Proton transfer reactions of hydrazine-boranes

Adamson, Aiko; Guillemin, Jean‐Claude; Burk, Peeter

doi:10.1002/poc.3401

Cited by 11 publications

(11 citation statements)

References 26 publications

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“…The calculations were carried out using the GAUSSIAN 09 program package under the programs default conditions (298.15 K and 1 atm) if not stated otherwise. In our work we used MP2 method with 6‐311 + G(d,p) basis set which has been shown to be adequate and relatively cheap method for calculating proton transfer reactions . In some cases, G2 method was also used to calculate energies for different deprotonation centers with close energies.…”

Section: Computational Detailsmentioning

confidence: 99%

“…In our work we used MP2 [18][19][20][21][22] method with 6-311 + G(d,p) basis set [23][24][25][26] which has been shown to be adequate and relatively cheap method for calculating proton transfer reactions. [27][28][29] In some cases, G2 method [30] was also used to calculate energies for different deprotonation centers with close energies. A full conformational search was done for each species and vibrational analyses for zero-point energies, and thermal corrections were performed.…”

Section: Computational Detailsmentioning

confidence: 99%

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Relative stability and proton transfer reactions of unsaturated isocyanides and cyanides

Adamson

Kaljurand

Guillemin

et al. 2016

J. Phys. Org. Chem.

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The typical Gibbs free energy difference between hydrocarbon substituted isocyanides and the corresponding cyanides is 25 to 28 kcal/mol in favor of the cyanides and is mostly independent of the substituent. Triple bonded species with a ―C ≡ C―RN,C (RN,C = CN, NC) structure can be considered as exceptions. Because isocyanide and cyanide species have very similar structures, the relative energy is independent of the pressure and temperature conditions. Theoretical and experimental gas‐phase investigations show that basicity of isocyanides ranges from 182.1 to 198.2 kcal/mol which is 14.0 to 19.7 kcal/mol higher than the basicity of respective cyanides. The most favored protonation centers are located on isocyanide or cyanide group depending on the species. The biggest increase of basicity was caused by bulkier substituents. The substitutions have greater influence on the basicity of cyanides than on the basicity of isocyanides. In regard to deprotonation, the cyanides are more acidic than the corresponding isocyanides. For most of the unsaturated cyanide and isocyanide species the (N,C)‐CHR′ hydrogen (the one connected to the carbon next to cyanide/isocyanide group) is the most acidic. Our work suggests that for derivatives bearing unsaturated substituent the favored deprotonation center may be different and some cyanides and isocyanides are unstable towards gas‐phase deprotonation equilibrium as the formed anion tends to isomerize. Copyright © 2016 John Wiley & Sons, Ltd.

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Section: Computational Detailsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Relative stability and proton transfer reactions of unsaturated isocyanides and cyanides

Adamson

Kaljurand

Guillemin

et al. 2016

J. Phys. Org. Chem.

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“…A mixture of noncovalent and covalent bonding is responsible for molecular recognition, proton transfer management and the structure and functions of proteins and DNA . Among many of the possible noncovalent bonding schemes, triel atoms (B, Al, etc) participate in the interactions of great chemical and biological significance with a variety of Lewis bases . A key property of triel species (for example, boron trihalides) is the presence of an unfilled p‐orbital on the triel center and the triel ability to be satisfied with only 6 paired electrons .…”

Section: Introductionmentioning

confidence: 99%

Triel‐Bonded Complexes between TrR₃ (Tr=B, Al, Ga; R=H, F, Cl, Br, CH₃) and Pyrazine

2018

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Complexes between TrR (Tr=B, Al, Ga; R=H, F, Cl, Br, CH ) molecules and pyrazine have been characterized at the MP2 and CCSD(T) levels of theory. The adducts can be grouped according to the type of molecular arrangement. The first situation places the Tr atom in the plane of the pyrazine ring and contains a triel bond to the N lone pair. For the boron complexes the orbital interaction energy is almost equal to the electrostatic component, while the former is only half the latter for Tr=Al and Ga. The two monomers are stacked above one another in the second configuration, which depends to a greater degree upon orbital interaction and dispersion. The former complexes are more strongly bonded than the latter. Interaction energies (E ) for the stronger complexes vary between -50 and -20 kcal/mol for BBr and Ga(CH ) paired respectively with pyrazine. E is much smaller for the stacked configurations, ranging from -8 for GaF to -1.4 kcal/mol for BF . The value of the maximum of the electrostatic potential correlates poorly with E , attributed in part to monomer distortions upon complexation.

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“…The role of boron center in different chemical and biochemical processes is a subject of numerous studies, both experimental and theoretical ones. [1,2] For example, in boron trihalides, the B-center is characterized by the p-orbital vacancy and the Lewis octet rule is not obeyed there. [3] Hence, boron often interacts strongly with Lewis bases complementing the octet structure by their electrons.…”

Section: Introductionmentioning

confidence: 99%

Two faces of triel bonds in boron trihalide complexes

Grabowski

2017

J Comput Chem

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The N⋅⋅⋅B triel bonds in complexes of boron trihalides, BX (X = F, Cl, Br, and I), with species acting as Lewis bases through the nitrogen center, NH , N , and HCN, are analyzed theoretically (MP2/aug-cc-pVTZ calculations). It is confirmed that stronger Lewis acid properties of the boron center are observed for the BCl moiety than for the BF one in complexes with the strong Lewis base (NH ); while the opposite order is observed for complexes with the weak Lewis base (N ). The BX NCH complexes (for X = Cl, Br, and I) are characterized by two tautomeric forms and by two corresponding N⋅⋅⋅B distances, the shorter one possesses characteristics of the covalent bond. In a case of the BF NCH complex one energetic minimum is observed. Ab initio calculations are supported by an analysis of molecular electrostatic potentials (EPs) and electron density distributions. The quantum theory of 'atoms in molecules' and the decomposition of the energy of interaction are applied. The aforementioned acidity orders as well as the existence of two tautomers for some of complexes result partly from the electrostatic interactions' balance; the EP distribution is different for the BF species than for the other BX species where X = Cl, Br, and I. © 2017 Wiley Periodicals, Inc.

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Proton transfer reactions of hydrazine-boranes

Cited by 11 publications

References 26 publications

Relative stability and proton transfer reactions of unsaturated isocyanides and cyanides

Relative stability and proton transfer reactions of unsaturated isocyanides and cyanides

Triel‐Bonded Complexes between TrR₃ (Tr=B, Al, Ga; R=H, F, Cl, Br, CH₃) and Pyrazine

Two faces of triel bonds in boron trihalide complexes

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Proton transfer reactions of hydrazine-boranes

Cited by 11 publications

References 26 publications

Relative stability and proton transfer reactions of unsaturated isocyanides and cyanides

Relative stability and proton transfer reactions of unsaturated isocyanides and cyanides

Triel‐Bonded Complexes between TrR3 (Tr=B, Al, Ga; R=H, F, Cl, Br, CH3) and Pyrazine

Two faces of triel bonds in boron trihalide complexes

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Triel‐Bonded Complexes between TrR₃ (Tr=B, Al, Ga; R=H, F, Cl, Br, CH₃) and Pyrazine