Synthesis and Reactivity of Iridium(I) Fluorido Complexes: Oxidative Addition of SF4 at trans-[Ir(F)(CO)(PEt3)2]

Article abstract of DOI:10.1002/zaac.202000026

The facile access to the Vaska type fluorido complexes trans-[Ir(F)(CO)(PR₃)₂] [6: R = Et, 7: R = Ph, 8: R = iPr, 9: R = Cy, 10: R = tBu] was achieved by halide exchange at trans-[Ir(Cl)(CO)(PR₃)₂] (1–5) with Me

Full text of DOI:10.1002/zaac.202000026

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.202000026
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Synthesis and Reactivity of Iridium(I) Fluorido Complexes:
Oxidative Addition of SF4 at trans-[Ir(F)(CO)(PEt3)2]
Nils Pfister,[a] Minh Bui,[a] Thomas Braun,*[a] Philipp Wittwer,[a] and Mike Ahrens[a]
Dedicated to Prof. Manfred Scheer on the Occasion of his 65th Birthday
Abstract. The facile access to the Vaska type fluorido complexes did not react. Reactivity studies revealed that 11 can selectively be
trans-[Ir(F)(CO)(PR3)2] [6: R = Et, 7: R = Ph, 8: R = iPr, 9: R = Cy,
10: R = tBu] was achieved by halide exchange at trans-[Ir(Cl)(CO)-
manipulated at the sulfur atom by hydrolysis or fluoride abstraction to
give cis,trans-[Ir(F)2(SOF)(CO)(PEt3)2] (12) and cis,trans-[Ir(F)2(SF2)-
(PR3)2] (1–5) with Me4NF. Furthermore, the reaction of complex 6 (CO)(PEt3)2][AsF6] (13), respectively.
with SF4 gave cis,trans-[Ir(F)2(SF3)(CO)(PEt3)2] (11), whereas 8–10
Introduction
trans-[Pt(F)(SF3)(PR3)2] (R = iPr, Cy) were applied in deoxy-
Fluorinated transition metal complexes are highly interest-
ing substances.[1] Fluorido complexes of late transition metals
can enable unique reaction pathways when compared to the
reactivity of the corresponding metal complexes of the heavier
halides.[1a,1b,2] The preparation of transition metal fluorido
complexes can be achieved either by treatment of metal fluor-
ides with ligand precursors, by fluorination of suitable com-
plexes or by the activation of element–fluorine bonds.[1a,1b,2l,3]
Apart from C–F bond activation reactions,[2e,2f,2h,2l,4] this also
includes reactions with SF4 or SF6.[5] SF4 is typically used as
a tool for the fluorination of oxygen containing compounds,
but has so far received only little attention in transition metal
chemistry.[5b,6] Replacement of a fluoride in SF4 by nitrogen
atoms or a bulky aryl group led to the discovery and commer-
cialization of several deoxyfluorinating agents like Fluolead™,
DAST, MOST or Deoxo-Fluor®.[7] The derivatives often show
a higher selectivity in fluorination, but they are not as versatile
when compared with SF4.[6b,8]
fluorination reactions of ethanol or benzophenone.[5e,5h,10]
Note that the reaction of SF4 with 7 at 178 K to form a mixture
of compounds with cis,trans-[Ir(F)2(SF3)(CO)(PPh3)2]
as main product was also reported.[5h] This demonstrates the
influence of the fluorido ligand on the S–F bond cleavage in
SF4, because the chlorido complex 2 did give the respective
SF3 complex only at 323 K.[5h] Other conversions at Vaska-
type rhodium complexes were described as well, but the pro-
cedures always resulted in a mixture of products.[5g] However,
we recently reported on the selective formation of cis,trans-
[Rh(F)2(SF3)(CO)(PEt3)2] by oxidative addition of SF4 at
trans-[Rh(F)(CO)(PEt3)2]. The complex was characterized by
NMR spectroscopy and is only stable at low temperature in
solution.[5f]
In this contribution we report on the development of a reac-
tion route to access iridium(I) fluorido carbonyl complexes.
trans-[Ir(F)(CO)(PEt3)2] (6) is a useful starting compound for
the synthesis of an iridium SF3 complex, which can be handled
in solution at room temperature. Reactivity studies towards hy-
drolysis and the Lewis acid AsF5 are also presented.
Examples for transition metal derivatives of sulfur fluorides
are scarce, but DFT calculations suggest the general feasibility
of metal bound SF units.[5e,5f,9] All experimentally available
SF3 complexes include only platinum group metal com-
pounds.[5b–5h] The most stable and best characterized
Results and Discussion
derivatives
are
trans-[Ir(Cl)(F)(SF3)(CO)(PEt3)2]
and
Treatment of trans-[Ir(Cl)(CO)(PR3)2] with Me4NF in
dichloromethane gave trans-[Ir(F)(CO)(PR3)2] [6: R = Et, 7:
R = Ph, 8: R = iPr, 9: R = Cy, 10: R = tBu] as the product of
chlorine-fluorine exchange reactions (Scheme 1). Furthermore,
trans-[Pt(F)(SF3)(PR3)2] (R = iPr, Cy).[5c–5h] The complexes
* Prof. Dr. T. Braun
E-Mail: thomas.braun@cms.hu-berlin.de
[a] Department of Chemistry
Humboldt Universität zu Berlin
Brook-Taylor-Straße 2
12489 Berlin, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.202000026 or from the au-
thor.
