More Electropositive is More Electronegative: Atom Size Determines C=X Group Electronegativity

Celine Nieuwland; Ron Verdijk; Célia Fonseca Guerra; F. Matthias Bickelhaupt

doi:10.1002/chem.202304161

More Electropositive is More Electronegative: Atom Size Determines C=X Group Electronegativity

Celine Nieuwland
, Ron Verdijk
, Célia Fonseca Guerra^*
, F. Matthias Bickelhaupt^*

^*Corresponding author for this work

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

Abstract

Opposite to what one might expect, we find that the C=X group can become effectively more, not less, electronegative when the Pauling electronegativity of atom X decreases down Groups 16, 15, and 14 of the Periodic Table. Our quantum-chemical analyses, show that, and why, this phenomenon is a direct consequence of the increasing size of atom X down a group. These findings can be applied to tuning and improving the hydrogen-bond donor strength of amides H₂NC(=X)R by increasingly withdrawing density from the NH₂ group. A striking example is that H₂NC(=SiR₂)R is a stronger hydrogen-bond donor than H₂NC(=CR₂)R.

Original language	English
Article number	e202304161
Pages (from-to)	1-8
Number of pages	8
Journal	Chemistry - A European Journal
Volume	30
Issue number	15
Early online date	20 Dec 2023
DOIs	https://doi.org/10.1002/chem.202304161
Publication status	Published - 12 Mar 2024

Bibliographical note

Publisher Copyright:
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

Funding

The authors thank Eveline H. Tiekink for the helpful discussions and the Dutch Research Council (NWO) for financial support. This work was carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative.

Funders
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

Keywords

Amides
Atomic size
Chemical bonding
Electronegativity
Hydrogen bonding
Supramolecular chemistry

Access to Document

10.1002/chem.202304161

Persistent URL (handle)

Persistent link

Cite this

@article{df524dabd2b14837ac7ab2b7883a7ea7,

title = "More Electropositive is More Electronegative: Atom Size Determines C=X Group Electronegativity",

abstract = "Opposite to what one might expect, we find that the C=X group can become effectively more, not less, electronegative when the Pauling electronegativity of atom X decreases down Groups 16, 15, and 14 of the Periodic Table. Our quantum-chemical analyses, show that, and why, this phenomenon is a direct consequence of the increasing size of atom X down a group. These findings can be applied to tuning and improving the hydrogen-bond donor strength of amides H2NC(=X)R by increasingly withdrawing density from the NH2 group. A striking example is that H2NC(=SiR2)R is a stronger hydrogen-bond donor than H2NC(=CR2)R.",

keywords = "Amides, Atomic size, Chemical bonding, Electronegativity, Hydrogen bonding, Supramolecular chemistry",

author = "Celine Nieuwland and Ron Verdijk and \{Fonseca Guerra\}, C{\'e}lia and Bickelhaupt, \{F. Matthias\}",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.",

year = "2024",

month = mar,

day = "12",

doi = "10.1002/chem.202304161",

language = "English",

volume = "30",

pages = "1--8",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley and Sons Inc.",

number = "15",

}

TY - JOUR

T1 - More Electropositive is More Electronegative

T2 - Atom Size Determines C=X Group Electronegativity

AU - Nieuwland, Celine

AU - Verdijk, Ron

AU - Fonseca Guerra, Célia

AU - Bickelhaupt, F. Matthias

PY - 2024/3/12

Y1 - 2024/3/12

N2 - Opposite to what one might expect, we find that the C=X group can become effectively more, not less, electronegative when the Pauling electronegativity of atom X decreases down Groups 16, 15, and 14 of the Periodic Table. Our quantum-chemical analyses, show that, and why, this phenomenon is a direct consequence of the increasing size of atom X down a group. These findings can be applied to tuning and improving the hydrogen-bond donor strength of amides H2NC(=X)R by increasingly withdrawing density from the NH2 group. A striking example is that H2NC(=SiR2)R is a stronger hydrogen-bond donor than H2NC(=CR2)R.

AB - Opposite to what one might expect, we find that the C=X group can become effectively more, not less, electronegative when the Pauling electronegativity of atom X decreases down Groups 16, 15, and 14 of the Periodic Table. Our quantum-chemical analyses, show that, and why, this phenomenon is a direct consequence of the increasing size of atom X down a group. These findings can be applied to tuning and improving the hydrogen-bond donor strength of amides H2NC(=X)R by increasingly withdrawing density from the NH2 group. A striking example is that H2NC(=SiR2)R is a stronger hydrogen-bond donor than H2NC(=CR2)R.

KW - Amides

KW - Atomic size

KW - Chemical bonding

KW - Electronegativity

KW - Hydrogen bonding

KW - Supramolecular chemistry

UR - https://www.scopus.com/pages/publications/85182236121

UR - https://www.scopus.com/pages/publications/85182236121#tab=citedBy

U2 - 10.1002/chem.202304161

DO - 10.1002/chem.202304161

M3 - Article

AN - SCOPUS:85182236121

SN - 0947-6539

VL - 30

SP - 1

EP - 8

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 15

M1 - e202304161

ER -

More Electropositive is More Electronegative: Atom Size Determines C=X Group Electronegativity

Abstract

Bibliographical note

Funding

Keywords

Access to Document

Persistent URL (handle)

Other files and links

Fingerprint

Cite this