Synthesis, structure and reactivity of iridium hydrido fluorido complexes

Article abstract of DOI:10.1002/ejic.201100917

The oxidative addition of HF at trans-[Ir(Ar^F) (η²-C₂H₄)(PiPr₃)₂] (1a: Ar^F = 4-C₅NF₄; 1b: Ar^F = 2-C₆H₃F₂) affords the fluorido complexes trans-[Ir(Ar^F)(F)(H)(PiPr₃)₂] (2a: Ar ^F = 4-C₅NF₄; 2b: Ar^F = 2-C ₆H₃F₂). The hydrido fluorido complex 2a is also accessible by means of the reaction of the hydroxido complex trans-[Ir(4-C ₅NF₄)(H)(OH)(PiPr₃)₂] (3a) with Et₃N·3HF. Both compounds 2a and 2b react with CO to give the carbonyl complexes trans-[Ir(4-C₅NF₄)(F)(H)(CO)(PiPr ₃)₂] (4a: Ar^F = 4-C₅NF₄; 4b: Ar^F = 2-C₆H₃F₂). In the presence of traces of water, a slow reaction of 2a with CO₂ yields the hydrogencarbonato complex trans-[Ir(4-C₅NF₄)(H)( ²-(O,O)-O₂COH)(PiPr₃)₂] (5a). Upon using 2a or 2b as fluorinating agent, Ph₃SiH could be converted into Ph₃SiF and CH₃C(O)Cl into CH₃C(O)F. The oxidative addition of HF at trans-[Ir(4-C₅NF₄) (I·²-C₂H₄)(PiPr₃) ₂] affords the fluorido complex trans-[Ir(4-C₅NF ₄)(F)(H)(PiPr₃)₂], which exhibits a square-pyramidal configuration. The latter reacts with acetyl chloride to yield acetyl fluoride and trans-[Ir(4-C₅NF₄)(Cl)(H)(PiPr ₃)₂].

Full text of DOI:10.1002/ejic.201100917

FULL PAPER
DOI: 10.1002/ejic.201100917
Synthesis, Structure and Reactivity of Iridium Hydrido Fluorido Complexes
Paul Kläring,[a] Ann-Katrin Jungton,[a] Thomas Braun,*[a] and Carsten Müller[b]
Keywords: Fluorinated ligands / Hydride ligands / Iridium / Fluorination
The oxidative addition of HF at trans-[Ir(ArF)(η2-C2H4)-
(PiPr3)2] (1a: ArF = 4-C5NF4; 1b: ArF = 2-C6H3F2) affords the
fluorido complexes trans-[Ir(ArF)(F)(H)(PiPr3)2] (2a: ArF = 4-
the carbonyl complexes trans-[Ir(4-C5NF4)(F)(H)(CO)(PiPr3)2]
(4a: ArF = 4-C5NF4; 4b: ArF = 2-C6H3F2). In the presence of
traces of water, a slow reaction of 2a with CO2 yields the
C5NF4; 2b: ArF = 2-C6H3F2). The hydrido fluorido complex 2a hydrogencarbonato complex trans-[Ir(4-C5NF4)(H)(κ2-(O,O)-
is also accessible by means of the reaction of the hydroxido
complex trans-[Ir(4-C5NF4)(H)(OH)(PiPr3)2] (3a) with
Et3N·3HF. Both compounds 2a and 2b react with CO to give
O2COH)(PiPr3)2] (5a). Upon using 2a or 2b as fluorinating
agent, Ph3SiH could be converted into Ph3SiF and CH3C-
(O)Cl into CH3C(O)F.
ever, the most common procedures represent halide ex-
change reactions when using metal fluorides such as KF,
CsF, TlF, AgF or other nucleophilic fluoride sources.[5,7,12]
Herein we report the synthesis of the IrIII–fluorido–hyd-
rido complexes trans-[Ir(ArF)(F)(H)(PiPr3)2] (2a: ArF = 4-
C5NF4; 2b: ArF = 2-C6H3F2) by oxidative addition of HF
when using Et3N·3HF as the HF source. Studies on their
reactivity towards CO, Ph3SiH and CH3C(O)Cl are also de-
scribed.