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH &
Co. KGaA. · This is an open access article under the terms of the
Creative Commons Attribution-NonCommercial-NoDerivs Li-
cense, which permits use and distribution in any medium, provided
the original work is properly cited, the use is non-commercial and
no modifications or adaptations are made.
Scheme 1. Preparation of trans-[Ir(F)(CO)(PR3)2] [6: R = Et, 7: R =
Ph, 8: R = iPr, 9: R = Cy, 10: R = tBu].
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the isotopologue of 6, trans-[Ir(F)(13CO)(PEt3)2] (6Ј) was ob- [Ir–C: 1.788(10) Å],[13] which is also observed when
tained when trans-[Ir(Cl)(13CO)(PR3)2] (6Ј) was treated with comparing the analogous rhodium complexes.[5f,13–14]
Me4NF. The complex trans-[Ir(F)(CO)(PPh3)2] (7) has been
described in the literature and was identified by its NMR and
IR spectroscopic data (Table 1).[11] Comparable fluorination
reactions with Me4NF in dichloromethane were reported be-
fore, for instance at rhodium and palladium complexes.[2c,5f]
The Ir–F distances [1.965(5) Å for 9, 1.9846(19) Å for 10] are
well comparable to these in other iridium(I) fluorido
complexes as well as to the one observed in trans-
[Ir(F)(CO)(P{C6H4-2-CH3)3}2].[15]
The 19F NMR spectrum of the complex 6 reveals one signal
at δ = –265 ppm which appears as a triplet (2JF,P = 33 Hz) and
can be assigned to an iridum(I) bound fluorine atom with two
phosphorus nuclei in a cis position.[11c,11d,12b,15a,15b,15e] The
isotopologue trans-[Ir(F)(13CO)(PEt3)2] (6Ј) shows a doublet
of triplets [2JC,F = 84 Hz], caused by the coupling of the carbon
atom of the carbonyl ligand to the fluorine atom in the trans
position.[5f,16] The 31P{1H} NMR spectrum of compound 6 ex-
hibits a single resonance at δ = 25.6 ppm showing the respec-
tive 2JP,F doublet coupling. An additional doublet coupling can
be detected for the 31P{1H} NMR spectrum of the isoto-
Table 1. Selected IR and NMR spectroscopic data for complexes
trans-[Ir(F)(CO)(PR3)2] (6–10) ( in cm–1, δ in ppm, J in Hz).
Complex
ν(CO)
δ(19F)
2JP,F
δ(31P)
6
7
8
9
1925
1943
1916
1924
1910
–265
–254
–256
–255
–243
33
30
26
26
24
25.6
24.4
49.5
39.3
71.5
[11]
10
Slow evaporation of a saturated n-hexane solution at room
temperature produced crystals suitable for X-ray diffraction of
9 (Figure 1, left) and 10 (Figure 1, right). The CO and fluorido
ligand in 9 are disordered. The asymmetric unit for complex
10 contains three molecules of which one reveals a disorder of
the F, Ir and CO positions (Figure S31, Supporting Infor-
mation). The bond lengths and angles found for all molecules
of 10 are comparable, and hence only one is discussed in the
following. The complexes trans-[Ir(F)(CO)(PCy3)2] (9) and
trans-[Ir(F)(CO)(PtBu3)2] (10) exhibit an approximately
square-planar coordination about the iridium center. Only a
slight deviation from the ideal geometry is found for trans-
[Ir(F)(CO)(PCy3)2] (9) with ligand–iridium–ligand angles of
88.37(2)° (F1–Ir1–P1) and 178.33(5)° (F1–Ir1–C1). A stronger
distortion is observed for trans-[Ir(F)(CO)(PtBu3)2] (10) indi-
cated by the F2–Ir2–C2 and P4–Ir2–P3 angles [169.88(13)°
and 172.98(3)°], most probably due to the sterical demand of
the tBu groups at the phosphorus atoms. A nearly linear coor-
dination of the carbonyl ligand to the metal center is revealed
by the Ir–C–O angles of 176.3(12)° (9) and 176.4(3)° for (10)
showing the expected bond lengths for the Ir–C [1.838(11) Å
for 9, 1.800(3) Å for 10] as well as for the C–O [1.156(11) Å
for 9, 1.174(4) Å for 10] distances.[12] The metal carbon
2
pologue 6Ј with a JC,P cis-coupling of 10 Hz.[17] Compound
6Ј reveals the expected doublet of triplet pattern in the
13C{1H} NMR spectrum in the range of iridium(I) bound carb-
onyl ligands at δ = 174.1 ppm.[17,18] A very intense absorption
band at 1925 cm–1 for the CO stretch mode can be detected in
the IR spectrum of 6 (1878 cm–1 for 6Ј) which is well compar-
able to the known iridium based Vaska type complexes.[12a,19]
Compound 6 shows a significantly lower wavenumber than the
compounds bearing heavier halogenido ligands.[19] This phe-
nomenon has already been discussed in the literature. It has
been proposed that the fluorido ligand acts as a better π-donor
than the other halogenido ligands.[1a–1d] A push-pull interac-
tion has also been reasoned for the stronger π backbonding
from the metal to the ligand.[2k,20] The NMR and IR spectro-
scopic data of the complexes 7–10 are very similar to those of
6 and are therefore not discussed (see Supporting Information
and Table 1).
