Dramatically Enhanced Solubility of Halide-Containing Organometallic Species in Diiodomethane: The Role of Solvent???Complex Halogen Bonding

Article abstract of DOI:10.1002/anie.201807642

In the current study, we evaluated the solubility of a number of organometallic species and showed that it is noticeably improved in diiodomethane when compared to other haloalkane solvents. The better solvation properties of CH₂I₂ w

Full text of DOI:10.1002/anie.201807642

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Accepted Article
Title: Solubility of halide-containing organometallics is dramatically
enhanced in diiodomethane: can the solvent***complex halogen
bonding be held responsible?
Authors: Mikhail A Kinzhalov, Mariya V Kashina, Alexander S
Mikherdov, Ekaterina A Mozheeva, Alexander S Novikov,
Andrey S Smirnov, Daniil M Ivanov, Mariya A Kryukova,
Aleksandr Yu Ivanov, Sergej N Smirnov, Vadim Yu
Kukushkin, and Konstantin V. Luzyanin
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201807642
Angew. Chem. 10.1002/ange.201807642
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10.1002/anie.201807642
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Solubility of halide-containing organometallics is dramatically
enhanced in diiodomethane: can the solvent•••complex halogen
bonding be held responsible?
Mikhail A. Kinzhalov,*[a] Mariya V. Kashina,[a] Alexander S. Mikherdov,[a] Ekaterina A. Mozheeva,[a]
Alexander S. Novikov,[a] Andrey S. Smirnov,[a] Daniil M. Ivanov,[a] Mariya A. Kryukova,[a]
Aleksandr Yu. Ivanov,[a] Sergej N. Smirnov,[a] Vadim Yu. Kukushkin,[a] Konstantin V. Luzyanin*[a, b]
Abstract: In the current study, we evaluated a solubility of a number
of organometallics and showed that it is noticeably improved in
diiodomethane when compared to other haloalkane solvents. Better
solvation properties of CH2I2 were associated with a dramatic growth
of the s-hole donating ability of this solvent, and that results in the
formation of the uniquely strong solvent-(metal complex) halogen
bonding. The strength of halogen bonding is attenuated by the
introduction of additional halogens to the organometallic species due
to the competitive formation of more favourable intermolecular
complex-complex halogen bonding. Exceptional solvation properties
of diiodomethane and its inertness towards organometallics make
of XB is rarely considered and clearly needs an in-depth study.
In this study, we examined the solvation properties of a
number of different haloalkane solvents using palladium- and
platinum-isocyanide species as solvation probes. Haloalkanes
are one of the most inert solvents used to solubilize
organometallics; they, and their deuterated versions, are widely
applied as media for solution NMR studies. Metal-isocyanides
are commonly used precursors to the metal-(acyclic
diaminocarbenes) that are of broad significance in catalysis.[3]
A series of new and known palladium- and platinum-
isocyanide complexes (1–16, Table 1) were prepared and
characterized by CHN elemental analyses, high-resolution mass
spectrometry (ESI+/‒-HRMS), FT-IR, and 1H and 13C{1H} NMR
spectroscopy (see Supplementary Information (SI) for more
details). The structures of complexes 10·2CH2I2, 11, 11·2CH2I2,
and 12 were established by single-crystal X-ray diffraction. The
geometry of all the complexes in solid state and in solution were
assigned on the basis of far-IR spectroscopy and X-ray
diffraction (see SI). All palladium complexes 1–12 are
isomerically pure in the solid state (cis for chloro, and trans for
bromo and iodo derivatives). In solution, chloro-complexes 1–4
were found to be a mixture of the cis and trans isomers (60–65%
of cis isomer at RT), whereas both the bromo and iodo species
5–12 contain more than 95% of the trans isomer. Platinum
complexes (13–16) are not subject to isomerization and are pure
cis in both solution and solid state.
this solvent
a good candidate for NMR solvent-of-choice, in
particular, for the acquisition of insensitive spins.
Insufficient solubility is one of the major problems limiting
structural characterization of compounds in solution, e.g. by
NMR spectroscopy and also their application in synthesis. In
particular, frequently higher reactivity and intrinsic instability of
organometallic species preclude the use of many common
solvents for their dissolution. Application of more inert, but often
less solubilizing solvents, limits the concentration of compound
resulting in significantly longer accumulation time upon NMR
acquisition of insensitive nuclei (13C, 15N, etc). Solvation, as a
process leading to a dissolution of compounds, encompasses
several different types of intermolecular interactions between a
solute and a solvent. These include van der Waals forces, ion-
dipole interactions, hydrogen bonding (HB), as well as halogen
bonding (XB) for halogen-containing species.[1] Although the
contribution of different interactions in solvation is recognized,
their interplay is rather complex and an empirical matching of the
solvent polarity to that of the solute continues to be the main
approach to improving solubility.[2] Among weak interactions,
contribution of HB is frequently taken into account, while impact
Table 1. The numbering scheme of prepared metal-isocyanide complexes
used as probes for solvation properties of haloalkanes.
