The Versatile Behavior of Platinum Alkyne Complexes towards XeF2: Formation of Fluorovinyl and Fluorido Complexes

Article abstract of DOI:10.1002/chem.201700403

Reactions of platinum(0) tolane complexes, bearing a chelating ligand with P and N donor atoms, with the electrophilic fluorinating agent XeF₂ give facile access to platinum(II) β-fluorovinyl fluorido complexes. A series of new platinum(II) β-fluorovinyl complexes have been synthesized and were structurally characterized. Further oxidation with XeF₂ led to ortho-metalated platinum(IV) fluorido compounds. Additional reactions of platinum(0) tolane complexes, bearing a chelating P,P donor ligand, with XeF₂ led to a variety of fluorido and fluorovinyl complexes.

Full text of DOI:10.1002/chem.201700403

A Journal of
Accepted Article
Title: The Versatile Behavior of Platinum Alkyne Complexes Towards
XeF2: Formation of Fluorovinyl and Fluorido Complexes
Authors: Thomas Braun, Josefine Berger, Theresia Ahrens, Paul
Kläring, Reik Laubenstein, and Beatrice Braun-Cula
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The Versatile Behavior of Platinum Alkyne Complexes Towards
XeF2: Formation of Fluorovinyl and Fluorido Complexes
Josefine Berger[a], Thomas Braun*[a], Theresia Ahrens[a], Paul Kläring[a], Reik Laubenstein[a], Beatrice
Braun-Cula[a]
ligands at ruthenium centers by an outer-sphere electrophilic
reaction pathway.[70] We reported on the reactivity of platinum(0)
alkyne complexes towards the electrophilic fluorinating agent
NFSI yielding for instance [Pt(PhC=CFPh){N(SOPh2)2}{κ2-(P,N)-
iPr2PC2H4NMe2}] which bears a β-fluorovinyl ligand.[71] Note that
in literature β-fluorovinyl gold complexes are discussed to be
intermediates in catalytic fluorination of symmetric and
asymmetrical internal alkynes to give fluorinated olefins.[72–78]
In this paper we present studies on the behavior of platinum(0)
tolane complexes towards the electrophilic fluorinating agent
XeF2. The conversions result in the formation of β-fluorovinyl
platinum(II) fluorido complexes. Difluorido platinum(IV)
complexes are identified as orthometalated products as a result
of C-H activation steps at the phenyl group of the β-fluorovinyl
ligand.
Abstract: Reactions of platinum(0) tolane complexes, bearing a
chelating ligand with P and N donor atoms, with the electrophilic
fluorinating agent XeF2 give facile access to platinum(II)-β-fluorovinyl
fluorido complexes.
A series of new platinum(II)-β-fluorovinyl
complexes have been synthesized and structurally characterized.
Further oxidation with XeF2 led to orthometalated platinum(IV)
fluorido compounds. Additional reactions of platinum(0) tolane
complexes, bearing a chelating P,P donor ligand, with XeF2 led to a
variety of fluorido and fluorovinyl complexes.
Introduction
Due to their unique properties fluorinated compounds play an
important role in medicine[1–9] as well as in agrochemical[10] and
material science.[11–19] One approach to access fluorinated
building blocks involves metal-mediated fluorination reactions,
which can often be regarded as efficient alternatives to
conventional fluorination methods.[20–39] The C−F bond formation
generally takes place either by electrophilic or nucleophilic
fluorination of the ligand or the metal. For the latter, metal
fluorido species can be intermediates which then for instance
undergo C−F reductive elimination.[23,27,40–52] Thus, Pd(IV) metal
fluorido complexes are accessible by electrophilic fluorination
and were for example reported by Ritter et al. and Sanford et
al.[20,23,29,53–62] It was shown that a C−F bond formation at an aryl
palladium(IV)-difluorido complex is feasible.[62–64] For the
electrophilic fluorination at diaryl platinum(II) complexes with
XeF2 a competing aryl-aryl elimination is favored over the C−F
Results and Discussion
Synthesis and reactivity of platinum(II) fluorido complexes
Treatment of the platinum(0) tolane complexes [Pt(L)(ƞ2-
PhC≡CPh)] (1, 2) (L = κ2-(P,N)-iPr2PC3H6NMe2: 1, κ2-(P,N)-
iPr2PC2H4NMe2: 2) with XeF2 in CH2Cl2 gave the platinum(II)
complexes [Pt(PhC=CFPh)(F){κ2-(P,N)-iPr2PC3H6NMe2}] (3) and
[Pt(PhC=CFPh)(F){κ2-(P,N)-iPr2PC2H4NMe2}] (4)
bearing
a
β-fluorovinyl as well as a fluorido ligand (Scheme 1). Thus, metal
and ligand fluorination occurred simultaneously.