Introduction
The interest in transition-metal-mediated fluorido com-
plexes has increased rapidly in the last two decades because
of their remarkable reactivity[1] and their role as possible
intermediates in C–F bond activation reactions[2] or transi-
tion-metal-mediated fluorination reactions.[3] Various tran-
sition-metal-mediated fluorination reactions can be ac-
complished by nucleophilic or electrophilic fluorination of
a transition-metal-bound substrate.[3,4] C–F bond-forming
reactions with the participation of transition-metal fluor-
ides are also known.[3,5] The formation of fluoroaromatics
by reductive elimination as C–F bond-forming step from
transition-metal aryl fluorides has been a challenge for a
long time, but considerable progress has been made in the
last decade.[3,6] Recently, Watson and Buchwald et al. devel-
oped a palladium catalyst that allows the catalytic fluorina-
tion of aryl halides and triflates when using CsF or AgF as
fluorinating agent.[7] In this case, the reductive elimination
of aryl fluorides is achieved by a decreased electron density
at the metal centre as a consequence of a sterically de-
manding phosphane ligand, which blocks the fourth coordi-
nation site at the palladium aryl fluorido intermediate.
Transition-metal fluorido complexes can, for instance, be
prepared by oxidative addition of a C–F bond.[2b–2e,2g,8]
Other reactions include the oxidation of a transition-metal
Results and Discussion
Treatment of the IrI ethylene complexes trans-[Ir(ArF)-
(η2-C2H4)(PiPr3)2] (1a: ArF = 4-C5NF4; 1b: ArF = 2-
C6H3F2)[13] with Et3N·3HF in THF at room temperature
led to the formation of fluorido hydrido complexes
trans-[Ir(ArF)(F)(H)(PiPr3)2] (2a: ArF = 4-C5NF4; ArF
=
2b: 2-C6H3F2) (Scheme 1). Compound 2a can also be syn-
thesized by a reaction of the hydrido hydroxido complex
trans-[Ir(4-C5NF4)(H)(OH)(PiPr3)2] (3a) with Et3N·3HF
(Scheme 1).[14] Mechanistically, this conversion might pro-
ceed by an oxidative addition of HF at a reactive 14-elec-
tron species, which can be formed by reductive elimination
of water from 3a. It was shown before that 3a is susceptible
to the reductive elimination of water.[14,15] However, a pro-
tonation of the hydroxido ligand to give water and 2a is
also conceivable.
[9]
complex with XeF2 or with elemental fluorine[10] as well
as conversions that involve HF or its derivatives.[11] How-
The 31P{1H} NMR spectrum of 2a displays a doublet of
4
doublets at δ = 39.5 ppm (2JF,P = 16.3 Hz, JF,P = 9.4 Hz)
[a] Humboldt-Universität zu Berlin,
for the phosphane ligands in a trans configuration. Four
multiplets in a 1:1:1:1 ratio can be found in the 19F{1H}
NMR spectrum for the fluorine atoms of the tetrafluoro-
pyridyl ligand. This indicates a hindered rotation about
the Ir–C bond.[13,16] A broad singlet at δ = –267.4 ppm veri-
fies the presence of the fluorido ligand.[9h,12a,17] The signal
remains broad at low temperature (223 K). The hydrido li-
Department of Chemistry,
Brook-Taylor-Straße 2, 12489 Berlin, Germany
Fax: +49-30-2093-3913
E-mail: thomas.braun@chemie.hu-berlin.de
[b] Freie Universität Berlin,
Department of Chemistry and Biochemistry,
Takustraße 3, 14195 Berlin, Germany
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201100917.
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Iridium Hydrido Fluorido Complexes
molecules 2a and 2b show an approximately square-planar
arrangement of the metal-bound fluorine atom, the metal-
bound carbon atom of the aryl unit and the phosphane
ligands, which are in a mutually trans configuration. The
hydrido ligand was located for neither 2a nor 2b but is ex-
pected to occupy an apical coordination site, which results
in an overall square-pyramidal structure. DFT calculations
for 2a and 2b verify the suggested square-pyramidal struc-
tures and the apical position of the metal-bound hydrogen
atoms (see the Supporting Information; Figures 3 and 4).
The Ir–F bond lengths [2a 2.039(2) Å, 2b 2.0508(17) Å] are
comparable to those in other IrIII fluorido complexes, as,
for example, in [Ir{η5-C5(CH3)4(CH2CH3)}(F)(Ph)(PMe3)]
[2.069(4) Å], [Ir(Cp*)(F)(RF)(PMe3)] [2.070(2) Å for
RF
= = CF2CF2CF3;
CF2CF3; 2.055(3) Å for RF
2.074(3) Å for RF = CF(CF3)2] and [Ir(F)(H)2(PtBu2Ph)2]
Scheme 1. Synthesis of the IrIII fluorido hydrido complexes 2a and
2b.
