19F NMR studies on positional variations of trifluoromethyl groups in CF3-substituted aromatic group 15 trivalent chlorides

Article abstract of DOI:10.1016/j.jfluchem.2015.11.005

Several Group 15 trivalent chlorides with CF₃-substituted aromatic groups R present, including at least one ortho-CF₃ substituent, R_nECl_3-n (n = 1 or 2; E = P, As, Sb or Bi) have been studied by ¹⁹F s

Full text of DOI:10.1016/j.jfluchem.2015.11.005

Journal of Fluorine Chemistry 181 (2016) 61–66
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
19F NMR studies on positional variations of trifluoromethyl groups in
CF3-substituted aromatic group 15 trivalent chlorides
a
b,
c
*
´
Stephanie M.M. Cornet , Keith B. Dillon , Bao Yu Xue
a OECD Nuclear Energy Agency, 12 boulevard des Iles, 92100 Issy-les-Moulineaux, France
b Chemistry Department, University of Durham, South Road, Durham DH1 3LE, UK
c Institute of Chemistry, Henan Academy of Sciences, Zhengzhou 450002, PR China
A R T I C L E I N F O
A B S T R A C T
Article history:
Several Group 15 trivalent chlorides with CF3-substituted aromatic groups R present, including at least
one ortho-CF3 substituent, RnECl3-n (n = 1 or 2; E = P, As, Sb or Bi) have been studied by 19F solution-state
NMR spectroscopy. In compounds with both ortho- and para-CF3 groups, the chemical shifts of the para-
CF3 fluorines are very similar, irrespective of the central element E. Much more variation is found in the
shifts of the ortho-CF3 fluorines, which may be correlated with the nature of the aromatic group, the
electronegativity of E and the occurrence of short E–F contacts, as demonstrated by previous
crystallographic studies of some of these compounds.
Received 10 September 2015
Accepted 10 November 2015
Available online 14 November 2015
Keywords:
19F NMR
CF3-substituted aromatics
Group 15
ß 2015 Elsevier B.V. All rights reserved.
Trivalent chlorides
1. Introduction
considered in detail until very recently, and then only for several
chloro-compounds of the Group 14 elements Si, Ge or Sn with Ar,
The bulky highly electronegative fluoromes ligand Ar (2,4,6-
(CF3)3C6H2) has been used extensively to stabilise both main group
and transition metal low-coordinate species [1–42]. This substitu-
ent is usually attached to the central element E by displacement of
halide, using the lithio-derivative ArLi of the parent hydrocarbon
1,3,5-(CF3)3C6H3 (ArH). Much less use has been made of the
fluoroxyl ligand 2,6-(CF3)2C6H3 (Ar0), because although the
precursor hydrocarbon 1,3-(CF3)2C6H4 (Ar0H) is readily available,
it can lithiate in two positions, giving rise to a mixture of 2,6-
(CF3)2C6H3 (Ar0) and 2,4-(CF3)2C6H3 (Ar00) derivatives [37–39,43–
50]. While both ligands are again highly electronegative, there is
clearly more steric protection in the ortho-positions for the Ar0
Ar0 or Ar00 substituents [54]. The results showed that in compounds
with para-CF3 groups their 19F chemical shifts were comparatively
little affected by changing the central element, whereas the shifts
of the ortho-CF3 groups showed much larger variations, which
could be correlated with both the electronegativity of the central
element and the existence of intramolecular E–F contacts between
the central element and fluorines in the o-CF3 groups, (at least one
interaction per CF3 group), at distances appreciably shorter than
the sum of the van der Waals radii. Analysis of the spectra enabled
structures to be assigned, even in mixtures of products. We have
now extended this study to a large number of chloro-derivatives of
Group 15 elements E (E = P, As, Sb or Bi) with Ar, Ar0, Ar00 or Ar000
substituents, using both data from the literature and some
recorded for new compounds. The 31P NMR solution-state spectra
have also been obtained for the phosphorus(III) species.
species.
A procedure has subsequently been described for
preparing 2,4-(CF3)2C6H3 (Ar00) derivatives, including Ar002PCl (7),
selectively in high yield [51]. More recently we have carried out
some reactions with 1,4-(CF3)2C6H4 (Ar000H). Monolithiation of
Ar000H leads to a single product Ar000Li, but this leads to one ortho-CF3
group only in the 2,5-(CF3)2C6H3 (Ar000)-substituted compounds,
hence giving less steric protection than in the Ar or Ar0 species, but
comparable with that in Ar00 derivatives [52,53]. While 19F
solution-state NMR spectra for the reaction products have been
recorded routinely in most instances, the results have not been
2. Results and discussion
The phosphorus compounds studied are shown in Fig. 1, and
their 19F and 31P NMR data are collected in Table 1. It is worth
noting that the more sterically hindered disubstituted possible
product Ar02PCl (6) from the reaction of the Ar0Li/Ar00Li mixture
with PCl3 was not detected in solution; the other two possible
disubstituted products Ar0Ar00PCl (11) and Ar002PCl (7) have both
been isolated from this mixture, and characterised by single-
crystal X-ray diffraction [37,46]. Nevertheless there is a report of
the crystal and molecular structures of Ar02PCl (6) in the Cambridge
*
Corresponding author. Tel.: +44 01913342004.
´
E-mail addresses: StephanieCornet@oecd.org (Stephanie M.M. Cornet),
k.b.dillon@durham.ac.uk (K.B. Dillon), byxue@hotmail.com (B.Y. Xue).
http://dx.doi.org/10.1016/j.jfluchem.2015.11.005
0022-1139/ß 2015 Elsevier B.V. All rights reserved.