The fluorido complex 6 readily reacted with equimolar
amounts of SF4 in [D8]THF, [D8]toluene or CD2Cl2 below
263 K to give cis,trans-[Ir(F)2(SF3)(CO)(PEt3)2] (11)
(Scheme 2). When introducing SF4 to 6Ј the formation of the
isotopomer cis,trans-[Ir(F)2(SF3)(13CO)(PEt3)2] (11Ј) was ob-
distance in 9 is longer than in trans-[Ir(Cl)(CO)(PCy3)2] (4) served. Attempts to isolate 11 resulted in the decomposition of
Figure 1. ORTEP diagram of trans-[Ir(F)(CO)(PCy3)2] (9) (left) and trans-[Ir(F)(CO)(PtBu3)2] (10) (right). Ellipsoids are drawn at 50% prob-
ability. All hydrogen atoms are omitted for clarity. Selected bond lengths /Å and angles /° with estimated standard deviations in parentheses: 9:
Ir1–F1 1.965(5), Ir1–C1 1.838(11), Ir1–P1 2.3266(4), O1–C1 1.156(11); F1–Ir1–P1 88.37(2), F1–Ir1–C1 178.33(5), Ir1–C1–O1 178.99(11); 10:
Ir2–F2 1.9846(19), Ir2–C2 1.800(3), Ir2–P3 2.3810(9), Ir2–P4 2.3901(8), O2–C2 1.174(4), P3–Ir2–P4 172.98(3), P4–Ir2–F2 85.17(6), P4–Ir2–
C2 93.96(10), F2–Ir2–C2 169.88(13), Ir2–C2–O2 176.4(3).
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the complex giving SPEt3 along with F2PEt3 and unidentified the sulfur atom, and the resonance at –64.9 ppm to the one in
iridium species.[21] Based on 19F NMR spectroscopy 11 was the equatorial position.[5d–5h] The signal for the sulfur bound
2
assumed to be one of four products in the reaction of trans- fluorine atom at higher field shows a JF,F triplet splitting of
[Ir(NCS)(CO)(PEt3)2] with SF4, which was reported by Mur- 71 Hz which is in good accordance with fluorine-fluorine
doch.[5h] No oxidative addition of SF4 was observed for 8–10 couplings in sulfur(IV) compounds.[5c,5e,7a,7b,23] When cooling
but the formation of traces of the respective difluorophos- the sample to 203 K the resonance for the axial fluorine atoms
phoranes and phosphine sulfides where detected by 19F and at sulfur splits into two broad signals, indicating a dynamic
31P{1H} NMR spectroscopy when the reaction mixtures were behavior on the NMR timescale.
heated up to 323 K.[21a,22] Comparable observations were re-
ported for analogous rhodium compounds, and it was reasoned
that the steric demand of the phosphine ligands plays a crucial
role.[5f]
Scheme 2. Formation of cis,trans-[Ir(F)2(SF3)(CO)(PEt3)2] (11).
DFT
calculations
were
carried
out
on
cis,trans-[Ir(F)2(SF3)(CO)(PR3)2] (11: R = Et; R = iPr) (see
SI), and both complexes converged into stable structures.
Furthermore, the calculated reaction enthalpies for the forma-
tion of cis,trans-[Ir(F)2(SF3)(CO)(PR3)2] (11: R = Et; R = iPr)
from trans-[Ir(F)(CO)(PR3)2] (6: R = Et, 8: R = iPr) and SF4
both indicate the general feasibility of these reactions, whereas
the formation of 11 was found to be more exergonic. However,
as stated above, cis,trans-[Ir(F)2(SF3)(CO)(PiPr3)2] was not
observed experimentally. The analysis of the frontier orbitals
of 11 reveals a HOMO, which is located at the sulfur atom and
resembles an electron lone pair (Figure 2). The λ4-trifluoro-
sulfanyl ligand should, therefore, be regarded as a one-electron
donor.[5e,5f,9g]
Figure 3. 19F NMR spectrum (282.4 MHz) of cis,trans-[Ir(F)2(SF3)-
(CO)(PEt3)2] (11) at 243 K (° SOF2; * SF6).
