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Larkin JD , Fossey JS , James TD , Brooks BR , Bock CW
A Computational Investigation of the Nitrogen-Boron Interaction in o-(N,N-Dialkylaminomethyl)arylboronate Systems
Journal of Physical Chemistry A. 2010 Dec;114(47) :12531-12539
PMID: ISI:000284454800021   
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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 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
Larkin, Joseph D. Fossey, John S. James, Tony D. Brooks, Bernard R. Bock, Charles W. NIH NHLBI ; University of Bath ; University of Birmingham ; ERDF AWMII This research was supported in part (J D L and B R B) by the Intramural Research Program of the NIH NHLBI The PQS Cluster Facility at Philadelphia University (C W B) was extensively used for the calculations described in this manuscript This study also utilized the high performance computational capabilities of the Biowulf Linux cluster at the National Institutes of Health Bethesda MD (http // biowulf nih gov) T D J thanks the University of Bath for support and J S F thanks the University of Birmingham and ERDF AWMII for support J D L also thanks Dr Yihan Shao of QChem for his helpful discussions with respect to the Incorporation of PBE1PBE-D functional 75 Amer chemical soc; 1155 16th st, nw, washington, dc 20036 usa 683ep