZ level in vacuo; for H3B3O3 the corresponding values in PCM:UFF implicit carbon tetrachloride and aqueous media were +11.2 and +9.8 kcal/mol, respectively. Based on our calculations, we recommend that ΔHf(298 K) for boroxine listed in the JANAF compilation needs to be revised from −290.0 kcal/mol to approximately −277.0 kcal/mol.

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The effectiveness of a primary aliphatic amino group as an internal Lewis base on the formation of a boron–oxygen–carbon linkage: a computational study

Cited by 17 publications

References 85 publications

A Computational Investigation of the Nitrogen−Boron Interaction in o-(N,N-Dialkylaminomethyl)arylboronate Systems

A Computational Investigation of the Nitrogen−Boron Interaction in o-(N,N-Dialkylaminomethyl)arylboronate Systems

Saccharide-Selective Boronic Acid Based Photoinduced Electron Transfer (PET) Fluorescent Sensors

Thermodynamics of Boroxine Formation from the Aliphatic Boronic Acid Monomers R–B(OH)₂ (R = H, H₃C, H₂N, HO, and F): A Computational Investigation

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The effectiveness of a primary aliphatic amino group as an internal Lewis base on the formation of a boron–oxygen–carbon linkage: a computational study

Cited by 17 publications

References 85 publications

A Computational Investigation of the Nitrogen−Boron Interaction in o-(N,N-Dialkylaminomethyl)arylboronate Systems

A Computational Investigation of the Nitrogen−Boron Interaction in o-(N,N-Dialkylaminomethyl)arylboronate Systems

Saccharide-Selective Boronic Acid Based Photoinduced Electron Transfer (PET) Fluorescent Sensors

Thermodynamics of Boroxine Formation from the Aliphatic Boronic Acid Monomers R–B(OH)2 (R = H, H3C, H2N, HO, and F): A Computational Investigation

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Thermodynamics of Boroxine Formation from the Aliphatic Boronic Acid Monomers R–B(OH)₂ (R = H, H₃C, H₂N, HO, and F): A Computational Investigation