For the two metal fluorido ligands in 11 sharp doublets of
triplets at δ = –314.6 and –366.6 ppm appear in the 19F NMR
spectrum at a characteristic chemical shift.[15a,24] Both show a
2JF,F coupling of 143 Hz indicating a mutual cis arrange-
ment.[15a,24b] Additionally the triplet couplings of 34 Hz and
29 Hz suggest that both metal fluorides have two phosphine
ligands in a cis position.[15a,24d] The 13C labeled isotopologue
11Ј doesn’t show further splitting of the signals for the sulfur
bound fluorine atoms, but an additional doublet splitting of
77 Hz and 5 Hz is observed for the resonances of the
metal fluorides at δ = –314.6 and –366.6 ppm, respec-
2
tively.[5f,16,24d–24f] A larger JF,C coupling of the carbonyl li-
gand to a fluoride in the trans position than to a fluoride in
the cis position has been observed before, and this allows for
an assignment of both resonances.[5f,24d–24f] Thus, the signal at
at δ = –314.6 ppm is attributed to the fluorido ligand trans to
the carbonyl ligand and the resonance at δ = –366.6 ppm to
the fluorido ligand cis to the carbonyl ligand.[5h,15a,24b,24e,24f]
At 203 K the 31P{1H} NMR spectrum of 11 shows one ex-
tremely broadened resonance at around δ ≈ 13 ppm (Figure 4).
This broadening is presumably due to a hindered rotation of
the λ4-trifluorosulfanyl group about the Ir–S bond. Similar
fluxionalities have been observed for the above mentioned irid-
ium, rhodium and platinum complexes.[5c–5h] Increasing the
temperature resulted at 298 K in a doublet of doublet pattern
due to coupling to the two fluorine atoms in the cis position
of the phosphines (Figure S15, Supporting Information). An
additional doublet splitting of 7 Hz is detected in the 31P{1H}
Figure 2. HOMO of the DFT-optimized structure of cis,trans-
[Ir(F)2(SF3)(CO)(PEt3)2] (11). Hydrogen atoms at the phosphine li-
gands are omitted for clarity.
At 243 K the 19F NMR spectrum of 11 shows four reso- NMR spectrum of 11Ј at 298 K indicating a cis arrangement
nances at δ = 67.5, –64.9, –314.6 and –366.6 ppm which inte- of the carbonyl ligand to the phosphine ligands. The above
grate in a ratio of 2:1:1:1 (Figure 3). The broad signal at δ = mentioned couplings are also observed in the 13C{1H} NMR
67.5 ppm can be assigned to the two fluorine atoms in the spectrum of 11Ј (Figure S19, Supporting Information), which
axial positions of the trigonal bipyramidal configuration about shows a doublet of triplets of doublets in the expected range
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2
position (2JP,P = 342 Hz).[5c,5g,5h,26] The JP,F couplings appear
in the typical range (A: 32, 28 Hz, B: 29, 33 Hz).[5c,5f,15a,24d,24f]
3
The JP,F couplings of the phosphine ligands to the sulfur
bound fluorine atom of 7 Hz (A) and 10 Hz (B) are comparable
to the ones found in trans-[Pt(F)(SOF)(PCy3)2] (18), trans-
[Ir(Cl)(F)(SF3)(CO)(PEt3)2] (14) and trans-[Pt(F)(SF3)(PR3)2]
(R = iPr, Cy) (15).[5c,5e]
Figure 4. Variable temperature 31P{1H} NMR spectra (121.5 MHz) of
cis,trans-[Ir(F)2(SF3)(CO)(PEt3)2] (11).
for CO ligands in iridium(III) carbonyl complexes at δ =
160.3 ppm.[24d,24f,25]
The trifluorosulfanyl complex 11 is very much prone to hy-
drolysis. Treatment of 11 with H2O in the presence of an ex-
cess of CsF resulted in the formation of cis,trans-[Ir(F)2(SOF)
(CO)(PEt3)2] (12) (Scheme 3). The addition of CsF or Et3N is
needed to remove the HF, which is formed by the hydrolysis.
However, complex 12 converts further into a mixture of com-
pounds within 2 days, of which 6, SPEt3 and F2PEt3 were
identified based on 31P{1H} and 19F NMR spectroscopy (Fig-
ure S21, Supporting Information).[21]
Figure 5. Section of the simulated (top) and experimental (bottom)
31P{1H} NMR spectrum of cis,trans-[Ir(F)2(SOF)(CO)(PEt3)2] (12) at
298 K. The following shifts and coupling constants were obtained from
2
2
2
the simulation: δ = 13.1 (Pa, JPa,Pb = 342.0, JPa,F = 27.6, JPa,F
=
3
2
2
33.6, JPa,F = 5.5 Hz) and 9.7 (Pb, JPa,Pb = 342.0, JPb,F = 32.6,
3
2JPb,F = 28.6, JPb,F = 10.8 Hz) ppm.
