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

J D Larkin, J S Fossey, Tony D James, B R Brooks, C W Bock

Research output: Contribution to journalArticle

47 Citations (Scopus)

Abstract

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 Moller-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-pVD7(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 behavior 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
Original languageEnglish
Pages (from-to)12531-12539
Number of pages9
JournalThe Journal of Physical Chemistry A
Volume114
Issue number47
DOIs
Publication statusPublished - 2 Dec 2010

Fingerprint

Boron
Hydrogen
Esters
boron
Nitrogen
nitrogen
Acids
Pulse code modulation
esters
Solvation
Density functional theory
acids
rings
ring structures
interactions
hydrogen
solvation
Geometry
energy
insertion

Cite this

A Computational Investigation of the Nitrogen-Boron Interaction in o-(N,N-Dialkylaminomethyl)arylboronate Systems. / Larkin, J D; Fossey, J S; James, Tony D; Brooks, B R; Bock, C W.

In: The Journal of Physical Chemistry A, Vol. 114, No. 47, 02.12.2010, p. 12531-12539.

Research output: Contribution to journalArticle

@article{85734e3287c84125be6cd60c31fb58e3,
title = "A Computational Investigation of the Nitrogen-Boron Interaction in o-(N,N-Dialkylaminomethyl)arylboronate Systems",
abstract = "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 Moller-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-pVD7(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 behavior 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",
author = "Larkin, {J D} and Fossey, {J S} and James, {Tony D} and Brooks, {B R} and Bock, {C W}",
year = "2010",
month = "12",
day = "2",
doi = "10.1021/jp1087674",
language = "English",
volume = "114",
pages = "12531--12539",
journal = "The Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "47",

}

TY - JOUR

T1 - A Computational Investigation of the Nitrogen-Boron Interaction in o-(N,N-Dialkylaminomethyl)arylboronate Systems

AU - Larkin, J D

AU - Fossey, J S

AU - James, Tony D

AU - Brooks, B R

AU - Bock, C W

PY - 2010/12/2

Y1 - 2010/12/2

N2 - 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 Moller-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-pVD7(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 behavior 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

AB - 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 Moller-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-pVD7(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 behavior 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

UR - http://www.scopus.com/inward/record.url?scp=78649563560&partnerID=8YFLogxK

UR - http://dx.doi.org/10.1021/jp1087674

U2 - 10.1021/jp1087674

DO - 10.1021/jp1087674

M3 - Article

VL - 114

SP - 12531

EP - 12539

JO - The Journal of Physical Chemistry A

JF - The Journal of Physical Chemistry A

SN - 1089-5639

IS - 47

ER -