62
S.M.M. Cornet et al. / Journal of Fluorine Chemistry 181 (2016) 61–66
CF3
CF3
CF3
CF3
PCl2
CF3
PCl2
PCl2
PCl2
CF3
F3C
F3C
CF3
1
2
3
4
F3C
CF3 F3C
CF3 F3C
CF3
P
P
CF3
CF3
CF3
CF3
CF3
Cl
Cl
5
6
CF3
CF3
F3C
CF3
P
P
CF3
CF3
CF3
Cl
Cl
7
8
F3C
F3C
CF3 F3C
CF3
CF3
P
P
CF3
CF3
CF3
CF3
Cl
Cl
9
10
CF3
CF3
P
CF3
CF3
Cl
11
Fig. 1. Structures of phosphorus(III) compounds (1)–(11).
Table 1
19F and 31P NMR data for P(III) chlorides (1)–(11).
Compound
Number
d 19F (ppm)
4JPF (Hz)
d 31P (ppm)
Ref.
ArPCl2
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
ꢀ53.7
ꢀ53.1a
ꢀ56.5
ꢀ56.8
ꢀ54.4
ꢀ64.6
61
61
84
84
42
144.7
146.6
151.6
151.2
74.9
[3]
Ar0PCl2
Ar00PCl2
Ar000PCl2
Ar2PCl
[43]
ꢀ63.6
ꢀ64.3
ꢀ64.1
this work
[52]
[37]
Ar02PCl
Ar002PCl
Ar0002PCl
ArAr0PCl
[57]
ꢀ57.3
ꢀ63.7
ꢀ64.5
ꢀ64.0b
66
66
42
42
68.3
67.6
76.6
[37]
ꢀ58.0
[52]
ꢀ54.1b
ꢀ54.3c
ꢀ55.5b*
ꢀ58.6
[52]
ArAr00PCl
Ar0Ar00PCl
(10)
(11)
ꢀ63.6b
ꢀ64.1
69.9
67.3
[37]
[46]
58
58
ꢀ55.0c,*
ꢀ58.9
ꢀ63.6
a
Converted from CF3COOH as reference;
Resonances for Ar group;
Resonance for Ar0 group;
Broad.
b
c
*

S.M.M. Cornet et al. / Journal of Fluorine Chemistry 181 (2016) 61–66
63
structural database [55,56], from
a
private communication
expected for compounds of the type RPCl2 (between 152 and
144 ppm), and R2PCl (between 77 and 67 ppm), where R is an
aromatic group (Table 1) [58].
19F NMR data for some analogous derivatives of arsenic(III),
antimony(III) and bismuth(III) are shown in Table 2, and their
structures are illustrated in Fig. 2. The results for Bi are limited to
(reference code BADLAU) [57], although no preparative details
or NMR data are available. Ar00PCl2 (3) could not be separated from
Ar0PCl2 (2), but was identified as a minor component in the solution
produced by a 1: 1 reaction between PCl3 and the Ar0Li/Ar00Li
mixture (Experimental section). All the 31P shifts are entirely as
Fig. 2. Structures of heavier Group 15 compounds (12)–(26).