Complex
X
X
X
N
N
N
N
X
I
Br
C
C
I
Cl
Cl
C
C
M
Pd
Pd
C
C
Br
N
N
[a]
Dr. M. A. Kinzhalov, M. V. Kashina, E. A. Mozheeva,
A. S. Mikherdov, Dr. D. M. Ivanov, Dr. A. S. Novikov,
Dr. A. S. Smirnov, M. A. Kryukova, A. Yu. Ivanov,
S. N. Smirnov, Prof. Dr. V. Yu. Kukushkin, Dr. K. V. Luzyanin
Saint Petersburg State University
7/9, Universitetskaya nab.,
X
X
X
H
Cl
Br
I
M = Pd 1, Pt 13
M = Pd 2, Pt 14
M = Pd 3, Pt 15
M = Pd 4, Pt 16
5
6
7
8
9
Saint Petersburg, 199034 Russia
E-mail: m.kinzhalov@spbu.ru
10
11
12
[b]
Dr. K. V. Luzyanin
Department of Chemistry
University of Liverpool
Crown Street,
Liverpool L69 7ZD, United Kingdom
E-mail: konstantin.luzyanin@liverpool.ac.uk
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201807642
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Table 2. Solubility for 4, 7, 11, and 12 in liquid haloalkanes, maximum
ESPs (VS(r)max, kcal·mol–1) on the Hal and H atoms in solvents, their dipole
moment (μ), and dielectric constant.
dropped on going from unsubstituted phenyl- to a p-chlorophenyl
isocyanide. We have also noted the variation in solubility in the
row of complexes containing different halogen-substituted
isocyanides (p-chloro- vs p-bromo- vs p-iodophenyl isocyanides,
e.g. 2–4, 6–8 or 10–12) although the exact effect was not clear.
For instance, in complexes 10–12 solubility decreases in CHCl3,
while it grows in CH2I2.
[b]
Vs(r)max
,
Dipole
moment,
μ
Dielectric
constant,
(T, °C)
Solubility, mg/mL
kcal·mol–1
Solvent
4
7
11
11
20
32
32
35
37
4
12
1
Hal
H
C2H4Cl2
CH2Cl2
CHCl3
1
9
–0.3
2.6
24.6
32.9
39.5
39.5
39.5
29.9
–
1.48
1.6
10.42(20)
8.93(20)
4.81(25)
4.81(25)
4.81(25)
7.77(10)
2.24(20)
5.316(25)
Table 3. The solubility and isomeric ratios of 1–16 in CHCl3 and CH2I2.
1
16
26
26
30
37
7
3
1
5
10.4
10.4
10.4
13.7
16.0
23.1
1.04
1.04
1.04
1.43
0
Complex
Hal
Solubility, mg/mL
CDCl3
1
5
X
CDСl3
CH2I2
Complex
[a]
CDCl3
1
5
H
Cl
Br
I
1
2
3
4
8
9
CH2Br2
CCl4
3
18
2
15
6
31
29
10
Cl
2
(M = Pd)
CH2I2
10
46
77
79
27.4
1.08
1
[a] For all experiments except this, 5 vol.% of acetone-d6 were added for the
NMR lock purpose; [b] Vs(r)max for all solvents, except for C2H4Cl2 and CDCl3,
were calculated in our previous work.[4]
H
Cl
Br
I
13
14
15
16
7
7
13
20
2
61
72
20
Cl
(M = Pt)
Solvation properties of various haloalkanes were initially
tested by measuring the solubility of representative complexes 4,
7, 11, and 12 (Table 2, SI: Figures S1–3). An approach based
on quantitative 1H NMR spectroscopy measurements[5] in the
presence of hexamethyldisiloxane as an internal standard was
preferred.
Amongst all haloalkane solvents studied, diiodomethane,
CH2I2, demonstrated the best solvation properties determined by
the highest solubility of all model compounds. Thus, the
solubility of 4, 7, 11, and 12 in CH2I2 was up to an order of
magnitude larger when compared to that in commonly used
CHCl3. In addition, similar trends were established for
isomerically pure 7, 11, and 12 and complex 4 that exists as an
isomeric mixture allowing exclusion of the influence of cis/trans
isomerization on solubility.