1
gand gives rise to a multiplet at δ = –40.28 ppm in the H
NMR spectrum, which simplifies to a triplet (2JH,P
=
12.0 Hz) upon 19F decoupling and to a doublet of doublets
upon 31P decoupling (2JH,F = 12.1 Hz, 4JH,F = 2.8 Hz). The
IR spectrum of 2a shows an absorption band at ν =
˜
455 cm–1, which could possibly be assigned to the Ir–F
stretching vibration.[18] A DFT frequency-mode analysis
shows frequencies at 445 cm–1 for a coupled H–Ir–F vi-
bration and at 2482 cm–1 (very weak) for the Ir–H stretch-
ing vibration. An absorption band for the Ir–H vibration
was not found in the IR spectrum of 2a. Comparable spec-
troscopic data were found for the difluorophenyl fluorido
complex trans-[Ir(2-C6H3F2)(F)(H)(PiPr3)2] (2b).
The molecular structures of 2a and 2b were determined
by X-ray diffraction analyses at 100 K (Figures 1 and 2).
Suitable crystals of 2a were grown from an n-pentane solu-
tion at 243 K; crystals of 2b were obtained by slow evapora-
tion of the solvent from an n-hexane solution. Selected
bond lengths and angles are summarized in Table 1. Both
Figure 2. An ORTEP diagram of 2b. Ellipsoids are drawn at the
50% level; hydrogen atoms at the aromatic ring and at the iPr
groups are omitted for clarity.
Table 1. Selected bond lengths [Å] and angles [°] in trans-[Ir(4-
C5NF4)(F)(H)(PiPr3)2] (2a) and trans-[Ir(2-C6H3F4)(F)(H)(PiPr3)2]
(2b) with estimated standard deviations in parentheses.
Compound 2a
Compound 2b
Ir1–P1
Ir1–P2
Ir1–F1
2.3425(9)
2.3518(10)
2.039(2)
1.998(3)
1.388(5)
1.397(7)
1.324(10)
1.293(10)
1.364(6)
1.401(5)
1.347(6)
1.334(7)
1.341(7)
1.359(6)
Ir1–P1
Ir1–P2
Ir1–F1
Ir1–C1
C1–C2
C2–C3
C3–C4
C4–C5
C5–C6
C1–C6
C20–F2
C21–F3
2.3292(7)
2.3255(7)
2.0508(17)
2.018(3)
1.392(4)
1.387(4)
1.381(5)
1.389(5)
1.387(4)
1.395(4)
1.371(3)
1.377(3)
Ir1–C19
C19–C20
C20–C21
C21–N1
C22–N1
C22–C23
C19–C23
C20–F2
C21–F3
C22–F4
C23–F5
P1–Ir1–P2
P1–Ir1–C19 93.30(11)
P2–Ir1–C19 96.81(11)
P1–Ir1–F1
P2–Ir1–F1
C19–Ir1–F1 172.39(13)
169.85(3)
P1–Ir1–P2
P1–Ir1–C1
P2–Ir1–C1
P1–Ir1–F1
P2–Ir1–F1
C1–Ir1–F1
170.24(3)
95.85(8)
92.90(8)
86.52(5)
86.44(5)
162.44(10)
85.99(8)
83.87(8)
Figure 1. An ORTEP diagram of 2a. Ellipsoids are drawn at the
50% level; hydrogen atoms at the iPr groups are omitted for clarity.
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P. Kläring, A.-K. Jungton, T. Braun, C. Müller
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[2.045(9) Å].[5a,12a,12c] The calculation of the structural in-
dex parameter τ, introduced by Addison and Reedijk et al.,
furnishes a value of τ = 0.04 for 2a and τ = 0.13 for 2b.[19]
Whereas τ is close to zero for square-pyramidal structures,
τ is equal to unity for trigonal-bipyramidal systems.
Scheme 2. Reactivity of 2a and 2b towards CO and CO2/H2O.
The 31P{1H} NMR spectrum of 4a displays a doublet at
2
δ = 21.4 ppm with a coupling constant of JF,P = 22.0 Hz,
Figure 3. DFT-optimized structure for 2a. The hydrogen atoms at
the iPr groups are omitted for clarity.
which indicates a cis configuration of the phosphane groups
and the fluorido ligand. Four multiplets in the 19F{1H}
NMR spectrum indicate a hindered rotation of the tetra-
fluoropyridyl ligand about the Ir–C bond.[13,16] A broad
singlet can be found at δ = –444.3 ppm for the metal-bound
1
fluorine atom.[5a,9h,17] The H NMR spectrum of 4a shows
a multiplet for the hydrido ligand at δ = –5.90 ppm. The
multiplet simplifies to a triplet (2JH,P = 15.2 Hz) upon 19F
decoupling and to a doublet of doublets (2JH,F = 14.8 Hz,
4JH,F = 9.6 Hz) upon 31P decoupling. The trans configura-
tion of the hydrido and the carbonyl ligand was verified by
2
determination of the JH,C coupling constant of 53.0 Hz in
the isotopomer trans-[Ir(4-C5NF4)(F)(H)(13CO)(PiPr3)2]
(4aЈ), which is characteristic of a trans arrangement.[21] The
IR spectrum of 4a exhibits an absorption band at 2170 cm–1
for the Ir–H vibration, and one at 2010 cm–1 for the
CϵO vibration of the carbonyl ligand.[13,14] Comparable
spectroscopic data have been found for trans-[Ir(2-
C6H3F2)(F)(H)(CO)(PiPr3)2]
(4b)
and
trans-[Ir(2-
C6H3F2)(F)(H)(13CO)(PiPr3)2] (4bЈ).
