Substituent-dependent reactivity of triarylantimony(iii) toward I2: isolation of [Ar3SbI]+salt

Article abstract of DOI:10.1039/d0nj02774j

The outcome of reactions of triarylantimony (Ar₃Sb) with diiodine in benzene is strongly affected by the identity of the substituents. For R = 4-MePh, 3-MePh and 4-FPh, they form Sb^Vderivatives Ar₃SbI₂, while fo

Full text of DOI:10.1039/d0nj02774j

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Substituent-dependent reactivity of triarylantimony(III) toward I2:
isolation of [Ar3SbI]+ salt
Vladimir V. Sharutin,a Olga K. Sharutina,a Alexander S. Novikovb and Sergey A. Adonin*a,c
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
The outcome of reactions of triarylantimony (Ar3Sb) with (R3As–I–I, R = Ph,11,12 4-Me, 2-MePh,13 Me14 etc.) or I (the
diiodine in benzene is strongly affected by the identity of cationic R3AsI+ the I– remaining aster I–I bond cleavage bonds
;
substituents. For R = 4-MePh, 3-MePh and 4-FPh, there form I2 to give triiodide counter-anion15). The R3AsI+ are especially
SbV deivatives Ar3SbI2, while for (2-MeO-5-BrC6H4)3Sb the interesting from the viewpoint of electronic structure and their
reaction results in [(2-MeO-5-BrC6H4)3SbI](I3) where I is ability to form noncovalent interactions: it can be expected
bound to the Sb center. The features of noncovalent that R3AsI+ has a energetically deep σ-hole on the I atom, so
interactions in the structure of the latter compound, as well that it can become a suitable building block for construction of
as electronic structure of the [(2-MeO-5-BrPh)3SbI]+ cation, halogen bonding-based supramolecular architectures.
were studied by theoretical methods.
Based on abovementioned ideas, we decided to perform a
series of experiments of general scheme “Ar3Sb + I2”, involving
Ar3Sb precursors with various aryl substituents with either
electron-donating or –withdrawing group or groups (see SI for
details). For Ar = 4-MePh, 3-MePh, and 4-FPh and the
equimolar amount of I2, these reactions proceeded in the
conventional way to achieve Ar3SbI2 (Scheme 1; Ar = 4-MePh
(1), 3-MePh (2), 4-FPh (3)) isolated in up to 92% yields (see SI).
In all cases, the coordination environment of Sb is trigonal
bipyramidal (Fig. 1). In the structures of 1–3, the Sb–I and Sb–C
bond lengths are 2.723-–2.841, 2.873–2.876, 2.848–2.896 Å
and 2.117, 2.119–2.126, 2.120–2.152 Å, respectively, being
The compounds belonging to the triarylantimony(III) family,
Ar3Sb, are known for more than a century and it is not
unexpected that many aspects of their structural chemistry
and reactivity were subjects of a substantial number of
reviews and text-book considerations.1–5 It is generally
believed that the most common redox reactivity mode of
Ar3Sb is their oxidation by dihalogens to give corresponding
triarylantimony(V) derivatives, Ar3SbX2. These reactions are
well-studied for X = Cl and Br6,7 and, to the best of our
knowledge, products or intermediates other than from the
most thermodynamically stable Ar3SbX2 were isolated or
identified in situ only in few cases.8 For diiodine, this
exhaustive oxidation was realized for Ph3Sb to furnish
Ph3SbI2.9,10 Taking into account that diiodine is significantly
weaker oxidant under the same conditions than Br2 and
especially Cl2, we assumed that its interplay with other Ar3Sb
could proceed differently to the conventional instances.
1
similar to those in Ph3SbI2.9 Both H and 13C NMR spectra (see
SI, Table S2) agree well with the molecular structures.
By planning this work, in addition, we were also inspired by the
reported reactivity of other trialkyl- or arylpnictogens (P and
As) toward I2. As the closest neighbor to Sb, As demonstrates
strikingly different behavior in the reactions between R3As and
I2, forming complexes with either linearly-coordinated I2
a. South Ural State University, Lenina St. 76 454080 Chelyabinsk, Russia
b. Saint Petersburg State University, Institute of Chemistry, Universitetskaya Nab. 7-
9, 199034 Saint Petersburg, Russia
c. Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentieva St. 3, 630090
Novosibirsk, Russia. E-mail: adonin@niic.nsc.ru
Fig. 1. Structure of (4-MePh)3SbI2; C is grey, Sb dark blue, I purple
Electronic Supplementary Information (ESI) available: Synthetic procedures, XRD
and NMR characterization details for 1-3 and 5, computational details. See
DOI: 10.1039/x0xx00000x
Interestingly, the crystal of 1 selected for XRD revealed the
presence of minor quantity of Br ligands co-occupying the
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same position as iodides. Considering that the nature of bulk 1 Inspection of the halogen···halogen distances in the structure
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was independently confirmed by element analysis, H and 13C of 4 and their comparison with the sumsDoOfI:t1h0e.10c3o9r/rDe0sNpJo0n2d77in4gJ
1
NMR (see SI for full details), we suggest that this artefact Bondi van der Waals radii21,22 indicate the presence of
appears due to contamination by bromide and preferential corresponding noncovalent interactions between I ligand and
–
crystallization of Br-containing substance in the beginning.
I3 (I···I 3.654 Å), which can be regarded as halogen bonding
(XB)23 (I–I–I 121.9°) based on the IUPAC distance and angle
The reaction with I2 (molar ratio 1:1) proceeds dramatically criteria.24 Besides, we also identified Type I23 packing-induced