By addition of equimolar amounts of AsF5 to 11 a sulfur
bound fluoride of the SF3 unit can be abstracted to give
cis,trans-[Ir(F)2(SF2)(CO)(PEt3)2][AsF6] (13) along with un-
known impurities (about 2% based on the 31P{1H} NMR spec-
trum; Figure S25, Supporting Information) (Scheme 3). Evapo-
ration of the solvent resulted in a brownish oil as well as in an
increasing amount of the side products. Similar reactions are
reported
trans-[Pt(F)(SF3)(PR3)2] (R
BF3
for
trans-[Ir(Cl)(F)(SF3)(CO)(PEt3)2]
and
=
iPr, Cy) yielding with
trans-[Ir(Cl)(F)(SF2)(CO)(PEt3)2][BF4]
and
trans-[Pt(F)(SF2)(PR3)2][BF4] (R = iPr, Cy), respectively.[5c,5e]
Four resonances were observed in the 19F NMR spectrum
of the SF2 complex 13 at δ = –36.8, –65.7, –334.8 and
–336.6 ppm in an integral ratio of 2:6:1:1 (Figure S26, Sup-
Scheme 3. Reactivity of cis,trans-[Ir(F)2(SF3)(CO)(PEt3)2] (11).
The 19F NMR spectrum of 12 shows three resonances at δ porting Information). The most lowfield shifted resonance ap-
3
= 0.7, –318.3 and –337.6 ppm of equal intensity. The broad pears as a triplet of doublet of doublets (3JF,P = 14, JF,F = 11,
multiplet at δ = 0.7 ppm can be assigned to the fluorine atom 3JF,F = 8 Hz) and is in good accordance with a cationic SF2
of the SOF unit, which is in accordance with literature da- ligand bound to a transition metal center.[5c,5e,5h] A broad sig-
ta.[5e,5h] A doublet of triplets for one of the iridium bound nal at δ = –65.7 ppm (Δν1/2 = 1190 Hz) appears for the anion
fluorides is observed at δ = –318.3 ppm exhibiting couplings AsF6–.[27] The two resonances for the metal bound fluorides in
to a fluoride as well as two phosphorus atoms in the cis posi- 13 at δ = –334.8 and –336.6 ppm show a typical 2JF,F coupling
2
tion (2JF,F = 140, JF,P = 32 Hz).[5c,5f,15a,24b,24d–24f] For the of 157 Hz accompanied by a strong roof effect for both doublet
other metal bound fluorine at δ = –337.6 ppm a broad doublet of triplet of triplets.[5f,15a,24b,24e] The coupling to the equivalent
2
with the JF,F of 140 Hz is detected.[5f,15a,24b,24e]
phosphorus atoms of the phosphine ligands in the cis position
In the 31P{1H} NMR spectrum of 12, an AB pattern can be results in a 2JF,P coupling constant of 32 Hz and 37 Hz, respec-
observed (Figure 5, bottom). The spectrum has been simulated tively.[5c,5f,15a,24d,24f] A coupling to the two sulfur bound fluor-
3
(Figure 5, top) and the phosphine ligands couple to three fluor- ine atoms is also observed in both resonances, exhibiting JF,F
ine atoms as well as the other phosphorus nucleus in the trans couplings of 11 Hz and 8 Hz. Comparable couplings have been
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an ATR unit (diamond). Mass spectra were measured with a Micro-
observed for other iridium(III) and platinum(II) complex-
es.[5c,5e,24d,24f,28]
mass Q-TOF-2 mass spectrometer, which was equipped with a Linden
LIFDI source (Linden CMS GmbH). Microanalyses were performed
with a HEKAtech Euro EA Elemental Analyzer.
At 263 K, the 31P{1H} NMR spectrum shows a doublet of
doublet of triplets at δ = 24.6 ppm for 13 with corresponding
coupling constants.[5c,5e] The IR spectrum of the obtained oil
shows prominent absorption bands at 692 cm–1 and 675 cm–1,
which can be attributed to modes of the hexafluoroarsenate
anion (Figure S37, Supporting Information).[27a,29] The CO
stretching mode at 2064 cm–1 confirms the presence of an irid-
ium compound in oxidation state +III.[15a,24c,30]
Structure Determination of Complexes 9 and 10: The data were
collected at a BRUKER D8 VENTURE area detector, Mo-Kα radiation
(λ = 0.71073 Å). All measurements were performed at 100(2) K.
Multi-scan absorption corrections implemented in SADABS were ap-
plied to the data.[32] The structures were solved by intrinsic phasing
method (SHELXT-2015) and refined by full-matrix least square pro-
cedures based on F2 with all measured reflections (SHELXL-2015)
with anisotropic temperature factors for all non-hydrogen atoms.[33]
All hydrogen atoms were added geometrically and refined on using a
riding model.
Conclusions
In conclusion, we reported on the selective formation of
cis,trans-[Ir(F)2(SF3)(CO)(PEt)2] (11) by reaction with SF4. As
starting compound trans-[Ir(F)(CO)(PR3)2] [6: R = Et, 7: R =
Ph, 8: R = iPr, 9: R = Cy, 10: R = tBu] has to be prepared by
exchange of the chlorido ligand. It is intriguing that only the
latter complex 6 and trans-[Ir(F)(CO)(PPh3)2] react with SF4
to yield the oxidative addition product, whereas
trans-[Ir(F)(CO)(PR3)2] [8: R = iPr, 9: R = Cy, 10: R = tBu]
do not react.
