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Stabilizing the E≡N triple bonds in pnictogen mononitrides

Chandran, Aswin LU ; Edin, Simon LU ; Tan, Mattias LU and Reinholdt, Anders LU (2026) In Dalton Transactions
Abstract

The viability of a main-group triple bond depends critically on the strength of its π-manifold. Among the 15 possible diatomic homo- and interpnictogens, EE′, (E, E′ = group 15 element), the NN linkage of dinitrogen stands out as one of the strongest triple bonds that exists, whereas the heavier pnictogens form thermodynamically unstable triple bond motifs that either decompose to single-bonded oligomers or extrude N2, under standard conditions. Considering the fundamentally simple chemistry of a diatomic molecule, coupled with the enticing synthetic challenge of accessing any other EE′ dipnictogen than N2, we here survey the chemistry of the mononitride family, EN (E = P, As, Sb, Bi). We describe how these unusual... (More)

The viability of a main-group triple bond depends critically on the strength of its π-manifold. Among the 15 possible diatomic homo- and interpnictogens, EE′, (E, E′ = group 15 element), the NN linkage of dinitrogen stands out as one of the strongest triple bonds that exists, whereas the heavier pnictogens form thermodynamically unstable triple bond motifs that either decompose to single-bonded oligomers or extrude N2, under standard conditions. Considering the fundamentally simple chemistry of a diatomic molecule, coupled with the enticing synthetic challenge of accessing any other EE′ dipnictogen than N2, we here survey the chemistry of the mononitride family, EN (E = P, As, Sb, Bi). We describe how these unusual bonding motifs were first observed as transient species in the gas phase, later isolated in cryogenic noble-gas matrix experiments, and recently have become the subject of synthetic studies in solution. We delineate strategies to tame the highly reactive EN motifs by incorporating them into adducts with organic fragments or transition metal nodes, enabling studies of their reaction chemistry under controlled conditions. These efforts have opened fascinating perspectives in pnictogen multiple-bond reactivity, spanning radical and closed-shell transformations, electrophilic as well as nucleophilic reactivity of the EN fragments, oxidative addition, oligomerization, cyclization, inorganic aromaticity, and even EN group transfer. Finally, we identify topics in the triple-bond chemistry of pnictogen mononitrides that remain ambiguous or poorly explored, pointing toward future directions in the field.

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author
; ; and
organization
publishing date
type
Contribution to journal
publication status
in press
subject
in
Dalton Transactions
publisher
Royal Society of Chemistry
external identifiers
  • scopus:105032439487
  • pmid:41810994
ISSN
1477-9226
DOI
10.1039/d6dt00293e
language
English
LU publication?
yes
additional info
Publisher Copyright: This journal is © The Royal Society of Chemistry, 2026
id
e5d91b09-1114-4649-b8de-3689c0fe4cbe
date added to LUP
2026-05-19 14:32:12
date last changed
2026-08-27 04:36:34
@article{e5d91b09-1114-4649-b8de-3689c0fe4cbe,
  abstract     = {{<p>The viability of a main-group triple bond depends critically on the strength of its π-manifold. Among the 15 possible diatomic homo- and interpnictogens, EE′, (E, E′ = group 15 element), the NN linkage of dinitrogen stands out as one of the strongest triple bonds that exists, whereas the heavier pnictogens form thermodynamically unstable triple bond motifs that either decompose to single-bonded oligomers or extrude N<sub>2</sub>, under standard conditions. Considering the fundamentally simple chemistry of a diatomic molecule, coupled with the enticing synthetic challenge of accessing any other EE′ dipnictogen than N<sub>2</sub>, we here survey the chemistry of the mononitride family, EN (E = P, As, Sb, Bi). We describe how these unusual bonding motifs were first observed as transient species in the gas phase, later isolated in cryogenic noble-gas matrix experiments, and recently have become the subject of synthetic studies in solution. We delineate strategies to tame the highly reactive EN motifs by incorporating them into adducts with organic fragments or transition metal nodes, enabling studies of their reaction chemistry under controlled conditions. These efforts have opened fascinating perspectives in pnictogen multiple-bond reactivity, spanning radical and closed-shell transformations, electrophilic as well as nucleophilic reactivity of the EN fragments, oxidative addition, oligomerization, cyclization, inorganic aromaticity, and even EN group transfer. Finally, we identify topics in the triple-bond chemistry of pnictogen mononitrides that remain ambiguous or poorly explored, pointing toward future directions in the field.</p>}},
  author       = {{Chandran, Aswin and Edin, Simon and Tan, Mattias and Reinholdt, Anders}},
  issn         = {{1477-9226}},
  language     = {{eng}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Dalton Transactions}},
  title        = {{Stabilizing the E≡N triple bonds in pnictogen mononitrides}},
  url          = {{http://dx.doi.org/10.1039/d6dt00293e}},
  doi          = {{10.1039/d6dt00293e}},
  year         = {{2026}},
}