Reactions of PhIX2I(iii) oxidants with heavy triphenyl pnictines

Article abstract of DOI:10.1039/d0dt00777c

The reactions of [PhI(pyridine)₂]²⁺, PhI(OAc)₂and PhI(OTf)(OAc) with Ph₃As, Ph₃Sb and Ph₃Bi are described. The reactions of [PhI(pyridine)₂]²⁺with Ph₃Sb and Ph₃Bi afford dicationic Pn(v) complexes ligated by pyridine in one step. These were previously reported by Burford in multi-step syntheses. Reactions with PhI(OAc)₂, which were already known for Sb and Bi giving Pn(v) diacetates, were confirmed to give the same type of compound for As. Reactions with PhI(OAc)(OTf) were less selective, resulting in the isolation of iodonium cations [Ph-I-Ph]⁺for As and Bi, while Ph₃Sb gave an oxobridged di-antimony species characteristic of the decomposition of a high valent triflate bound species.

Full text of DOI:10.1039/d0dt00777c

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14 March 2017
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Reactions of PhIX2 I(III) oxidants with heavy triphenyl pnictines
Sathsara Egalahewa, Antonino Aprile, and Jason L. Dutton*
Department of Chemistry and Physics, La Trobe Institute for Molecular Science, La
Trobe University, Melbourne, Victoria, Australia, 3086
ABSTRACT
The reactions of [PhI(pyridine)2]2+, PhI(OAc)2 and PhI(OTf)(OAc) with Ph3As, Ph3Sb and Ph3Bi
are described. The reactions of [PhI(pyridine)2]2+ with Ph3Sb and Ph3Bi affords dicationic Pn(V)
complexes ligated by pyridine in one step. These were previously reported by Burford in multi-
step syntheses. Reactions with PhI(OAc)2, which were already known for Sb and Bi giving Pn(V)
diacetates, were confirmed to give the same type of compound for As. Reactions with
PhI(OAc)(OTf) were less selective, resulting in the isolation of iodonium cations [Ph-I-Ph]+ for
As and Bi, while Ph3Sb gave an oxobridged di-antimony species characteristic of the
decomposition of a high valent triflate bound species.
1

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Introduction
The synthesis of polycationic species of the heavier late p-block elements has seen little
investigation as compared to the lighter elements due to reactivity of the intermediates and target
complexes as well as the requirement of a main-group halide starting material which can be
difficult to handle.1 Much of the work utilises halide abstraction resulting in triflate containing
species which can be used in further ligand exchange with other mono-, di- and tridentate ligands.2
Work by Burford et al. highlights this as using the above method they were able to isolate the bis-
triflate bismuth(V) compound 1 followed by exchange with pyridine ligands to give the dicationic
bismuth species 2 and monocationic species 3 (Scheme 1).3 The corresponding chemistry for
antimony was also reported by the Burford group.4
2+
Ph
Ph
Ph
P
Ph
Ph
O
-
Bi
2OTf
O
OPPh3
eqiv.
2
P
OTf
Cl
Ph
2 eqiv. AgOTf
- 2 AgCl
SO2Cl2
Bi OTf
Bi
Bi Cl
2
NMe2
+
2
eqiv.
4-DMAP
1
N
Bi
N
TfO
-
OTf
NMe2
3
Scheme 1. Isolation of bismuth(V) complexes 2 and 3 using triphenylbismuth.
2

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This strategy is a general route to ligand stabilized polycations in groups 15 and 16. As shown in
Scheme 2, the commonly used route in the literature is the abstraction of a halide with a species
that introduces triflate or another good leaving group, with some examples requiring a specific
halide for this reaction to proceed as well as the element in the correct oxidation state.5 Addition
of ligands to late main group halides can result in spontaneous reduction reactions, with
elimination of elemental halogen as a possible by-product leading to deleterious effects.6 The
triflate adducts can be very sensitive to moisture and air making them relatively difficult to store
and handle.
n
L
L
L
L
A
L
A
L
X
L
X
L
Halide Abstraction
L
L
Ligand Exchange
A-
E
E
E
EXn
E = p-block element
X = Halide
Decomposition
+ E0
X2
L = Neutral Mono\Bidentate Ligands
A = Anionic Ligand i.e. Triflate
Scheme 2. The common method utilised for the isolation of cationic p-block species showing
possible undesired outcomes.
The issues of intermediate stability and the side reactions that can occur during the isolation of
these molecules make a more direct route potentially attractive. Our group has been examining the
chemistry of dicationic I(III) reagents [PhI(Pyr)2]2+ (Pyr = Pyridine, 4-DMAP, 4-Cyanopyridine)
with a major feature of their chemistry being of simultaneous oxidation of a metal along with
delivery of the pyridine ligands. An example is the generation of Au(III) trications 5 from Au(I)
precursor 4 (Scheme 3).7
3