64
S.M.M. Cornet et al. / Journal of Fluorine Chemistry 181 (2016) 61–66
Table 2
Table 3
19F NMR data for group 15 compounds (12)–(26).
Electronegativities and van der Waals Radii for elements E [59].
Compound
Number
d 19F (ppm)
Reference
E
Electronegativity
van der Waals
Sum of van der
˚
˚
Radius (A)
Waals Radii (A)
ArAsCl2
(12)
(13)
(14)
(15)
(16)
(17)
ꢀ53.5
ꢀ52.9
ꢀ57.7
ꢀ54.5
ꢀ58.4
ꢀ54.8a
ꢀ58.8b
ꢀ55.6
ꢀ53.2
ꢀ54.9
ꢀ55.1
ꢀ55.1
ꢀ58.4
ꢀ55.5a
ꢀ58.4b
ꢀ56.2
ꢀ56.0
ꢀ64.2
[25]
Ar0AsCl2
Ar00AsCl2
Ar2AsCl
This work
This work
[33]
P
2.20
2.28
1.97
1.93
1.95
2.05
2.25
2.35
3.42
3.52
3.72
3.82
ꢀ63.7
ꢀ63.9
ꢀ63.6
As
Sb
Bi
Ar002AsCl
Ar0Ar00AsCl
This work
[37]
ꢀ63.5
ꢀ64.9
Results for Ar000 are only available for phosphorus, where replace-
ment of Ar00 by Ar000 leads to an even lower frequency shift for both
RPCl2 and R2PCl. For Sb, while Ar0 gives rise to the highest frequency
shift again, there is a discrepancy in the sequence for Ar and Ar00
substituents between RSbCl2, where the reported shift for Ar00SbCl2
is at higher frequency than that for ArSbCl2, and R2SbCl, where the
compounds follow the same shift sequence as in the P and As
compounds. Thisvariationwithsubstituent isparticularlyevidentin
mixed species R1R2ECl, where R1 has two o-CF3 groups and R2 only
has one. The results for ArAr00PCl (ꢀ55.5 and ꢀ58.6 ppm), Ar0Ar00PCl
(ꢀ55.0 and ꢀ58.9 ppm), Ar0Ar00AsCl (ꢀ54.8 and ꢀ58.8 ppm) and
Ar0Ar00SbCl (ꢀ55.5 and ꢀ58.4 ppm) fall into this category, with the
higher frequency shift in each compound for the substituent with
two o-CF3 groups. This property can, of course, be used diagnosti-
cally in the analysis of mixtures of products in solution (see Fig. 3).
The electronegativities of the elements E are listed in Table 3,
together with their van der Waals radii, and, on the assumption of a
ArSbCl2
(18)
(19)
(20)
(21)
(22)
(23)
(24)
This work
[50]
Ar0SbCl2
Ar00SbCl2
Ar2SbCl
ꢀ63.6
ꢀ63.6
[50]
[14]
Ar02SbCl
Ar002SbCl
Ar0Ar00SbCl
[50]
ꢀ63.7
[50]
[50]
ꢀ63.6b
See text
ꢀ63.3
ArBiCl2
Ar2BiCl
(25)
(26)
[9]
[9]
a
Resonance for Ar0 group.
Resonances for Ar00 group.
b
literature data for Ar2BiCl (26), which has been fully characterised
by single-crystal X-ray diffraction, and a mention in the same
paper of a very weak 19F NMR signal at ꢀ56.2 ppm, ascribed to the
fluorines from the ortho-CF3 groups of ArBiCl2 (25), which is a
probable precursor [9]. The non-observation of the signal for the
para-CF3 group fluorines from (25), which would be half the
intensity of that from the ortho-CF3 group fluorines, is thus not
surprising. Results are included for three new arsenic compounds
(13), (14) and (16), and one new antimony compound (18)
(Experimental section), as shown in Table 2. The 19F NMR spectra
for the Ar0Li/Ar00Li–AsCl3 reaction mixture, together with those for
Ar0Ar00AsCl, which has been characterised crystallographically [37],
and for Ar002AsCl, are shown as a stackplot in Fig. 3.
Asinthe Group 14elements, the 19F NMR signalsfor p-CF3 groups