When compared to the analogous rhodium compound
cis,trans-[Rh(F)2(SF3)(CO)(PEt)2], complex 11 shows an en-
hanced stability allowing for manipulations at room tempera-
ture, although an isolation was not possible. SF3 complexes
are very rare, but the hydrolysis of 11 as well as the reaction
with a Lewis acid is in accordance with the behavior of other
transition metal or organo substituted λ4-trifluorosulfanyl
units.[5c,5e,7a,7c,31]
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.
Copies of the data can be obtained free of charge on quoting the de-
pository numbers CCDC-1976836 (9) and CCDC-1976842 (10)
(Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://
www.ccdc.cam.ac.uk).
General Procedure for the Synthesis of trans-[Ir(F)(CO)(PR3)2]: A
PFA tube was loaded with Me4NF (1.2 equiv.) and [Ir(Cl)(CO)(PR3)2]
(1–5) (1 equiv.) dissolved in CH2Cl2 was added. After 15 min the sol-
vent was removed in vacuo and the residue was extracted with n-
hexane. Removing all volatiles from the extract gave 6 as a yellow oil
and 7–10 as yellow powders in 98%, 80%, 97%, 82% and 93% yield.
Analytical
Data
for
trans-[Ir(F)(CO)(PEt3)2]
(6):
1H
NMR (300.1 MHz, C6D6, 298 K): δ = 1.81 (mq, 3JH,H = 7.5 Hz, 12 H,
3
3
PCH2CH3), 1.06 ppm (mt, JH,H = 7.5 Hz, 18 H, PCH2CH3); JH,H
-
3
and JH,P-coupling constants were determined from a 1H{31P} NMR
spectrum. 19F NMR (282.4 MHz, C6D6, 298 K): δ = –264.8 ppm (t,
2JF,P = 33 Hz). 31P{1H} NMR (121.5 MHz, C6D6, 298 K): δ =
25.9 ppm (d, 2JP,F = 33 Hz) ppm. MS (LIFDI TOF, toluene): calcd. for
Experimental Section
+
C13H30FIrOP2 [M+]: m/z 476.5, found: 476.2. IR (ATR, diamond): ν˜
General Methods and Instrumentation: The synthetic work was car-
ried out with a Schlenk line or in a glove box in an atmosphere of
argon. All reactions involving SF4 and AsF5 were performed on a
stainless steel vacuum line with a defined volume. The reactions were
performed in 15 mm o.d. and 3.8 mm o.d. PFA tubing.
= 1925 (vs, CO), 490 (m, Ir–F) cm–1. Complex trans-[Ir(F)(13CO)
(PEt3)2] (6Ј) was prepared in a similar manner by using trans-[Ir(Cl)
(13CO)(PEt3)2] (1Ј). Selected spectroscopic data for 6Ј: 13C{1H}
2
NMR (75.5 MHz, [D8]toluene, 298 K): δ = 174.1 ppm (dt, JC,F = 84,
2JC,P = 10 Hz). 19F NMR (282.4 MHz, C6D6, 298 K): δ = –264.8 ppm
2
2
(dt, JC,F = 84, JF,P = 33 Hz). 31P{1H} NMR (121.5 MHz, [D8]tol-
Caution! Sulfur tetrafluoride and arsenic pentafluoride are highly toxic
gases. Exposure to these chemicals can cause serious injuries.
2
2
uene, 298 K): δ = 25.9 ppm (dd, JP,F = 33, JC,P = 10 Hz). IR (ATR,
diamond): ν˜ = 1878 (vs, 13CO) cm–1.
All solvents were purified and dried by conventional methods and dis-
tilled under an atmosphere of argon before use or directly condensed
into the reaction vessel. The complexes trans-[Ir(Cl)(CO)(PR3)2][1:
R = Et , 2: R = Ph, 3: R = iPr, 4: R = Cy] were prepared based on
Analytical Data for trans-[Ir(F)(CO)(PiPr3)2] (8): 1H
3
NMR (300.1 MHz, C6D6, 298 K): δ = 2.48 [mhept, JH,H = 7.2 Hz, 6
3
H, PCH(CH3)2], 1.31 ppm [md, JH,H = 7.2 Hz, 36 H, PCH(CH3)2];
3JH,H -coupling constants were determined from a 1H{31P} NMR spec-
literature-known
procedures.
The
preparation
of
trans-
2
trum. 19F NMR (282.4 MHz, C6D6, 298 K): δ = –256.0 ppm (t, JF,P
[Ir(Cl)(CO)(PtBu3)2] (5) was done analogous. SF4 (99%), AsF5
(99.9%) and Me4NF were obtained from ABCR and used without fur-
ther purification. Traces of thionyl fluoride and SF6 were present in
sulfur tetrafluoride but did not interfere with the chemistry. The NMR
spectra were acquired with a Bruker DPX 300 or a Bruker Avance
300 spectrometer. The 1H and 13C{1H} NMR chemical shifts were
referenced to residual C6D5H at δ = 7.15 ppm CDHCl2 at δ = 5.32 ppm
or toluene-d7 at δ = 2.09 ppm. The 13C{1H} NMR chemical shifts were
= 26 Hz). 31P{1H} NMR (121.5 MHz, C6D6, 298 K): δ = 49.45 ppm
+
(d, 2JP,F = 26 Hz). MS (LIFDI TOF, toluene): calcd. for C19H42FIrOP2
[M+]: m/z 560.2, found: 560.5. IR (ATR, diamond): ν˜ = 1916 (vs, CO),
487 (m, Ir–F) cm–1. C19H42FIrOP2 (560.23): calcd. C 40.77, H 7.56%;
found C 41.15, H 7.64%.