Treatment of a solution of 2a with CO2 showed initially
no reactivity of 2a towards CO2. However, after several
days the formation of trans-[Ir(4-C5NF4)(H){κ2-(O,O)-
O2COH}(PiPr3)2] (5a) could be detected by NMR spec-
Figure 4. DFT-optimized structure for 2b. The hydrogen atoms at
the aromatic ring and at the iPr groups are omitted for clarity.
Treatment of 2a or 2b with CO afforded the formation troscopy (Scheme 2).[14] We presume that in the presence
of the carbonyl complexes trans-[Ir(ArF)(F)(H)(CO)- of adventitious water the hydrido hydroxido complex trans-
(PiPr3)2] (4a: ArF = 4-C5NF4; 4b: ArF = 2-C6H3F2) [Ir(4-C5NF4)(H)(OH)(PiPr3)2] was generated, which reacts
(Scheme 2). In solution, 4a decomposes slowly at room tem- rapidly with CO2 to give 5a, which was reported pre-
perature to form the IrI carbonyl complex trans-[Ir(4- viously.[14]
C5NF4)(CO)(PiPr3)2] (6a), which was characterized be-
Tertiary silanes can be considered to be good reagents
fore.[13] An insertion of the carbonyl ligand into the Ir–F for the replacement of a fluorido by a hydrido ligand.[22]
bond to give a fluoroacyl species[9a,9b] was not observed. Indeed, treatment of 2a or 2b with an excess amount of
We also have no indication for the reductive elimination of Ph3SiH afforded the formation of Ph3SiF and the corre-
2,3,5,6-tetrafluoropyridine or even pentafluoropyr- sponding dihydrido complexes trans-[Ir(ArF)(H)2(PiPr3)2]
idine.[6,7,20]
(7a: ArF = 4-C5NF4; 7b: ArF = 2-C6H3F2) (Scheme 3),
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Eur. J. Inorg. Chem. 2012, 1430–1436

Iridium Hydrido Fluorido Complexes
which were described and characterized before.[13] In ad-
A reaction of the fluorido hydrido carbonyl complex
dition to the signals of 7a or 7b, the 19F NMR spectra of trans-[Ir(4-C5NF4)(F)(H)(CO)(PiPr3)2] (4a) with acetyl
the reaction mixtures showed a singlet at δ = –169.2 ppm chloride gave also acetyl fluoride and trans-[Ir(4-
with 29Si satellites (1JF,Si = 282.5 Hz) for Ph3SiF.[23] The C5NF4)(Cl)(H)(CO)(PiPr3)2] (9a) (Scheme 4). A singlet at δ
presence of Ph3SiF was also confirmed by an 1H,29Si = 13.1 ppm in the 31P{1H} NMR spectrum of 9a could be
HMBC NMR spectrum, which shows a doublet at δ(29Si) assigned to the phosphanes in a mutual trans position.
= –3.5 ppm (1JF,Si = 284 Hz).[23] Note that complex 4a does Again four multiplets in the 19F{1H} NMR spectrum indi-
not react with Ph3SiH (Scheme 4).
cate a restricted rotation of the tetrafluoropyridyl ligand
1
about the Ir–C bond.[13,16] The H NMR spectrum of 9a
shows a multiplet at δ = –7.99 ppm, which simplifies to a
triplet upon 19F decoupling (2JH,P = 16.2 Hz) and to a
doublet upon 31P decoupling (4JH,F = 15.3 Hz). For the iso-
topomer trans-[Ir(4-C5NF4)(Cl)(H)(13CO)(PiPr3)2] (9aЈ) a
carbon–hydrogen coupling of 54.4 Hz indicates a trans ar-
rangement of the hydrido and the carbonyl ligand. The IR
spectrum of 9a displays two absorption bands at ν =
˜
2276 cm–1 for the Ir–H moiety and at ν = 2015 cm–1 for the
˜
CϵO vibration.