different for (2-MeO-5-BrC6H4)3Sb,16 to give the product which interactions involving the Br atom of the 2-MeO-5-Br
resembles several of the abovementioned organoarsenic substituent and the triiodide (Br···I 3.692 Å) so that there form
derivatives. In this case, there forms the triiodide salt of the supramolecular dimers (Fig. 3).
[(2-MeO-5-BrPh)3SbI]+ cation (4) (Fig. 2). To our best
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knowledge, this is the first structurally characterized example
of such Sb derivatives. Earlier, Prtichard et al. reported on the
reaction between Ph3SbI2 and metallic Co that leads to the
product with the “Co(SbPh3)I4” brutto-formula. Since no X-ray
characterization was performed, the structure was
conditionally attributed to [Ph3SbI][Co(SbPh3)I3], following the
analogy with related phosphines.17 Chlorine-containing
compounds with [R3SbCl]+ cations were described as well.18,19
Also, similar observations were made by Tailor et al.:8,20 in the
course of studies of reactions between Ph3Sb and I2 in water-
containing organic solvents, compounds containing (Ph3SbI)2O
Fig. 3. Halogen···halogen contacts (dashed) in the structure of 4.
units were isolated and characterized.
To estimate the energies of the abovementioned
halogen···halogen contacts, we performed DFT calculations at
R = 3-MePh, 4-MePh,
the M06/DZP-DKH level of theory and topological analysis of
the electron density distribution (QTAIM method)25 for the
model tetrameric supramolecular associate {[(2-MeO-5-BrPh)3
4-FPh
R3SbVI2
benzene, r.t.
R3SbIII + I2
-
SbI]+}2···{I3 }2 based on the experimental X-ray geometry of 4
R = 2-MeO-5-BrC6H4
(see SI for details; this approach was previously used by us for
analysis of other relevant systems26–30). Depending on the
applied method (see SI31), the strength of I···I and I···Br
interactions vary in the 2.9–3.0 and 2.1–2.5 kcal/mol ranges;
such values are relatively common for typical XBs.28,32,33
According to the criteria proposed by Espinosa et al.34 and
Johnson et al.,35 it can be stated that these interactions are
purely noncovalent and attractive.
The distribution of frontier molecular orbitals in the optimized
equilibrium structure of [Ar3SbI]+ is shown on Fig. 4. LUMO is
mainly associated with antibonding σ*-orbitals located on the
Sb–I fragment, whereas HOMO is localized exclusively on the
Ar moieties.
(R3SbI)I3
Scheme 1. Pathways of reactions between R3Sb and I2
In 4, the Sb–C bond lengths fall in the 2.037–2.079 Å range,
being noticeably shorter than those in parent compound
(2.166–2.174 Å, respectively16); this shortening favours strong
electron-withdrawing effect of I. The Sb–I distance is 2.639 Å,
which is significantly less than those in 1–3. The tetrahedral
geometry of the Sb center in 4 is only slightly distorted ((X–
Sb–X) are 106.6–114.0°).
Fig. 4. Distribution of frontier molecular orbitals in the optimized equilibrium
structure of [Ar3SbI]+
Fig. 2. Structure of the [(2-MeO-5-BrC6H4)3SbI]+ cation. C is grey, Sb dark blue, Br
olive-green, O red, I purple; H atoms were omitted for the clarity.
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Results of electrostatic surface potential (ESP) calculations
reveal the presence of σ-hole regions on the Sb (86 kcal/mol,
the global surface maxima), I (73 kcal/mol, the local surface
maxima) and Br (60 kcal/mol, the local surface maxima) atoms
in the optimized equilibrium structure of [Ar3SbI]+ (Fig. 5).
Thus, potentially, this iodine-containing positively charged
system is perspective for noncovalent catalyst involving
simultaneous pnictogen/halogen bonding.
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Fig. 5. Visualization of ESP distribution in the optimized equilibrium structure of
[Ar3SbI]+.
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In summary, we provided the experimental evidence that the
reactions between Ar3Sb and I2 proceeds by two different
routes depending on the identity of Ar: most commonly, those
results in the oxidation to give R3SbVI2, and we reported here
on the unconventional route to achieve the Ar3SbI+ cation. The
latter reactivity mode of Ar3Sb is similar to that of R3As, and it
can be theoretically expected that other scenarios (i.e. “linear
coordination” of I2) are possible. The facile generation of
Ar3SbI+ deserves further investigation utilizing a broader range
of substrates; corresponding experiments are underway in our
group. Besides, analysis of the electronic structure of [(2-MeO-
5-BrPh)3SbI]+ demonstrates the simultaneous presence of σ-
holes on I and Sb atom, so that such cations can be considered
as very promising building blocks for XB-based supramolecular
architectures and XB-involving noncovalent organic
catalysis.36–39
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Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
The work was supported by Act 211 Government of the
Russian Federation, contract No 02.A03.21.0011. ASN is 19
grateful to the Russian Science Foundation for support of his
theoretical studies of noncovalent interactions in 5 (Grant No. 20
19-73-00001). The authors thank Prof. Kukushkin (Saint
Petersburg State University) for his valuable suggestions. Also, 21
we kindly thank the Referee responsible for evaluation of XRD 22
part of this work for his/her criticism and suggestions and Dr.
P.A. Abramov (NIIC SB RAS) for his recommendations regarding 23
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