Analytical
Data for
trans-[Ir(F)(CO)(PCy3)2] (9): 1H
2.43 [m, H,
PCH(CH2)2(CH2)2CH2], 2.19 [m, 12 H, PCH(CH2)2(CH2)2CH2],
referenced to [D8]toluene at δ = 137.84 ppm. The 19F NMR spectra NMR (300.1 MHz, C6D6, 298 K):
were referenced to external CFCl3 at δ = 0.0 ppm and the 31P{1H}
δ
=
6
NMR spectra to external 85% H3PO4 at δ = 0.0 ppm. IR spectra were 1.76 [m, 24 H, PCH(CH2)2(CH2)2CH2], 1.26 ppm [m, 24 H,
recorded with a Bruker Vertex 70 spectrometer that was equipped with PCH(CH2)2(CH2)2CH2]. 19F NMR (282.4 MHz, [D8]toluene, 298 K):
Z. Anorg. Allg. Chem. 2020, 1–9
www.zaac.wiley-vch.de
5
© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
δ = –255.0 ppm (t, 2JF,P = 26 Hz). 31P{1H} NMR (121.5 MHz, [D8]tol-
steel line. After a reaction time of 12 h at 263 K the mixture was
uene, 298 K): δ = 39.3 ppm (d, JP,F = 26 Hz). MS (LIFDI TOF, tolu- degassed and equimolar amounts of AsF5 were condensed onto the
2
ene): calcd. for C37H66FIrOP2 [M+]: m/z 800.4, found: 800.7.
IR (ATR, diamond): ν˜ = 1924 (vs, CO), 490 (m, Ir–F) cm–1.
C37H66FIrOP2 (644.33): calcd. C 55.54, H 8.31; found C 55.41, H
8.27.
solution. The PFA tube was sealed and transferred to the NMR spec-
trometer. The formation of cis,trans-[Ir(F)2(SF2)(CO)(PEt)2][AsF6]
(13) was observed by NMR spectroscopy upon thawing of the mixture.
+
1
Spectroscopic data for 13: H NMR (300.1 MHz, CD2Cl2, 263 K): δ
3
3
= 2.21 (mq, JH,H = 7.7 Hz, 12 H, PCH2CH3), 1.22 ppm (mt, JH,H
=
Analytical Data for trans-[Ir(F)(CO)(PtBu3)2] (10): 1H
NMR (300.1 MHz, [D8]toluene, 298 K): δ = 1.60 (pseudo triplet,
I3JH,P+5JH,PI = 11.8 Hz). 19F NMR (282.4 MHz, [D8]toluene, 298 K):
δ = –243.3 ppm (t, 2JF,P = 24 Hz). 31P{1H} NMR (121.5 MHz, [D8]tol-
7.7 Hz, 18 H, PCH2CH3); the 3JH,H-coupling constant was determined
by a 1H{31P} NMR spectrum. 19F NMR (282.4 MHz, CD2Cl2, 263 K):
δ = –36.8 (tdd, 2F, SF2), –65.7 (br., 6F, AsF6), –334.8 (dtt, 2JF,F = 157,
2JF,P = 32, JF,P = 11 Hz, 1F, IrF), –336.6 ppm (dtt, JF,F = 157, JF,P
3
2
2
2
= 37, JF,F = 8 Hz, 1F, IrF). 31P{1H} NMR (121.5 MHz, CD2Cl2,
3
uene, 298 K): δ = 71.5 ppm (d, JP,F = 24 Hz). MS (LIFDI TOF, tolu-
+
ene): calcd. for C25H54FIrOP2 [M+]: m/z 644.3, found: 644.6.
2
2
3
263 K): δ = 24.6 ppm (ddt, JF,P = 37, JP,F = 32, JP,F = 14 Hz).
IR (ATR, diamond): ν˜ = 2064 (s, CO), 692 (vs, AsF6), 675 (vs, AsF6)
cm–1.
IR (ATR, diamond): ν˜ = 1910 (vs, CO), 492 (m, Ir–F) cm–1.
C25H54FIrOP2 (644.33): calcd. C 46.64, H 8.45; found C 46.78, H
8.54.
Supporting Information (see footnote on the first page of this article):
Spectra, computational details, crystallographic data.