bond
formation.[56,65–67]
Vigalok
and
coworkers
also
demonstrated a selective reductive elimination of a C(aryl)−F
bond at the platinum(IV) complex [Pt(Mes)(F)2(py){κ2-(P,O)-
Ad2PC6H4O}] (Mes = mesityl, py = pyridine, Ad = adamantyl).[57]
Gagné et al. reported on C(sp3)−F bond formation reactions and
also propose a reductive C−F elimination at a cationic Pt(IV)
center.[68,69]
[Pt(alkyl)(PPP)]BF4
Cationic
platinum
alkyl
complexes
like
(PPP = bis(2-diphenylphosphinoethyl)-
phenylphosphine) convert with electrophilic fluorinating agents
such as XeF2 or N-Fluorobenzenesulfonimid (NFSI) into
fluorinated organic alkyl compounds, like benzylfluoride.[68]
Scheme 1. Fluorination of the platinum(II) tolane complexes 1, 2.
Examples for which
a fluorinated ligand remains in the
coordination sphere of the metal after the C-F bond formation
step are very rare.[55,66] Lynam, Slattery and coworkers
described recently the formation fluorinated alkenyl and alkyl
Complex
4
was synthesized before by
a
reaction of
with
[Pt(PhC=CFPh){N(SOPh2)2}{κ2-(P,N)-iPr2PC2H4NMe2}]
tetra-n-butylammoniumfluoride (tbaf).[71] The NMR data of 3 are
comparable to those of 4. The 31P{1H} NMR spectrum of 3
shows
a
doublet at δ = 6.6 ppm with 195Pt satellites
(2JP,Ftrans = 179 Hz, JPt,P = 4369 Hz). The resonance for the
metal-bound fluorido ligand appears in the 19F{1H} NMR
spectrum (Figure 1) as a doublet of doublets at high field with
1
[a]
Dr. J. Berger, Prof. Dr. T. Braun, Dipl.-Chem. T. Ahrens, Dr. P.
Kläring, Dipl.-Chem. R. Laubenstein, Dr. B. Braun-Cula
Department of Chemistry, Humboldt-Universität zu Berlin
Brook-Taylor Str. 2, 12489 Berlin (Germany)
195Pt satellites (δ = -206.9 ppm, JF,F = 3 Hz, JP,Ftrans = 179 Hz,
1JPt,F = 156 Hz). The chemical shift as well as the coupling
constant are characteristic of a transition metal bound fluorido
ligand.[20,23,41,67,79–86] The β-fluorine atom causes a doublet with
195Pt satellites at δ = -91.9 ppm (4JF,F = 3 Hz, 3JPt,F = 260 Hz),
4
2
E-mail: thomas.braun@chemie.hu-berlin.de
Supporting information (crystallographic data and NMR spectra) for
this article is given via a link at the end of the document.
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NaBF4 in thf led to a cationic platinum species, which can be
assigned
iPr2PC2H4NMe2}]BF4 (5) (Scheme 2). The 31P{1H} NMR
spectrum of shows
singlet with 195Pt satellites at
to
be
[Pt(PhC=CFPh)(thf){κ2-(P,N)-
5
a
δ = 34.5 ppm (1JPt,P = 4716 Hz). The 19F{1H} NMR spectrum of 5
displays two singlets at δ = -92.5 and δ =-153.6 in a ratio of 1:4.
The former exhibits 195Pt satellites (3JPt,F = 235 Hz). The
coordination of a thf molecule to the platinum was confirmed by
1H NMR spectroscopy. In the spectrum appears an additional
set of thf signals at δ = 3.61 ppm and δ = 1.77ppm in a ratio of
1:1 next to the signals of the d7-thf solvent signal.[91] LIFDI-MS
data reveal a peak at m/z = 581 which was assigned to the [M-
thf]+ ion.