Conclusion
In this paper, we have reported the synthesis of the fluor-
ido hydrido complexes trans-[Ir(ArF)(F)(H)(PiPr3)2] (2a:
ArF = 4-C5NF4; 2b: ArF = 2-C5H3F2) by oxidative addition
of HF at trans-[Ir(ArF)(η2-C2H4)(PiPr3)2] (1a: ArF = 4-
C5NF4; 1b: ArF = 2-C6H3F2) species. Reactivity studies re-
veal that trans-[Ir(4-C5NF4)(F)(H)(PiPr3)2] (2a) and its de-
rivative trans-[Ir(4-C5NF4)(F)(H)(CO)(PiPr3)2] (4a) act as a
source of fluoride to convert acetyl chloride into acetyl
fluoride. However, we did not observe the formation of
C–H or C–F bonds by reductive elimination, whereas an
HF elimination occurs from trans-[Ir(4-C5NF4)(F)(H)(CO)-
(PiPr3)2] (4a) to yield trans-[Ir(4-C5NF4)(CO)(PiPr3)2] (6a).
Scheme 3. Reactivity of 2a towards Ph3SiH and CH3C(O)Cl.
Experimental Section
General: All experiments were performed with a Schlenk line under
an atmosphere of argon or in an argon-filled glovebox with oxygen
levels below 10 ppm. All solvents were dried by stirring with Na/K
and then distilled under an atmosphere of argon. 13CO was com-
mercially available from Sigma Aldrich. Compounds trans-[Ir(4-
C5NF4)(η2-C2H4)(PiPr3)2] (1a) and trans-[Ir(2-C6H3F2)(η2-
C2H4)(PiPr3)2] (1b) were prepared according to the literature.[13]
The NMR spectra were recorded with a Bruker DPX 300 NMR
spectrometer at 298 K. The 1H NMR spectroscopic chemical shifts
were referenced to residual C6D5H at δ = 7.16 ppm or [D7]THF at
δ = 1.72 ppm. The 19F NMR spectra were referenced to external
C6F6 at δ = –162.9 ppm and the 31P{1H} NMR spectra were refer-
enced externally to H3PO4 at δ = 0.0 ppm. Microanalyses were per-
formed with a HEKAtech Euro EA elemental analyzer. Infrared
spectra were recorded with a a Bruker Vertex 70 spectrometer
equipped with an ATR unit (diamond).
Scheme 4. Reactivity of 4a towards CH3(O)Cl.
Upon treatment of 2a with acetyl chloride, a quantitative
conversion occurs at room temperature within a few min-
utes. Acetyl fluoride and the hydrido chlorido complex
trans-[Ir(4-C5NF4)(Cl)(H)(PiPr3)2] (8a) were detected by
NMR spectroscopy (Scheme 3). The 31P{1H} NMR spec-
trum shows a singlet at δ = 33.5 ppm for the phosphane
ligands, which are in a mutual trans configuration. Four
signals in the 19F NMR spectrum can be assigned to the
fluorine atoms of the tetrafluoropyridyl ligand in 8a. A
quartet at δ = 48.6 ppm (3JH,F = 7.2 Hz) indicates the pres-
ence of acetyl fluoride.[24] In the 1H NMR spectrum, a
doublet of triplets at δ = –41.15 ppm (2JH,P = 12.4 Hz, 4JH,F
= 5.7 Hz) can be found for the hydrido ligand.
trans-[Ir(4-C5NF4)(F)(H)(PiPr3)2] (2a): A solution of trans-[Ir(4-
C5NF4)(η2-C2H4)(PiPr3)2] (1a) (238 mg, 0.345 mmol) in THF
(21 mL) was treated with Et3N·3HF (23 μL, 0.141 mmol) at room
temperature. The reaction mixture turned from dark red to orange.