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+
2+
NMe2
N
NMe2
3+
NMe2
Me2N
N
I
N
N
N
N
3OTf -
2OTf -
OTf -
+
Au
Au
- PhI
N
N
Me2N
NMe2
5
NMe2
NMe2
4
Scheme 3. Isolation of cationic gold species 5 via oxidation with [PhI(Pyr)2]2+ oxidants.
These I(III) pyridyl compounds were first reported in 1994 by Weiss and later reinvestigated by
Zhdankin.8-10 Ritter also used the oxidant to access pyridine stabilized Pd(IV) complexes, where
the pyridine could be displaced with 18F labelled fluoride to generate PET labelling agents.11
Wengryniuk has recently shown the efficacy of these oxidants in oxidative ring formation
reactions.12-14
In the main group we have explored the chemistry of these dicationic I(III) oxidants with aromatic
group 16 rings, which largely resulted in electrophilic aromatic substitution type reactions on the
ring or ring substitutents.15, 16 We also reported one reaction in group 15, the reaction of Ph3P with
[PhI(4-DMAP)2]2+, which resulted in oxidation of phosphorus to P(V) and ligation of a 4-DMAP
giving dicationic complex 6 (Scheme 4),17 previously reported by Burford using the
oxidation/halide abstraction method from the phosphine.18 No reaction is observed between PPh3
and PhI(OAc)2. For PhI(OAc)(OTf) oxidation occurs giving a proposed P(V) triflate ligated
intermediate which rapidly decomposes to Ph3P=O and triflic anhydride.
4

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2+
NMe2
2+
N
I
2OTf -
- PhI
PPh3
+
Ph3P N
NMe2
N
6
NMe2
Scheme 4. Oxidation and delivery of 4-DMAP ligand to triphenylphoshpine giving dication 6.
We initially viewed these reactions as indicating that I(III) oxidants are incompatible with
phosphine ligands, although have since found in some cases they are compatible when the
phosphine is bound to a metal.19 In light of Burford’s work on heavier pnictogen(V) dications
described above, we wondered if these I(III) dications could be an effective reagent for their
generation, circumventing the steps involving halogenation/halide abstraction.
In this study we examined the ability of iodine(III) oxidants with anionic and neutral ligands as
potential reagents to isolate dicationic complexes of arsenic, antimony and bismuth using AsPh3,
SbPh3 and BiPh3 as starting materials.
Results and Discussion
Arsenic
Triphenylarsine was stirred with 1 equivalent of [PhI(Pyr)2][OTf]2 in CD3CN for 4 hours resulting
in a colourless solution. Acetonitrile was employed as reactions in CDCl3 or CD2Cl2 resulted in
1
the immediate formation of complex mixtures. The H NMR spectrum of the in situ CD3CN
5

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reaction had peaks corresponding to PhI indicating that an oxidation has occurred, at least one
other phenyl containing species and protonated pyridine as compared with an authentic sample. A
colourless single crystal was grown from the solution left to stand at -30oC for 24 hours. X-ray
crystallography revealed the product to be bis-As(V) cation (7) with a completely depronotated
acetonitrile fragment bridging the two As(V) centres. This compound has been reported via a
different route.20 We surmise in this case that acetonitrile coordinates to the oxidized arsenic
centres, rendering the hydrogen atoms more acidic, resulting in deprotonation by pyridine and
eventual rearrangement to the observed product. It should be noted here that the As analogue of 3
is not known and may not be stable as it is for Bi and Sb.
+
2+
N
N
C
OTf-
2OTf-
As
As
I
As
+
C
- PhI
N
- [HPyr][OTf]
7
Scheme 5. Oxidation of Ph3As using [PhI(Pyr)2][OTf]2 giving 7.
6