H
Cl
Br
I
5
6
7
8
65
72
30
2
94
73
46
12
Br
H
Cl
Br
I
9
157
82
35
5
215
19
10
11
12
I
77
79
Given CH2I2 demonstrated the greatest solvation properties,
it was chosen for further experiments on the comparative
solubility of all isocyanide complexes 1–16 (Table 3); results
were compared to CDCl3, a commonly used organic solvent for
NMR spectroscopy. In addition, CDCl3 has comparable polarity
to that of CH2I2 (dipole moment, μ: 1.04 for CDCl3 vs 1.08 for
CH2I2), matching the contribution of solvent polarity to solubility
of organometallics studied. For all complexes 1–16 excluding 10,
CH2I2 remains the solvent with superior solvating properties
towards both platinum (14–16) and palladium (1–4) derivatives.
The solubility of complexes increases upon the transition from
cis-chloro complexes (1–4) to trans-bromo (5–8) and, to a
greater degree, trans-iodo derivatives (9–12). Although trans-
complexes have a symmetric ligand arrangement at metal, it is
known that those in solutions are significantly distorted when
compared to the solid state.[6] Isocyanide ligands, i.e. those in 5–
12 are not monoatomic; they can easily bend and that will lead
to the appearance of the dipolar moment.
To further attest the scope of this approach and usefulness
of CH2I2 as solvent for NMR studies, we evaluated solubilities in
CDCl3 – taken for comparison as the most common NMR
solvent – and in CH2I2 of various kinetically inert metal
complexes including square-planar cis and trans non-electrolyte
species bearing halide ligands and also halide-free complexes of
different configuration (see Table S3). For the vast majority of
platinum- and palladium halide species (entries 1–16), the
solubility in CH2I2 was found to be notably higher than that in
CDCl3. Halide complexes of other metals (entries 19–21) as well
as those without halide- but with acetylacetonate ligands (entries
17–18) demonstrate a similar trend. It is noteworthy that lone
pairs of metal-bound acac ligands exhibit
a pronounced
tendency to form XB with suitable XB donors.[7] So far we found
only one exception from the observed solubility trend when we
tested metal species with aromatic ring ligands exhibiting
rotational freedom (entries 24–31). We assume that the known[8]
X–H/π (X = C, N, O) interactions with the acidic H atom of
chloroform[9] contribute towards a better solubility of those
species in this solvent.
Placement of the secondary halogen atom into the structure
of the isocyanide ligands alters the solubility of 1–16 (Table 3).
For both palladium (1–4) and platinum (13–16) dichloride
complexes, upon going from unsubstituted phenyl- to a p-
chlorophenyl isocyanide, the solubility is significantly increased.
For palladium dibromide (5–8) and diiodide (9–12) complexes,
an opposite effect was observed: the solubility is significantly
Intrigued by our findings on different solvation properties of
structurally and chemically related haloalkanes, we attempted to
rationalize them. Insofar as one can reasonably exclude the
effect of different polarity of haloalkanes studied on the solubility
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10.1002/anie.201807642
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of model compounds, we focused our attention on weak
interactions such as halogen bonding.[10]
with CH2I2 (10·2CH2I2 and 11·2CH2I2, Figure 1) and two
individual iodo complexes (11 and 12, Figure 2) were evaluated;
ESP distribution for complexes 10–12 (Figure 3, Table 4) was
also calculated. According to the computations, the iodides
ligated to palladium have negative ESP on the whole of their
surface and can act only as XB acceptors. At the same time, the
halogen atoms in isocyanide ligands have areas with positive
ESP corresponding to s-hole position which makes these
halogens potential XB donors. Complexes 10 and 11 form the
CH2I2 isomorphic solvates upon crystallization from their CH2I2
solutions. In 10·2CH2I2 (Figure 1, left) and 11·2CH2I2 (Figure 1,
right), the H2C(I)–I•••I–Pd XBs between each molecule of
complex and four molecules of CH2I2 were found. The calculated
energy of each solvent-complex XB was 2.2–2.5 kcal/mol, and
their contribution to the lattice energy in each case appears to
be the most significant.
The phenomenon of halogen bonding has recently attracted
great attention due to relevance of XBs to pharmaceutical
chemistry and drug design,[11] polymer and materials science,[12]
organocatalysis[13] and crystal engineering.[14] XB is defined as a
non-covalent interaction between a localized positive region on a
halogen atom in the extension of the covalent bonds (σ-hole)
and electron donor species serving as XB acceptors. From this
perspective, an emergence of XB between halogen-containing
organometallics (as a solute) and solvent or vice versa can have
an impact on solvation. However, a quantitative effect of XBs on
solubility of organometallics has never been verified.