show little variation (Tables 1 and 2); the entire range of shifts for p-
CF3 substituents is onlyfromꢀ63.3to ꢀ64.9 ppm, irrespectiveof the
central element E. Significant differences are found for ortho-CF3 19F
resonances, however. There are variations depending on the nature
of the organic group attached to E, on the element E itself, and on the
probable number of short E–F contacts between fluorines from
ortho-CF3 groups and E, as shown in some instances by X-ray
crystallography. These aspects are discussed in more detail below.
For all P and As compounds, the 19F NMR shift sequences for the
o-CF3 fluorines follow the frequency pattern Ar0 > Ar > Ar00, with a
larger difference between the values for Ar and Ar00 (Tables 1 and 2).
˚
van der Waals radius for fluorine of 1.47 A, the sum of these radii
for E and fluorine [59]. For most types of compound studied,
including ArECl2, Ar0ECl2 (no Bi data) and Ar2ECl, the 19F NMR shifts
of the ortho-CF3 groups follow the frequency sequence
As > P > Sb > Bi, which parallels the order of electronegativities
of E. There tends to be only a small difference between the values
for As and P in corresponding compounds, but a larger change from
P to Sb, again in accordance with electronegativity values (Table 3).
This behaviour is parallel to that observed in Group 14 derivatives
[54]. The exception appears to be for Ar00ECl2, where the frequency
order is Sb > P > As (there are again no data for Bi). There is no
obvious explanation for this apparent discrepancy.
Some of the species in this work have been previously
characterised by single-crystal X-ray diffraction; these comprise
compounds (5), [37] (6), [57] (7), [37] (8), [52] (11), [46] (15), [33]
(17), [37] (21) [33] and (26).[9] In all instances, careful examina-
tion of the molecular structures in the Cambridge Structural
Database [55,56] confirms that there is at least one E–F contact at a
˚
distance less than 3.2 A for the fluorines in every ortho-CF3 group.
(Some of these have been mentioned in the relevant papers, but in
other compounds they were not discussed.) As shown in Table 3,
these distances are appreciably shorter than the sum of the van der
Waals radii for the elements concerned. The shortest E–F contact
distance in each of these compounds is listed in Table 4. Although
Table 4
Shortest E–F distances in compounds of known structure.
Compound
Number
Shortest E–F
Temperature
(K)
Reference
˚
distance (A)
Ar2PCl
(5)
2.843
2.800*
2.874
2.709
2.890
2.991
2.935
2.701
2.821
2.885*
[37]
[57]
[37]
[52]
[46]
[33]
Ar02PCl
Ar002PCl
Ar0002PCl
Ar0Ar00PCl
Ar2AsCl
(6)
2.817a,*
(7)
(8)
(11)
(15)
130(2)
296(1)
Ar0Ar00AsCl
Ar2SbCl
(17)
(21)
(26)
[37]
[33]
[9]
Ar2BiCl
19
Fig. 3. Stackplot of F NMR spectra for the products of the AsCl3–Ar0Li/Ar00Li
reaction where: (a) initial reaction mixture, showing Ar0AsCl2/Ar00AsCl2/Ar0Ar00AsCl/
Ar002AsCl; (b) Ar002AsCl; (c) Ar0Ar00AsCl.
a
Two molecules in the unit cell.
*
Calculated from the Cambridge Structural Database.

