A theoretical study on borenium ion affinities toward ammonia, formaldehyde and chloride anions
Abstract
Various borenium ion affinities toward three ligands (L' = NH3, HCHO and Cl-) have been evaluated by DFT calculations in the gas-phase and in solvent (CH2Cl2). The gas-phase results have been rationalized on the basis of quantitative decomposition of the total binding energy into contributions from electrostatic, orbital, dispersion and Pauli interactions, and energy needed to deform the interacting fragments from their optimal geometry to that they adopt in an adduct. Twenty six borenium cations, differing in the type of the two R/R' substituents covalently bound to the boron atom and the neutral stabilizing ligand L, have been examined. With a few exceptions, the most important stabilizing interaction is electrostatic, more pronounced in the case of the charged ligand Cl-. Next come orbital interactions, involving the coordinate covalent bond formation, other charge transfer interactions between the cation and ligand, and polarization. Dispersion forces provide the smallest attractio...n, except in four complexes with long B-L' distances. We present how substituent (R/R')/ligand (L) variations affect binding enthalpies (Delta H)/energies (Delta E). Our results also show that the observed trend in the magnitudes of Delta Hs/Delta Es represents an interplay of the above mentioned (de) stabilizing energies, and can be explained by consideration of the boron-ligand distance and all charge/orbital interactions, rather than partial ones involving boron and ligand L'. Under solvent conditions, the Cl- affinities are drastically reduced and made very similar to NH3 affinities, but still larger than HCHO affinities.
Source:
RSC Advances, 2015, 5, 93, 75895-75910Publisher:
- Royal Soc Chemistry, Cambridge
Funding / projects:
- Experimental and theoretical study of reactivity and biological activity of stereodefined thiazolidines and their synthetic analogues (RS-MESTD-Basic Research (BR or ON)-172020)
DOI: 10.1039/c5ra13825f
ISSN: 2046-2069
WoS: 000361387300008
Scopus: 2-s2.0-84941670845
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Institution/Community
IHTMTY - JOUR AU - Stojanović, Milovan AU - Baranac-Stojanović, Marija PY - 2015 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1711 AB - Various borenium ion affinities toward three ligands (L' = NH3, HCHO and Cl-) have been evaluated by DFT calculations in the gas-phase and in solvent (CH2Cl2). The gas-phase results have been rationalized on the basis of quantitative decomposition of the total binding energy into contributions from electrostatic, orbital, dispersion and Pauli interactions, and energy needed to deform the interacting fragments from their optimal geometry to that they adopt in an adduct. Twenty six borenium cations, differing in the type of the two R/R' substituents covalently bound to the boron atom and the neutral stabilizing ligand L, have been examined. With a few exceptions, the most important stabilizing interaction is electrostatic, more pronounced in the case of the charged ligand Cl-. Next come orbital interactions, involving the coordinate covalent bond formation, other charge transfer interactions between the cation and ligand, and polarization. Dispersion forces provide the smallest attraction, except in four complexes with long B-L' distances. We present how substituent (R/R')/ligand (L) variations affect binding enthalpies (Delta H)/energies (Delta E). Our results also show that the observed trend in the magnitudes of Delta Hs/Delta Es represents an interplay of the above mentioned (de) stabilizing energies, and can be explained by consideration of the boron-ligand distance and all charge/orbital interactions, rather than partial ones involving boron and ligand L'. Under solvent conditions, the Cl- affinities are drastically reduced and made very similar to NH3 affinities, but still larger than HCHO affinities. PB - Royal Soc Chemistry, Cambridge T2 - RSC Advances T1 - A theoretical study on borenium ion affinities toward ammonia, formaldehyde and chloride anions VL - 5 IS - 93 SP - 75895 EP - 75910 DO - 10.1039/c5ra13825f ER -
@article{ author = "Stojanović, Milovan and Baranac-Stojanović, Marija", year = "2015", abstract = "Various borenium ion affinities toward three ligands (L' = NH3, HCHO and Cl-) have been evaluated by DFT calculations in the gas-phase and in solvent (CH2Cl2). The gas-phase results have been rationalized on the basis of quantitative decomposition of the total binding energy into contributions from electrostatic, orbital, dispersion and Pauli interactions, and energy needed to deform the interacting fragments from their optimal geometry to that they adopt in an adduct. Twenty six borenium cations, differing in the type of the two R/R' substituents covalently bound to the boron atom and the neutral stabilizing ligand L, have been examined. With a few exceptions, the most important stabilizing interaction is electrostatic, more pronounced in the case of the charged ligand Cl-. Next come orbital interactions, involving the coordinate covalent bond formation, other charge transfer interactions between the cation and ligand, and polarization. Dispersion forces provide the smallest attraction, except in four complexes with long B-L' distances. We present how substituent (R/R')/ligand (L) variations affect binding enthalpies (Delta H)/energies (Delta E). Our results also show that the observed trend in the magnitudes of Delta Hs/Delta Es represents an interplay of the above mentioned (de) stabilizing energies, and can be explained by consideration of the boron-ligand distance and all charge/orbital interactions, rather than partial ones involving boron and ligand L'. Under solvent conditions, the Cl- affinities are drastically reduced and made very similar to NH3 affinities, but still larger than HCHO affinities.", publisher = "Royal Soc Chemistry, Cambridge", journal = "RSC Advances", title = "A theoretical study on borenium ion affinities toward ammonia, formaldehyde and chloride anions", volume = "5", number = "93", pages = "75895-75910", doi = "10.1039/c5ra13825f" }
Stojanović, M.,& Baranac-Stojanović, M.. (2015). A theoretical study on borenium ion affinities toward ammonia, formaldehyde and chloride anions. in RSC Advances Royal Soc Chemistry, Cambridge., 5(93), 75895-75910. https://doi.org/10.1039/c5ra13825f
Stojanović M, Baranac-Stojanović M. A theoretical study on borenium ion affinities toward ammonia, formaldehyde and chloride anions. in RSC Advances. 2015;5(93):75895-75910. doi:10.1039/c5ra13825f .
Stojanović, Milovan, Baranac-Stojanović, Marija, "A theoretical study on borenium ion affinities toward ammonia, formaldehyde and chloride anions" in RSC Advances, 5, no. 93 (2015):75895-75910, https://doi.org/10.1039/c5ra13825f . .