Haloalkanes, apart from positive H centers responsible for
HBs, feature an alternative type of partially positive charge
centers, viz. the s-holes[15] of covalently bound halogen atoms
capable of non-covalent interactions. We have previously
showed[4, 16] that the values of the electrostatic potential of the s-
holes (VS(r)max), and subsequently the ability to form XBs,
depend on the nature and number of halogen atoms in the
structure of haloalkanes. The value of VS(r)max on halogen atom
grows in the row Cl < Br < I and with increase in electron-
withdrawing ability of the substituent by a halogen atom, viz. a
number of halogen atoms at the C atom for haloalkanes. Note
that DFT calculations of electrostatic potentials (ESPs) at M06-
2X/CEP-121G theory level revealed that CH2I2 exhibits the
largest positive potential on the halogen s-holes (23.1 kcal·mol–
1) among all studied haloalkanes (Table 2).
In both 10 and 11, Vs(r)max value on the halogen atom in the
isocyanide ligand is lower than that for iodine in CH2I2 making it
a better XB donor for Pd-bound iodide.
For all the complexes, the relationship between the positive
potential on the halogen atom (Vs(r)max) and solubility as a rule
increases symbiotically with s-hole donating ability of a solvent
(Figure S1, SI), except for CCl4. Tetrachloromethane possesses
a high positive potential on the chlorine atom, but a null dipolar
moment being the only non-polar solvent among those studied.
Highest solubility of model compounds was observed for CH2I2
as a solvent with the largest maximum positive potential on the
halogen s-holes, i.e. it is 10 times higher (10 mg/mL) for 4 and
ca. 79 times (79 mg/mL) for 12 when compared against C2H4Cl2
as solvent with the lowest halogen s-hole donating properties
(Vs(r)max = –0.3 kcal·mol–1). Generally, when the quantity of
halogen atoms present is increased and their polarizability
(greater s-hole) is increased (Cl < Br < I), better solubility of
complexes is more likely due to the formation of solvent–
complex XBs in solution. Apparently, the acidity of H atoms
(represented by the maximum positive potential on the H, Table
1, Figure S2) does not play a significant role in the solvation
process. At this point, one can reasonably suggest that the
emergence of XBs between molecules of complex and solvent
plays the key role in the dissolution process.
Figure 1. The H2C(I)–I•••I–Pd XBs in 10·2CH2I2 (left) and 11·2CH2I2 (right).
Figure 2. The C–X2•••I–Pd (X2 = Br, I) XBs between two complex molecules
in 11 (top) and 12 (bottom).
Crystals of 11 grown from the less s-hole donating solvent,
CHCl3 (Vs(r)max
=
10.4 kcal·mol–1) contain only individual
Since non-covalent interactions can hardly be studied in
solution, we examined those in the XRD structures of some of
our complexes. This canonical approximation is widely used to
evaluate the XB situation and properties of solvates for different
compounds. Halogen···halogen interactions can be assigned to
one of two types on basis of their geometry.[17] Contacts of the
type 1 are mainly of dispersion nature, whereas those of the
type 2 are driven by electrostatic interactions between the polar
and equatorial regions. In all contacts described below, the
Hal···Hal distances are less than the sum of their Bondi vdW
radii,[18] while the corresponding angles C−Hal···Hal and
Hal···Hal–Pd are in the range 160−180° and 90−120°,
respectively (Tables S7–9). In accord with the IUPAC criteria,
these interactions are recognised as the type 2.[10] Two solvates
molecules of the complex with the intermolecular C–Br•••I–Pd
XBs (Figure 2, top structure). Energy of C–Br•••I–Pd XBs
interaction in this crystal is lower and such non-covalent contacts
are less numerous when compared to the H2C(I)–I•••I–Pd XBs in
solvate 11·2CH2I2. This leads to an assumption that in the
presence of CH2I2 the system prefers to form solvate. However,
in less s-hole donating solvents a competition between complex–
complex and solvent–complex XBs could occur during dissolution
process. Using a more s-hole donating solvent (CH2I2, Vs(r)max
=
23.1 kcal·mol–1) leads to an increase in the number of solvent-
complex XBs and good solubility, whereas in CDCl3 (Vs(r)max
=
10.4 kcal·mol–1) the complex–complex interactions (C–Br•••I–Pd
XBs, Vs(r)max(CNC6H4–Br) = 19.8 kcal·mol–1) is more preferable
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10.1002/anie.201807642
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COMMUNICATION
and works towards a precipitation of complex. These results
agree with the changes in solubility of 11, vis. from 35 mg/mL in
CDCl3 to 70 mg/mL in CH2I2.
available,[19] a deuterated version of CH2I2 might be prepared,[20]
if necessary. The strength of XBs is influenced by the
introduction of additional halogens to the organometallic species.