After stirring for 16 h, all the volatile compounds were removed
under vacuum and the residue was then extracted with n-pentane
(10 mL). The volatile compounds were evaporated under vacuum
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P. Kläring, A.-K. Jungton, T. Braun, C. Müller
FULL PAPER
from the extract and a yellow powder remained; yield 161 mg
(68%). C23H43F5IrNP2 (682.75): calcd. C 40.46, H 6.35, N 2.05;
temperature. The solution turned from yellow to pale yellow within
seconds. All volatile compounds were removed under vacuum to
found C 40.89, H 6.36, N 2.10. IR (ATR): ν = 455 cm–1 (Ir–F). 1H yield a yellow residue; yield 170 mg (93%). IR (ATR): ν = 2209
˜
˜
3
2
NMR (300.1 MHz, C6D6): δ = 2.17 (dsept, JH,H = 7.1, JH,P
7.1 Hz, 6 H, CH), 1.01 (dd, JH,H = 7.1, JH,P = 7.1 Hz, 18 H,
CH3), 0.98 (dd, JH,H = 7.1, JH,P = 7.1 Hz, 18 H, CH3),
=
(Ir–H), 2003 cm–1 (CϵO). 1H NMR (300.1 MHz, C6D6): δ = 6.76–
3
3
3
2
6.49 (br. m, 3 H, 2-C6H3F2), 2.28 (dsept, JH,H = 7.1, JH,P =
3
3
3
3
7.1 Hz, 6 H, CH), 1.19 (dd, JH,H = 7.1, JH,P = 7.1 Hz, 18 H,
2
2
4
3
3
–40.28 ppm (tdd, JH,P = 12.0, JH,F = 12.1, JH,F = 2.8 Hz, 1 H,
CH3), 1.10 (dd, JH,H = 7.1, JH,P = 7.1 Hz, 18 H, CH3), –5.51
IrH); the coupling constants were obtained from 1H{19F} and
(tdd, 2JH,P = 15.7, 2JH,F = 9.3, 4JH,F = 14.0, 1 H, IrH); the coupling
1H{31P} NMR spectra. 19F{1H} NMR (282.4 MHz, C6D6): δ = constants were obtained from the 1H{31P} and 1H{19F} NMR
–98.8 (m, 1 F), –102.3 (m, 1 F), –123.8 (m, 1 F), –126.4 (m, 1 F),
spectra. 19F NMR (282.4 MHz, C6D6): δ = –73.4 (m, 1 F), –76.8
–267.4 ppm (br. s, 1 F). 31P{1H} NMR (121.5 MHz, C6D6): δ = (m, 1 F), –441.0 (br. s, 1 F). 31P{1H} NMR (121.5 MHz, C6D6): δ
2
4
2
39.5 ppm (dd, JF,P = 16.3, JF,P = 9.4 Hz).
= 20.0 (d, JF,P = 19.5 Hz). Treatment with 13CO forms the iso-
topomer trans-[Ir(2-C6H3F2)(F)(H)(13CO)(PiPr3)2] (4bЈ). 31P{1H}
trans-[Ir(2-C6H3F2)(F)(H)(PiPr3)2] (2b): Et3N·3HF (150 μL,
0.920 mmol) was added to a solution of trans-[Ir(2-C6H3F2)(η2-
C2H4)(PiPr3)2] (1b) (300 mg, 0.459 mmol) in THF (20 mL). The
solution turned from dark red to orange while being stirred at room
temperature. After 16 h, all the volatile compounds were removed
under vacuum and the residue was washed with n-pentane (10 mL)
to yield 226 mg of an oily orange residue. The residue was then
dissolved in THF (15 mL), and the solution was treated with CsF
(798 mg, 5.253 mmol) at 323 K for 2 h to remove residual HF. After
filtration, the volatile compounds were removed under vacuum
2
NMR for 4bЈ (121.5 MHz, C6D6): δ = 20.7 ppm (dd, JF,P = 19.3,
2JC,P = 6.0 Hz).
Treatment of trans-[Ir(4-C5NF4)(F)(H)(PiPr3)2] (2a) with Ph3SiH:
Compound 2a (6 mg, 0.009 mmol) was dissolved in C6D6 (0.7 mL).
Then Ph3SiH (15 mg, 0.058 mmol) was added to the solution,
which turned from yellow to orange within minutes. cis–trans-[Ir(4-
C5NF4)(H)2(PiPr3)2] (7a) and Ph3SiF could be detected by NMR
spectroscopy. Complex 7a was identified by comparison of the
NMR spectroscopic data with the literature data.[13] Analytical
data for Ph3SiF: 19F NMR (282.4 MHz, C6D6): δ = –169.2 ppm (s,
1
from the filtrate. An orange oil remained; yield 221 mg (74%). H
1
1
with 29Si satellites, JF,Si = 282.5 Hz). H,29Si HMBC (79.5 MHz,
C6D6): δ(29Si,1H) = –3.5/7.7 ppm (d, 1JF,Si = 284 Hz); 2b reacts with
Ph3SiH in a similar manner to form Ph3SiF and 7b.
