Nucleophilicity of the boron atom in compounds R-B, (R = F, Cl, Br, I, CN, NC, CH3, SiH3, CF3, H): a new look at the inductive effects of the group R

Ibon Alkorta; Anthony Legon

doi:10.1039/d2cp01565j

Nucleophilicity of the boron atom in compounds R-B, (R = F, Cl, Br, I, CN, NC, CH₃, SiH₃, CF₃, H): a new look at the inductive effects of the group R

Ibon Alkorta, Anthony Legon^*

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › peer-review

11 Citations (Scopus)

Abstract

Nucleophilicities N_R-B of molecules R-B (R = F, Cl, Br, I, CN, NC, CH₃, SiH₃, CF₃, H) are determined from the equilibrium dissociation energies D_e of 70 hydrogen-bonded complexes R-B⋯HX (X = F, Cl, Br, I, HCN. HCCH, HCP). The change in N_R-B relative to N_H-B of H-B allows a quantitative measure of the inductive effect I_R of each group R because only the group R affects the electron density associated with the axial non-bonding electron pair carried by the boron in R-B. An alternative definition of I_R, suggested by the strong correlation of the N_R-B values with the minimum value σ_min of the molecular electrostatic surface potential on the 0.001 e Bohr⁻³ iso-surface along the R-B axis leads to excellent agreement between the two definitions.

Original language	English
Pages (from-to)	12804-12807
Number of pages	4
Journal	Physical Chemistry Chemical Physics
Volume	24
Issue number	21
DOIs	https://doi.org/10.1039/d2cp01565j
Publication status	Published - 13 May 2022

Bibliographical note

Funding Information:
ACL thanks the University of Bristol for a Senior Research Fellowship. IA thanks the Ministerio de Ciencia e Innovación of Spain (PGC2018-094644-B-C22 and PID2021-125207NB-C32) and Comunidad de Madrid (P2018/EMT-4329 AIRTEC-CM) for financial support.

Publisher Copyright:
© 2022 The Royal Society of Chemistry.

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@article{db685f8fb0d14661bcab5da723607094,

title = "Nucleophilicity of the boron atom in compounds R-B, (R = F, Cl, Br, I, CN, NC, CH3, SiH3, CF3, H): a new look at the inductive effects of the group R",

abstract = "Nucleophilicities NR-B of molecules R-B (R = F, Cl, Br, I, CN, NC, CH3, SiH3, CF3, H) are determined from the equilibrium dissociation energies De of 70 hydrogen-bonded complexes R-B⋯HX (X = F, Cl, Br, I, HCN. HCCH, HCP). The change in NR-B relative to NH-B of H-B allows a quantitative measure of the inductive effect IR of each group R because only the group R affects the electron density associated with the axial non-bonding electron pair carried by the boron in R-B. An alternative definition of IR, suggested by the strong correlation of the NR-B values with the minimum value σmin of the molecular electrostatic surface potential on the 0.001 e Bohr−3 iso-surface along the R-B axis leads to excellent agreement between the two definitions.",

author = "Ibon Alkorta and Anthony Legon",

note = "Funding Information: ACL thanks the University of Bristol for a Senior Research Fellowship. IA thanks the Ministerio de Ciencia e Innovaci{\'o}n of Spain (PGC2018-094644-B-C22 and PID2021-125207NB-C32) and Comunidad de Madrid (P2018/EMT-4329 AIRTEC-CM) for financial support. Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

year = "2022",

month = may,

day = "13",

doi = "10.1039/d2cp01565j",

language = "English",

volume = "24",

pages = "12804--12807",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "Royal Society of Chemistry",

number = "21",

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TY - JOUR

T1 - Nucleophilicity of the boron atom in compounds R-B, (R = F, Cl, Br, I, CN, NC, CH3, SiH3, CF3, H)

T2 - a new look at the inductive effects of the group R

AU - Alkorta, Ibon

AU - Legon, Anthony

N1 - Funding Information: ACL thanks the University of Bristol for a Senior Research Fellowship. IA thanks the Ministerio de Ciencia e Innovación of Spain (PGC2018-094644-B-C22 and PID2021-125207NB-C32) and Comunidad de Madrid (P2018/EMT-4329 AIRTEC-CM) for financial support. Publisher Copyright: © 2022 The Royal Society of Chemistry.

PY - 2022/5/13

Y1 - 2022/5/13

N2 - Nucleophilicities NR-B of molecules R-B (R = F, Cl, Br, I, CN, NC, CH3, SiH3, CF3, H) are determined from the equilibrium dissociation energies De of 70 hydrogen-bonded complexes R-B⋯HX (X = F, Cl, Br, I, HCN. HCCH, HCP). The change in NR-B relative to NH-B of H-B allows a quantitative measure of the inductive effect IR of each group R because only the group R affects the electron density associated with the axial non-bonding electron pair carried by the boron in R-B. An alternative definition of IR, suggested by the strong correlation of the NR-B values with the minimum value σmin of the molecular electrostatic surface potential on the 0.001 e Bohr−3 iso-surface along the R-B axis leads to excellent agreement between the two definitions.

AB - Nucleophilicities NR-B of molecules R-B (R = F, Cl, Br, I, CN, NC, CH3, SiH3, CF3, H) are determined from the equilibrium dissociation energies De of 70 hydrogen-bonded complexes R-B⋯HX (X = F, Cl, Br, I, HCN. HCCH, HCP). The change in NR-B relative to NH-B of H-B allows a quantitative measure of the inductive effect IR of each group R because only the group R affects the electron density associated with the axial non-bonding electron pair carried by the boron in R-B. An alternative definition of IR, suggested by the strong correlation of the NR-B values with the minimum value σmin of the molecular electrostatic surface potential on the 0.001 e Bohr−3 iso-surface along the R-B axis leads to excellent agreement between the two definitions.

UR - https://www.scopus.com/pages/publications/85132372553

U2 - 10.1039/d2cp01565j

DO - 10.1039/d2cp01565j

M3 - Article (Academic Journal)

C2 - 35593316

AN - SCOPUS:85132372553

SN - 1463-9076

VL - 24

SP - 12804

EP - 12807

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 21

ER -