S.M.M. Cornet et al. / Journal of Fluorine Chemistry 181 (2016) 61–66
65
the remaining species in Tables
1 and 2 have not been
characterised crystallographically, it seems a reasonable assump-
tion that similar short E–F interactions will be found in each case.
Such interactions have been considered to contribute to the
stabilities of both main group and transition metal derivatives in
the solid state. As pointed out above, in mixed derivatives R1R2ECl
with one aromatic group having two ortho-CF3 groups and the
other having only one, the shift is invariably at higher frequency for
the fluorines in the R group which has two ortho-CF3 substituents.
Hence the number of E–F interactions is likely to be higher, and
may make a significant contribution to the observed shifts.
Scheme 1. Reactions for formation of Group 15 chloro-derivatives from ArLi and
Ar000Li.
Scheme 2. Reactions of ECl3 with a mixture of Ar0Li and Ar00Li.
3. Conclusions
Detailed investigation of the 19F NMR solution-state shifts of a
large number of Group 15 chloro-derivatives R1ECl2 or R1R2ECl (R1
and R2 are aromatic substituents with at least one o-CF3 group;
E = P, As, Sb or Bi) has shown that the shifts for p-CF3 fluorines are
very little affected by variation in E, R1 or R2. The shifts of the
o-CF3fluorines are much more sensitive, and may be correlated
with the nature of the substituents R1 and R2, the electronegativity
of the element E (apart from one apparent exception), and the
occurrence of short E–F contacts. In compounds which have been
previously characterised crystallographically, for every o-CF3
4.3. Synthesis of Ar00PCl2 (3)
Ar00PCl2 (3) was prepared in a mixture with Ar0PCl2 (4), which
could not be separated by distillation in vacuo. A solution of Ar0Li/
Ar00Li (96 mmol) was added dropwise over 20 min to a solution of
PCl3 (25.2 g, 16 ml, 183 mmol) in diethyl ether (100 ml) at ꢀ78 8C.
The mixture was allowed to warm to room temperature and
stirred for 4 h. The white solid (LiCl) which appeared was
removed by filtration, and solvent and any excess PCl3 removed in
vacuo, giving a brown oil. The product was purified by distillation
under vacuum (Bp 86 8C, 0.01 Torr). The components were
identified by 19F and 31P solution-state NMR spectroscopy
(Table 1).
˚
group there is at least one such contact at a distance of 3.2 A or
less, appreciably shorter than the sum of the van der Waals radii. In
mixed species (R1 R2), the fluorines for R groups with two o-CF3
substituents resonate at higher frequency than those with only one
o-CF3 group, irrespective of E. This may be correlated with the
increased number of E–F interactions in the former case, and may
be useful diagnostically in the analysis of mixtures of products, as
in the reaction of the Ar0Li/Ar00Li mixture with ECl3.
4.4. Synthesis of Ar0AsCl2 (13)/Ar00AsCl2 (14)/Ar0Ar00AsCl (17)/Ar002AsCl
(16)
A solution of Ar0Li/Ar00Li (100 ml, 94 mmol) in diethyl ether was
added dropwise to a solution of AsCl3 (13.5 ml, 160 mmol) in
hexanes (100 ml) over a period of 20 min at ꢀ78 8C. The mixture
was allowed to warm to room temperature and stirred for 4 h. A
precipitate of LiCl formed. This was filtered off and the solvents and
excess AsCl3 removed in vacuo, leaving a brown oil. This was
distilled under reduced pressure (0.01 Torr), and fractions were
collected at 115 8C (a mixture of all four products) and 145 8C
(mainly Ar0Ar00AsCl (17)). Some solid appeared in the first fraction.
This was separated, redissolved in CH2Cl2 and left in the freezer,
producing a white microcrystalline product unsuitable for X-ray
diffraction. 19F solution-state NMR spectroscopy showed that this
product was Ar002AsCl (16). The solid isolated from the higher-
boiling fraction was successfully recrystallized from hexane, and
has been fully characterised as Ar0Ar00AsCl (17) by single-crystal X-
ray diffraction [37].
4. Experimental
4.1. General
All manipulations, including NMR sample preparation, were
carried out either under dry N2 or in vacuo, by means of standard
Schlenk procedures or a glovebox. Chemicals of the best available
commercial grades were used, in general without further
purification. 19F solution-state NMR spectra were usually recorded
on a Varian Mercury 200 spectrometer at 188.18 MHz, and
chemical shifts are expressed in ppm relative to external
CFCl3. Occasionally 19F spectra were recorded on a Bruker AC
250 (235.36 MHz), Varian VXR 400 (376.35 MHz) or Varian Inova
500 (470.26 MHz) instrument. 31P NMR spectra were similarly
recorded at the apposite frequencies, and chemical shifts are given
relative to external 85% H3PO4.
4.5. Synthesis of ArSbCl2 (18)
4.2. Lithiations
ArLi (100 ml, 45 mmol, 0.45 M solution in Et2O) was added
dropwise over 10 min to a stirred solution of SbCl3 (10.8 g,
47.3 mmol) in Et2O (50 ml) at ꢀ78 8C. An orange-brown
solution was formed, with no visible precipitation of LiCl.
The reaction mixture was stirred for 2 h at room temperature.
Pentane (150 ml) was added, and the mixture was shaken
vigorously. Two layers formed. The lower dense brown oil gave
no 19F NMR signal, so was thought to be excess SbCl3 and LiCl.
The pentane was removed in vacuo from the upper layer,
yielding a yellow powdery solid which was recrystallized from
CH2Cl2 (25 ml). The isolated solid was extremely unstable, even
in a glovebox, and rapidly turned into a red oil. Nevertheless
the 19F solution-state NMR spectrum was successfully recorded
(Table 2).
ArH and Ar000H were treated separately with 2.5 M BuLi in Et2O
at ꢀ788 C (acetone/dry ice bath) to produce ArLi or Ar000Li,
respectively, according to the methods of Goodwin and Roden
[12,46]. Ar0H reacted with BuLi under the same conditions to yield
a mixture of Ar0Li and Ar00Li, in a ca. 1: 1 ratio as shown by NMR
spectroscopy. WARNING It is important in these reactions to
maintain a slight excess of the hydrocarbon with respect to BuLi at
all times, to avoid any attack on a CF3 group and the possible
explosive formation of LiF. The reactions for formation of Group
15 chloro-derivatives from ArLi and Ar000Li are shown in Scheme
1. The more complicated reactions of ECl3 with a mixture of Ar0Li
and Ar00Li are depicted in Scheme 2.

66
S.M.M. Cornet et al. / Journal of Fluorine Chemistry 181 (2016) 61–66
[28] J.-T. Ahlemann, H.W. Roesky, R. Murugavel, E. Parisini, M. Noltemeyer, H.-G.
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