NMR (300.1 MHz, C6D6): δ = 6.76–6.49 (br. m, 3 H, 2-C6H3F2),
3
2
3
2.35 (dsept, JH,H = 7.1, JH,P = 7.1 Hz, 6 H, CH), 1.15 (dd, JH,H
3
= 7.1, JH,P = 7.1 Hz, 36 H, CH3), –40.08 ppm (m, 1 H, IrH);
the JH,H coupling constant was determined by a 31P decoupling
3
Treatment of trans-[Ir(4-C5NF4)(F)(H)(PiPr3)2] (2a) with CH3C-
(O)Cl: CH3C(O)Cl (6 μL, 0.084 mmol) was added to a solution of
2a (53 mg, 0.078 mmol) in THF (12 mL). NMR spectra of the mix-
ture revealed the presence of trans-[Ir(4-C5NF4)(Cl)(H)(PiPr3)2]
(8a) and CH3C(O)F only. Compound 8a was isolated by evapora-
tion of the volatile compounds from the reaction mixture. Analyti-
cal data for 8a: C23H43ClF4IrNP2 (699.21): calcd. C 39.51, H 6.20,
N 2.00; found C 39.17, H 6.29, N 1.49. 1H NMR (300.1 MHz,
C6D6): δ = 2.34 (dsept, 3JH,H = 7.1, 2JH,P = 7.1 Hz, 6 H, CH), 0.98
(dd, 3JH,H = 7.1, 3JH,P = 7.1 Hz, 36 H, CH3), –41.15 ppm (dt, 2JH,P
experiment. 19F{1H} NMR (282.4 MHz, C6D6): δ = –88.3 (m, 1 F),
–91.3 (m, 1 F), –267.0 ppm (br. s, 1 F). 31P{1H} NMR (121.5 MHz,
2
4
C6D6): δ = 37.7 ppm (dd, JF,P = 17.2, JF,P = 4.3 Hz).
trans-[Ir(4-C5NF4)(F)(H)(CO)(PiPr3)2] (4a): A solution of trans-
[Ir(4-C5NF4)(F)(H)(PiPr3)2] (2a) (21 mg, 0.031 mmol) in C6D6
(0.6 mL) was treated with CO gas at room temperature. The solu-
tion turned pale yellow within seconds. The NMR and IR spectra
revealed
a quantitative conversion into trans-[Ir(4-C5NF4)-
(F)(H)(CO)(PiPr3)2] (4a). After storage at room temperature for
several days, the formation of trans-[Ir(4-C5NF4)(CO)(PiPr3)2] (6a)
was detected in the reaction mixture. Analytical data for trans-[Ir(4-
4
= 12.4, JH,F = 5.7 Hz, 1 H, IrH). 19F NMR (282.4 MHz, C6D6):
δ = –99.5 (m, 1 F), –101.3 (m, 1 F), –121.6 (m, 1 F), –127.6 ppm
(m, 1 F). 31P{1H} NMR (121.5 MHz, C6D6): δ = 33.5 ppm (s).
Analytical data for CH3C(O)F: 19F NMR (282.4 MHz, C6D6): δ =
C NF )(F)(H)(CO)(PiPr ) ] (4a): IR (ATR): ν = 2170 (Ir–H), 2010
˜
5
4
3 2
cm–1 (CϵO). H NMR (300.1 MHz, C6D6): δ = 2.10 (dsept, JH,H
1
3
3
48.6 ppm (q, JH,F = 7.2 Hz).
2
3
3
= 7.1, JH,P = 7.1 Hz, 6 H, CH), 1.03 (dd, JH,H = 7.1, JH,P
=
3
3
7.1 Hz, 18 H, CH3), 0.98 (dd, JH,H = 7.1, JH,P = 7.1 Hz, 18 H,
Treatment of trans-[Ir(4-C5NF4)(F)(H)(CO)(PiPr3)2] (4a) with
CH3C(O)Cl: A solution of 4a (18 mg, 0.025 mmol) in C6D6
(0.7 mL) was treated with CH3C(O)Cl (2 μL, 0.028 mmol). The
quantitative formation of trans-[Ir(4-C5NF4)(Cl)(H)(PiPr3)2] (9a)
and CH3C(O)F was detected by NMR spectroscopy. Evaporation
of the volatile compounds afforded complex 9a as a pale yellow
powder. Analytical data for 9a: C24H43ClF4IrNOP2 (727.22): calcd.