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The addition of 1 equivalent of PhI(OAc)(OTf) to triphenylarsine in CDCl3 resulted in an
1
immediate change in H NMR with all starting material consumed within minutes and the
formation of a complex mixture. A vapor diffusion of the solution with n-hexane led to colourless
crystals. X-ray crystallography of a single crystal revealed a diaryliodonium triflate salt (8) via
unit cell analysis (Scheme 6),21 this cation was also observed in the mass spectrum of the reaction
mixture. No oxidized arsenic species could be identified in the mass spectrum. Compound 8 is
known and most commonly synthesized by the reaction of iodoarenes with a suitable oxidant.22
+
I+
-
PhI(OAc)(OTf)
OTf
+
As
I
8
Scheme 6. Addition of PhI(OAc)(OTf) to Ph3As results in isolation of 8. The fate of the As could
not be determined.
1
Next, triphenylarsine was reacted with PhI(OAc)2 in CDCl3. The H NMR spectrum of the
colourless reaction mixture confirmed that reaction was driven to completion with no starting
material after stirring for 24 hours. The spectrum had peaks corresponding to PhI and another
species which indicates the possible formation of As(V) as the iodine became reduced. Colourless
crystals were grown at -30oC. The crystals were of poor quality, but X-ray crystallography allowed
for structural confirmation of the formation of triphenylarsine diacetate (9, Scheme 7 ). Compound
9 is a known compound and has been synthesized by other routes.23
Attempts to exchange the acetate groups in 9 for triflates as a better leaving group using TMS-OTf
resulted in no reaction. In summary, reactions of these I(III) oxidants with triphenylarsine did not
result in productive advances.
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OAc
OAc
OTf
OTf
2 eqiv. TMS-OTf
PhI(OAc)2
As
As
As
9
Scheme 7. Isolation of 9 utilizing PhI(OAc)2 and attempted ligand exchange with TMS-OTf.
Antimony
The addition of [PhI(Pyr)2][OTf]2 to a CD3CN solution of triphenylantimony did not give an
1
immediate reaction as monitored by H NMR spectroscopy. Upon overnight stirring the NMR
showed the oxidant had been consumed, with PhI and a new species generated. A white powder
was obtained by removing the volatiles in vacuo.
2+
2+
N
N
I
2OTf-
2OTf-
Sb
+
Sb
N
- PhI
N
10
Scheme 8. Oxidation of Ph3Sb using [PhI(Pyr)2][OTf]2 yielding 10.
8

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Single crystals were grown from a CH2Cl2 solution of the isolated material via vapour diffusion
into n-hexane. X-ray crystallographic studies revealed the target dicationic antimony(V) complex
10 (Scheme 8), previously reported by Burford via the multistep route outlined in Scheme 1 using
4-DMAP ligands.3 The two pyridyl groups are coordinated axial to the central antimony with the
three phenyl rings in the equatorial positions. One triflate anion with an Sb-O distance of 2.760 Å
completes a distorted octahedral geometry. Overall the structure is very similar to that determined
by Burford using 4-DMAP ligands.3
Figure 1. Solid-state structure of 10. Chloroform and acetonitrile solvate and hydrogen atoms
omitted for clarity. Thermal ellipsoids are shown at the 50% probability level. Selected bond
distances (Å): Sb(1)-C(1) 2.100(4), Sb(1)-C(2) 2.124(4), Sb(1)-C(3) 2.111(4), Sb(1)-N(1)
2.272(4), Sb(1)-N(2) 2.264(4).
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TfO
OTf
Sb
MeCN
- PhI
Ph3Sb + PhI(OAc)(OTf)
Sb
O
11
Scheme 9. The reaction of PhI(OAc)(OTf) with Ph3Sb giving 11.
The 1:1 reaction of Ph3Sb and PhI(OAc)(OTf) in CD3CN resulted in a yellow solution after stirring
1
for 2 hours. The H NMR spectrum of the reaction mixture showed a clean spectrum with the
peaks associated with PhI(OAc)(OTf) being replaced with PhI, indicating an oxidation had taken
place, as well as other peaks associated with phenyl fragments. Addition of n-hexane resulted in
precipitation of a white powder, for which the isolated material returned a similar proton NMR to
the in situ reaction mixture, without the PhI. A CDCl3 solution of the isolated material was held at
-30C overnight yielding colorless crystals. Unit cell analysis by X-ray diffraction, then confirmed
by partial refinement revealed the product to be an oxo-bridged Sb(V) species 11 with a single
oxygen in the centre and each antimony capped with a triflate (Scheme 9). This compound has
been previously reported and structurally characterized using a different route in which
triphenylantimony oxide is reacted with triflic acid in acetone.24, 25 This result is reminiscent of the
outcome with Ph3P with the PhI(OAc)(OTf) oxidant, in which the proposed P(V)-OTf
intermediates decompose into phosphine oxide species.17 In the case of the phosphine anhydrides
could be observed in the reaction mixture, however in this case neither triflic or acetic anhydride
were observed in the in situ reaction mixture. We do not believe the Sb-O-Sb unit arises from
hydrolysis as PhI(OAc)(OTf) is highly sensitive to water (as is [PhI(Pyr)2][OTf]2) and thus
rigorously anhydrous methods and solvents are used.
10