Herein, we demonstrated that strength of XBs and subsequently
the solubility decreases with the rise of the positive potential on
halogen moieties placed on isocyanide ligands due to the
formation of more favourable intermolecular complex-complex
XBs. Further studies on understanding the role of XBs and their
application in organometallic chemistry, are currently underway
in our group.
For 12, crystallization from even the strongest s-hole
donating solvent as CH2I2 does not lead to any solvates and the
crystals contain only individual molecules of the complex. They
are isomorphic to 11 (Figure 2, bottom) and possess a similar
pattern of intermolecular XBs C–I•••I–Pd (energy 2.2–2.5
kcal/mol). In this case, emergence of complex–complex XBs C–
I•••I–Pd is preferable to solvent-complex XBs H2C(I)–I•••I–Pd
presumably due to higher positive ESP on p-iodide substituents
in isocyanide ligands of 12 than on iodine in CH2I2, viz. 28.7
kcal·mol–1 vs. 23.1 kcal·mol–1 (Figure 3). This tendency of
palladium complexes with p-iodo substituted isocyanides to form
strong intermolecular complex-complex interactions could
explain why they have the poorest solubility of the isocyanide
derivatives studied.
Acknowledgements
These studies were funded by the Russian Foundation for Basic
Research (grant 16-33-60123 mol_a_dk for MAK). Solid state
studies and quantum chemical calculations were supported by
the Russian Foundation for Basic Research (projects 18-29-
04006 and 16-03-00441). KVL thanks the University of Liverpool
for support. Measurements were performed at Center for
Magnetic Resonance, Center for X-ray Diffraction Studies,
Center for Chemical Analysis and Materials Research, and
Chemistry Educational Centre (all belonging to Saint Petersburg
State University).
Table 4. The solubility of 10–12 in CDCl3 and CH2I2 and maximums
electrostatic potentials (VS(r)max, kcal·mol–1) on the X in 10–12 and halogen
in haloalkanes.
Solubility, mg/mL
Vs(r)max, kcal·mol–1
Complex
CDCl3
82
CH2I2
XC6H4
8.4
CDCl3
CH2I2
23.1
10
11
12
19
79
77
Keywords: halogen bonding • solvation• organometallics •
35
19.8
28.7
10.4
haloalkanes • isocyanide complexes
5
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theory). Blue color – negative ESP, red color – positive ESP.
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To conclude, we scrutinized the solvation properties of a
number of haloalkane solvents against
a
series of
organometallic species. Using NMR measurements, we
established that CH2I2 demonstrated the best solvation
properties among all haloalkanes studied; solubility values for
organometallics were improved by up to an order of magnitude
when compared to the commonly used CHCl3. Since no
correlation between the polarity of haloalkanes and the solubility
of all model complexes was observed, we looked for an
alternative explanation. We anticipated that better solvation
properties of CH2I2 are related to a dramatic growth of the s-hole
donating ability of this solvent when compared to others, and
that results in the formation of strong solvent-(metal complex)
halogen bonding. The emergence of these uniquely strong XBs
in diiodomethane and its inertness towards organometallics
make this solvent a good candidate for NMR solvent-of-choice,
in particular, for the acquisition of insensitive spins, where the
concentration of an analyte is crucial. Whereas a number of
methods to suppress an undesired solvent signal in 1H NMR are
[7]
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10.1002/anie.201807642
Angewandte Chemie International Edition
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Entry for the Table of Contents
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Unique solvation properties of
diiodomethane towards halide-
containing organometallics are
associated with its enhanced σ-hole
donating ability leading to stronger
solvent-(metal complex) halogen
bonding.
M. A. Kinzhalov,* M. V. Kashina,
A. S. Mikherdov, E. A. Mozheeva,
A. S. Novikov, A. S. Smirnov,
D. M. Ivanov, M. A. Kryukova,
A. Yu. Ivanov, S. N. Smirnov,
V. Yu. Kukushkin, K. V. Luzyanin*
Page No. – Page No.
Solubility of halide-containing
organometallics is dramatically
enhanced in diiodomethane: can the
solvent•••complex halogen bonding
be held responsible?
This article is protected by copyright. All rights reserved.