2
2
4
CH3), –5.90 ppm (tdd, JH,P = 15.2, JH,F = 9.6, JH,F = 14.8 Hz,
1 H, IrH); the coupling constants were obtained from the H{31P}
1
and H{19F} NMR spectra. 19F{1H} NMR (282.4 MHz, C6D6): δ
1
= –98.5 (m, 1 F), –98.9 (m, 1 F), –109.4 (m, 1 F), –113.5 (m, 1 F),
–444.3 ppm (br. s, 1 F). 31P{1H} NMR (121.5 MHz, C6D6): δ =
2
21.4 ppm (d, JF,P
= 22.0 Hz). The isotopomer trans-[Ir(4-
C5NF4)(F)(H)(13CO)(PiPr3)2] (4aЈ) can be prepared analogously
C 39.64, H 5.96, N 1.93; found C 39.68, H 6.48, N 1.93. IR (ATR):
upon treatment of 2a with 13CO. Analytical data for 4aЈ: 1H NMR
1
ν = 2276 (Ir–H), 2015 cm–1 (CϵO). H NMR (300.1 MHz, C6D6):
˜
3
2
3
2
(300.1 MHz, C6D6): δ = 2.10 (dsept, JH,H = 7.1, JH,P = 7.1 Hz, 6
H, CH), 1.03 (dd, JH,H = 7.1, JH,P = 7.1 Hz, 18 H, CH3), 0.98
δ = 2.16 (dsept, JH,H = 7.1, JH,P = 7.1 Hz, 6 H, CH), 1.06 (dd,
3
3
3JH,H = 7.1, JH,P = 7.1 Hz, 18 H, CH3), 0.95 (dd, JH,H = 7.1,
3
3
3
3
3JH,P = 7.1 Hz, 18 H, CH3), –7.99 ppm (dt, JH,P = 16.2, JH,F
=
2
4
(dd, JH,H = 7.1, JH,P = 7.1 Hz, 18 H, CH3), –5.90 ppm (tddd,
2JH,C = 53.0, JH,P = 15.2, JH,F = 9.6, JH,F = 14.8 Hz, 1 H, IrH);
the coupling constants were obtained from the 1H{31P} and
1H{19F} NMR spectra. 31P{1H} NMR (121.5 MHz, C6D6): δ =
2
2
4
15.3 Hz, 1 H, IrH). 19F NMR (282.4 MHz, C6D6): δ = –97.4 (m, 1
F), –97.8 (m, 1 F), –105.4 (m, 1 F), –110.0 ppm (m, 1 F). 31P{1H}
NMR (121.5 MHz, C6D6): δ = 13.1 ppm (s).
2
2
21.4 ppm (dd, JF,P = 22.0, JC,P = 6.2 Hz). Complex 6a was iden-
tified by comparison of the NMR spectroscopic data with the lit-
erature data.[13]
Structure Determination: Yellow crystals of 2a were obtained by
slow evaporation of the solvent from an n-pentane solution at 243
K. Suitable crystals of 2b were grown from an n-hexane solution
trans-[Ir(2-C6H3F2)(F)(H)(CO)(PiPr3)2] (4b): A slow stream of CO at room temperature. The diffraction data were collected with a
was bubbled through solution of trans-[Ir(2-C6H3F2)- STOE IPDS 2Θ diffractometer at 100 K. Crystallographic data are
(F)(H)(PiPr3)2] (2b) (175 mg, 0.271 mmol) in THF (5 mL) at room depicted in Table 2. The structures were solved with direct methods
a
1434
www.eurjic.org
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 1430–1436

Iridium Hydrido Fluorido Complexes
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(SHELXTL PLUS or SIR97) and refined with the full-matrix least-
squares method on F2 (SHELXL-97).[25] Hydrogen atoms were
placed at calculated positions and refined using a riding model.
The hydrogen atoms bound at iridium were not located.
Table 2. Crystallographic data.
2a
2b
Crystal dimensions [mm3] 0.07ϫ0.06ϫ0.05 0.32ϫ0.30ϫ0.08
Crystal colour
Empirical formula
Mr
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
orange
C23H43F5IrNP2
682.75
monoclinic
P21/n
9.2726(2)
24.0899(4)
11.8937(3)
–
90.025(2)
–
2656.77(10)
4
1.707
5.193
yellow
C24H46F3IrP2
645.78
triclinic
[3]
¯
P1
8.3249(3)
10.2917(3)
16.4867(5)
79.991(2)
83.239(3)
71.438(2)
1315.73(7)
2
1.630
5.226
2.11 to 29.18
24890
7075
γ [°]
V [Å3]
Z
Dcalcd. [mgm–3]
μ(Mo-Kα) [mm–1]
θ range [°]
Reflns. collected
Indep. reflns.
Rint
[4]
2.35 to 30.49
15607
8092
0.0289
0.1067
Completeness
Absorption correction
GoF on F2
R1, wR2 (all data)
R1, wR2 [I0 Ͼ2σ(I0)]
99.7
numerical
0.992
99.5
numerical
1.126
0.0247, 0.0670
0.0225, 0.0664
1.204 / –3.237
0.0418, 0.0785
0.0316, 0.0758
Max diff. peak/hole [eÅ–3] 1.363 / –2.404
CCDC-841984 (for 2a) and -841983 (for 2b) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[5]
[6]
Supporting Information (see footnote on the first page of this arti-
cle): Computational details for 2a and 2b for this article is available.
Acknowledgments
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The authors gratefully acknowledge support from the GRK “Flu-
orine as a Key Element” funded by the Deutsche Forschungsge-
meinschaft. We would like to thank Dr. B. Braun and Dr. S. Mebs
for helpful discussions concerning the X-ray crystal-structure
analyses as well as Prof. B. Paulus (FU Berlin) for support with
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Received: August 31, 2011
Published Online: December 21, 2011
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