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The reaction of Ph3Sb with PhI(OAc)2 has been previously reported to oxidize the antimony and
give the expected diacetoxy Sb(V) complex.26
Bismuth
Ph3Bi was added to a CD2Cl2 solution of [PhI(4-DMAP)2][OTf]2. CD2Cl2 solvent was chosen to
match observations from Burford’s oxidation/halide abstraction route as their NMR studies for the
expected compound were done in CD2Cl2.3 1H NMR of the solution after 2 hours showed little
conversion and the mixture was left to stir overnight. After 16 hours complete conversion of the
oxidant to PhI was observed, as well as one set of signals identical to that observed by Burford in
CD2Cl2 for 12 (Scheme 10). In a bulk synthesis in CH2Cl2 compound 12 could be isolated in a
single step with a 66% yield, an improvement over Burford’s yield (41%).
NMe2
NMe2
2+
2+
N
N
I
2OTf-
2OTf-
Bi
+
Bi
N
N
- PhI
NMe2
NMe2
12
Scheme 10. The reaction of [PhI(4-DMAP)2]2+ with Ph3Bi giving 12.
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The addition of 1 equivalent of PhI(OAc)(OTf) to triphenylbismuth (Ph3Bi) in chloroform resulted
in an immediate change in the 1H NMR from the 2 starting materials. Placing the solution in the
freezer overnight resulted in the precipitation of colourless crystals.
+
I+
-
PhI(OAc)(OTf)
+
OTf
Bi
13
Scheme 11. Addition of PhI(OAc)(OTf) to Ph3Bi results in isolation of 13.
X-ray diffraction studies showed via unit cell analysis27 that the result was a diaryliodonium triflate
salt 13 (Scheme 11) with 1H NMR of the crystals also matching literature reports.28 Compound 13
has been synthesised via numerous different methods one of which is known to involve a
diarylstannane reagent.29, 30 The proposed mechanism for the formation of these diaryliodonium
salts is thought to be by a ligand exchange reaction with a nucleophilic arylating reagent containing
silicon, tin or mercury.
In some experiments the in situ mass spectrum of the reaction mixture showed a signal that could
be attributed to diphenylbismuth acetate, indicating a possible aryl exchange process giving 13 but
this could not be observed reliably.
The reaction of PhI(OAc)2 with Ph3Bi is known to give the triphenylbismuth(V) diacetate.31 As
with arsenic, an attempted synthesis of a bis-triflate complex via metathesis with TMS-OTf from
triphenylbismuth(V) diacetate resulted in no reaction.
12

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Conclusion
For bismuth and antimony, use of the [PhI(pyr)2][OTf]2 class of oxidants allows for the formation
of dicationic Sb(V) and Bi(V) pyridyl complexes in one step from Ph3Pn(III) starting compounds,
demonstrating the potential efficacy of this I(III) reagent in isolating high oxidation state main
group compounds. However, this method was not able to access the as yet unknown As analogue.
PhI(OAc)2 gave the expected Ph3As(OAc)2 product when reacted with Ph3As, complementing the
already reported chemistry for Sb and Bi. The more powerful PhI(OAc)(OTf) oxidant in reactions
with Ph3Pn gave varied and generally unproductive results.
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Experimental Section
All manipulations were performed under a dry N2 atmosphere in a glovebox. Bulk solvents were
dried using an Innovative Technologies Solvent Press with dual alumina columns and stored over
3 Å molecular sieves in the glovebox. NMR solvents were dried for 2 days over CaH2, distilled
and then stored in the glovebox over 3 Å molecular sieves. PhI(OAc)2, TMS-OTf, pyridine, 4-
DMAP, Ph3Sb and Ph3As were obtained from Sigma-Aldrich and used as received. Ph3Bi,
[PhI(pyr)2][OTf]2, [PhI(4-DMAP)2][OTf]2 and PhI(OAc)(OTf) were synthesized according to
literature procedures.3, 8
Synthesis of 7:
Ph3As (100 mg, 0.326 mmol) was dissolved in a small amount of CD3CN (3 mL) and added to a
solution of [PhI(pyr)2][OTf]2 (215 mg, 0.326 mmol; 3 mL). The mixture was stirred for 4 hr and
examined by 1H NMR. The CD3CN solution was left at -35oC overnight to afford large colourless
crystals. Yield 34 mg 64% 1H NMR (400 MHz, CDCl3): δ 7.70 (m, 12H), 7.54 (m, 18H); 19F{1H}
NMR (376 MHz, CDCl3): -78.41
Synthesis of 8:
Ph3As (100 mg, 0.326 mmol) was dissolved in CDCl3 (3 mL) and added to a solution of freshly
prepared PhI(OAc)(OTf) (0.326 mmol; 3 mL). The mixture was stirred for 1 hr and examined by
1H NMR. Colourless crystals where grown by a vapour diffusion of hexane/chloroform. 1H NMR
(400 MHz, CDCl3): δ 7.82 (m, 4H), 7.73 (m, 4H), 7.64 (m, 1H); 19F{1H} NMR (376 MHz, CDCl3):
-78.06
14