Figure 1. 19F{1H} NMR spectrum of 3 in CD2Cl2 (*denotes the 195Pt satellites).
which appears in the typical area for a β-fluorovinyl ligand.[71]
LIFDI-MS data reveal a peak at m/z 614 which can be assigned
to the [M]+ ion.
The molecular structure of 3 in the solid state was also
confirmed by X-ray analysis (Figure 2). The structure reveals a
square-planar arrangement of the chelating ligand and the vinyl-
and fluorido ligands at the platinum center. The Pt(1)−P(1) and
Pt(1)−N(1) bond lengths of 2.2060(6) Å and 2.173(2) Å are
consistent with those of other platinum(II) complexes bearing a
P,N-chelating ligand.[71,87,88] The Pt(1)−C(12) as well as the
Pt(1)−F(1) bond lengths of 2.024(2) Å and 2.0736(14) Å are
comparable with the Pt−C and Pt−F distances in
[Pt(PhC=CFPh)(FHF){κ2-(P,N)-iPr2PC2H4NMe2}]
[Pt−C:
2.0185(19) Å; Pt-F: 2.0948(11) Å].[71] The F(1)-Pt(1)-C(12) angle
of 87.01(7)° in 3 is slightly smaller than the analogous angle in
[Pt(PhC=CFPh)(FHF){κ2-(P,N)-iPr2PC2H4NMe2}]
(F-Pt-C
= 89.23(6)°). This is due to the larger bite angle of P(1)-Pt(1)-
Scheme 2. Synthesis of the platinum(II) complexes 5-9.
N(1) = 97.56(5)° in 3.[89,90]
However, the reaction of [Pt(PhC=CFPh)(thf){κ2-(P,N)-
iPr2PC2H4NMe2}]BF4 (5)
[Pt(PhC=CFPh)(CO){κ2-(P,N)-iPr2PC2H4NMe2}]BF4 (6). In the
absence of CO the complex converted into
with
CO
gave
slowly
6
[Pt(PhC=CFPh)(thf){κ2-(P,N)-iPr2PC2H4NMe2}]BF4 (5) at room
temperature over several days. There are no indications for an
insertion of CO into the Pt-C bond of the vinyl ligand.[92] The
31P{1H} NMR spectrum of 6 displays a doublet at δ = 49.91 ppm
with 195Pt satellites (4JP,F = 3 Hz, 1JPt,P = 3347 Hz). The
Pt,P-coupling constant is comparable with these found for other
literature known cationic platinum(II) complexes.[93,94] The
P,F-coupling constant was also observed in the 19F{1H} NMR
spectrum which reveals a doublet at δ = –91.3 ppm with195Pt
satellites (3JPt,F = 150 Hz) for the β-fluorovinyl ligand. The IR
spectrum of 6 reveals a ṽ(CO) absorption band at 2125 cm-1.
The value is in agreement with those found for other cationic
platinum carbonyl complexes.[93,95,96] The electron-poor nature of
the metal center in 6 is also in accordance with the high-field
Figure 2. ORTEP diagram of 3. Ellipsoids are drawn at the 50 % probability
level. The hydrogen atoms are omitted for clarity. Selected bond lengths [Å]
and angles [°] of complex 3: Pt(1)-N(1) 2.173(2), Pt(1)-P(1) 2.2060(6), Pt(1)-
C(12) 2.024(2),
Pt(1)-F(1) 2.0736(14),
C(12)-C(13) 1.334(3),
C(13)-
F(2) 1.401(3); F(1)-Pt(1)-C(12) 87.01(7), P(1)-Pt(1)-N(1) 97.56(5), C(12)-Pt(1)-
P(1) 91.61(6), Pt(1)-C(12)-C(13) 123.34(19), F(1)-Pt(1)-N(1) 83.77(7), C(12)-
C(13)-F(2) 117.8(2).
shift
of
the
13C
NMR
carbonyl
resonance
at
δ = 172.73 ppm.[93,95,96] The signal appears as a doublet, due to
the trans P,C-coupling of 2JP,C = 132 Hz.