Formation of cis,trans-[Ir(F)2(SF3)(CO)(PEt)2] (11): In a PFA tube
trans-[Ir(F)(CO)(PEt3)2] (6) (23 mg, 0.05 mmol) was dissolved in
[D8]toluene. The solution was degassed in vacuo and 1 equiv. of SF4
(0.05 mmol) was condensed into the PFA tube at 77 K. After sealing
the PFA tube and storing the reaction mixture at 243 K for 16 h,
cis,trans-[Ir(F)2(SF3)(CO)(PEt)2] (11) was identified by NMR spec-
troscopy. Selected spectroscopic data for 11: 1H NMR (300.1 MHz,
Acknowledgements
We acknowledge the DFG (Deutsche Forschungsgemeinschaft) for fin-
ancial support. We also thank Stefan Sander for scientific discussions.
3
[D8]toluene, 298 K): δ = 1.94 (mq, JH,H = 7.5 Hz, 12 H, PCH2CH3),
3
3
0.96 ppm (mt, JH,H = 7.6 Hz, 18 H, PCH2CH3); the JH,H-coupling
constant was determined by
1H{31P} NMR spectrum. 19F
NMR (282.4 MHz, [D8]toluene, 243 K): δ = 67.5 (br., 2F, IrSF2F),
Keywords: Sulfur fluorides; Iridium; S–F activation; Fluor-
ido complexes; Sulfur tetrafluoride
a
2
2
2
–64.9 (t, JF,F = 71 Hz, 1F, IrSF2F), –314.6 (dt, JF,F = 143, JF,P
=
34 Hz, 1F, IrF), –366.6 ppm (2JF,F = 143, JF,P = 29 Hz, 1F, IrF).
2
31P{1H} NMR (121.5 MHz, [D8]toluene, 298 K): δ = 11.7 ppm (dd,
References
2JP,F = 34, JP,F = 29 Hz).
2
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Complex cis,trans-[Ir(F)2(SF3)(13CO)(PEt)2] (11Ј) was prepared in a
similar manner by using trans-[Ir(F)(13CO)(PEt3)2] (6Ј). Selected spec-
troscopic data for 11Ј: 13C{1H} NMR (75.5 MHz, [D8]toluene, 298 K):
2
2
2
δ = 160.33 ppm (dtd, JC,F = 77, JC,P = 7, JC,F = 5 Hz). 19F
NMR (282.4 MHz, [D8]toluene, 298 K): δ = 67.5 (br., 2F, IrSF2F),
2
2
2
–64.9 (br., 1F, IrSF2F), –314.6 (dtd, JF,F = 143, JF,P = 34, JF,C
=
77 Hz, 1F, IrF), –366.6 ppm (2JF,F = 143, JF,P = 29, JF,C = 5 Hz, 1F,
IrF). 31P{1H} NMR (121.5 MHz, [D8]toluene, 298 K): δ = 11.7 ppm
(ddd, JP,F = 34, JP,F = 29, JC,P = 7 Hz). MS (LIFDI TOF, toluene):
calcd. for C1213CH30F4IrOP2S+ [M+-F]: m/z 566.11; found: m/z 566.13
2
2
2
2
2
Formation of cis,trans-[Ir(F)2(SOF)(CO)(PEt3)2] (12): A sample of
cis,trans-[Ir(F)2(SF3)(CO)(PEt)2] (11) (0.09 mmol) was prepared as
described above, but either in the presence of 30 equivalents of CsF
or 10 equivalents of Et3N. The purity of the sample was verified by
NMR spectroscopy at 243 K. The PFA tube was placed in a Young
NMR tube, opened and 2 μL (1.2 Eq., 0.11 mmol) of H2O was added
with a microliter syringe at room temperature. The formation of 12
was monitored by NMR spectroscopy. Selected spectroscopic data for
1
12: H NMR (300.1 MHz, [D8]toluene, 298 K): δ = 2.06–1.73 (m, 12
H, PCH2CH3), 0.96 ppm (m, 18 H, PCH2CH3). 19F NMR (282.4 MHz,
[D8]toluene, 298 K): δ = 0.7 (br. m, 1F, SOF), –318.3 (dt, 2JF,F = 140,
2
2JF,P = 32.4 Hz, 1F, IrF), –337.6 ppm (dm, JF,F = 140 Hz, 1F, IrF).
31P{1H} NMR (121.5 MHz, [D8]toluene, 298 K): δ = 11.3 ppm (m,
2
2
2
2
3
2JP,P = 342, JP,F = 33, JP,F = 32, JP,F = 29, JP,F = 28, JP,F = 10,
3JP,F = 7 Hz). The chemical shift and the coupling constants of the
31P{1H} NMR spectrum were obtained by simulation.
Treatment of cis,trans-[Ir(F)2(SF3)(CO)(PEt)2] (11) with AsF5: A
sample of cis,trans-[Ir(F)2(SF3)(CO)(PEt)2] (11) (0.09 mmol) was pre-
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Journal of Inorganic and General Chemistry
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Zeitschrift für anorganische und allgemeine Chemie
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Received: January 23, 2020
Published Online: ᭿
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Journal of Inorganic and General Chemistry
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N. Pfister, M. Bui, T. Braun,* P. Wittwer, M. Ahrens ...... 1–9
Synthesis and Reactivity of Iridium(I) Fluorido Complexes:
Oxidative Addition of SF4 at trans-[Ir(F)(CO)(PEt3)2]
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