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Synthesis of 9:
Ph3As (100 mg, 0.326 mmol) was dissolved in CDCl3 (3 mL) and added to a solution of PhI(OAc)2
(105 mg, 0.326 mmol; 3 mL). The mixture was stirred for 24 hr and examined by 1H NMR. The
CDCl3 solution was left at -35oC overnight to afford large colourless crystals. Yield 46 mg 79%1H
NMR (400 MHz, CDCl3): δ 8.05 (m, 8H), 7.51 (m, 12H), 1.72 (s, 6H).
Synthesis of 10:
Ph3Sb (100 mg, 0.281 mmol) was dissolved in MeCN (3 mL) and added to a solution of
[PhI(Pyr)2][OTf]2 (186 mg, 0.281 mmol; 5 mL). The mixture was stirred for 1 hr and the volatiles
where removed in vacuo leaving a white powder. Colourless crystals where grown by a vapour
diffusion of hexane/CH2Cl2. Yield 136 mg 51 % 1H NMR (400 MHz, CDCl3): δ 8.91 (d, 4H, J =
4 Hz) 8.63 (d, 2H, J = 4 Hz), 8.03 (d, 4H, J = 4 Hz), 7.59 (t, 3H, J = 4 Hz) 7.54 (d, 6H, J = 4 Hz),
19
13
7.45 (t, 6H, J = 4Hz); F{1H} NMR (376 MHz, CDCl3): -78.29, C{1H} NMR 146.4, 142.1,
134.6, 133.8, 133.2, 133.0, 130.5, 130.4, 127.6, Mp: 144-148oC.
Synthesis of 11:
Ph3Sb (100 mg, 0.281 mmol) was dissolved in CD3CN (3 mL) and added to a solution of
PhI(OAc)(OTf) in CD3CN (114 mg, 0.281 mmol; 3 mL). The mixture was stirred for 1hr and
examined by 1H NMR. The CD3CN solution was left at -35oC overnight to afford large colourless
crystals. Yield 75 mg 53 % 1H NMR (400 MHz, CDCl3): δ 8.02 (m, 12H), 7.76 (m, 18H); 19F{1H}
NMR (376 MHz, CDCl3): -77.5
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Synthesis of 12:
Ph3Bi (100 mg, 0.227 mmol) was dissolved in CH2Cl2 (3 mL) and added to a solution of
[PhI(DMAP)2][OTf]2 (169 mg, 0.227 mmol; 3 mL). The mixture was stirred for overnight and
filtered to remove unreacted oxidant. Et2O (5 mL) was added to the solution resulting in
precipitation of a colourless solid. The solution was decanted and the solid dried in vacuo. Yield
148 mg 66%. 1H NMR (400 MHz, CD2Cl2): δ 7.9 (br, 4H), 7.77 (d, 8H), 7.59 (br, 7H), 6.64 (br,
2H), 3.13 (s, 12H); 19 F{1H} NMR (376 MHz, CDCl3): -78.8
Synthesis of 13:
Ph3Bi (100 mg, 0.227 mmol) was dissolved in CDCl3 (3 mL) and added to a solution of
PhI(OAc)(OTf)(114 mg, 0.227 mmol; 3 mL). The mixture was stirred for 1 hr and stored overnight
at -35oC. Large colourless crystals were isolated from the solution followed by removal of the
solution in vacuo. Yield 34 mg 35% 1H NMR (400 MHz, DMSO): δ 8.25 (m, 6H), 7.67 (d, 6H),
7.41 (m, 6H); 19 F{1H} (376 MHz, DMSO): -77.74
16

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DOI: 10.1039/D0DT00777C
2+
2+
N
N
I
2OTf-
2OTf-
Pn
+
Pn
N
- PhI
N
Pn = Sb, Bi
Oxidation of heavy triphenyl pnictines with Weiss’ reagent ([PhI(Pyr)2]2+) gives dicationic
Pn(V) coordination complexes in a single step