The
[Pt(PhC=CFPh)(CO){κ2-(P,N)-
We did not observe any C-F reductive elimination at 3 or
4.[23,29,31,40,41,43,48,53] However, to evaluate the properties of the
fluorido complexes, reactivity studies at [Pt(PhC=CFPh)(F){κ2-
(P,N)-iPr2PC2H4NMe2}] (4) were carried out. Treatment of 4 with
identity
of
iPr2PC3H6NMe2}]BF4 (6) was further confirmed by X-ray
crystallography. Colorless crystals were obtained from a thf
solution of 6 under CO atmosphere (Figure 3). Crystals of 6 are
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twinned and have been refined as a two domain twin. The
asymmetric unit consists of two molecules which both have
essentially the same geometry; therefore only one will be
discussed. The platinum metal center exhibits an approximately
square planar geometry with P(1), N(1), C(11) and C(12)
occupying the four coordination sites. The Pt(1)−P(1),
Pt(1)−N(1) and Pt(1)−C(12) bond lengths are in good agreement
with the ones in complex 3. The distance C(11)−O(1) with
1.124(19) Å is similar to the bond length in the CO molecule
(1.128 Å).[95,97] This results in a rather long Pt(1)−C(11) bond
distance of 2.064(17) Å in comparison with, for example, the one
in
the
pincer
complex
[{C6H3(CH2PiPr2)2}Pt(CO)]OTf
(Pt−C = 1.919(3) Å).[95]
Figure 4. ORTEP diagram of 7. Ellipsoids are drawn at the 50 % probability
level. The hydrogen atoms are omitted for clarity. Selected bond lengths [Å]
and angles [°] of complex 7: Pt(1)-N(1) 2.186(2), Pt(1)-C(12) 2.021(2), Pt(1)-
P(1) 2.2708(6),
C(12)-C(13) 1.342(3),
Pt(1)-C(11) 2.131(2),
C(13)-
F(1) 1.398(3), C(11)-Pt(1)-C(12) 88.45(9), Pt(1)-P(1)-C(2) 103.04(8), C(12)-
Pt(1)-P(1) 96.07(7), Pt(1)-N(1)-C(1) 110.48(15), C(11)-Pt(1)-N(1) 90.72(8),
Pt(1)-C(12)-C(13) 127.24(18),
F(1) 117.5(2).
P(1)-Pt(1)-N(1) 84.55(6),
C(12)-C(13)-
the one in 3. Treatment of 4 with AgF and CF3SiMe3 under
sonication led to the generation of the trifluoromethyl complex
[Pt(PhC=CFPh)(CF3){κ2-(P,N)-iPr2PC2H4NMe2}] (8). Note that
the reaction does not occur on using
a
mixture of
CsF/CF3SiMe3.[99–105] It is likely that AgCF3 is formed
intermediately.[99,100,106–108] The 31P{1H} NMR spectrum of 8
reveals a quartet of doublets with 195Pt satellites at δ = 41.3 ppm
Figure 3. ORTEP diagram of the cation in 6. Ellipsoids are drawn at the 50 %
probability level. The hydrogen atoms and the BF4- anion are omitted for clarity.
Selected bond lengths [Å] and angles [°] of complex 6: Pt(1)-N(1) 2.176(11),
4
(3JP,F = 50 Hz, JP,F = 3.5 Hz, 1JPt,P = 2245 Hz). The P,F-coupling
C(11)-O(1) 1.124(19),
Pt(1)-P(1) 2.297(4),
C(12)-C(13) 1.35(2),
Pt(1)-
constant of 50 Hz indicates the trans arrangement of the CF3
ligand and the phosphorus atom.[109] The 19F{1H} NMR spectrum
display two signals in a ratio of 3:1. The signal for the CF3 ligand
appears as a doublet of doublets with 195Pt satellites at
C(11) 1.917(16), C(13)-F(1) 1.378(17), Pt(1)-C(12) 2.064(17), C(11)-Pt(1)-
C(12) 86.4(7),Pt(1)-C(12)-C(13) 120.1(13), C(12)-Pt(1)-P(1) 93.5(5), C(12)-
C(13)-F(1) 118.0(15), C(11)-Pt(1)-N(1) 96.4(6), Pt(1)-C(11)-O(1) 171.3(16),
P(1)-Pt(1)-N(1) 84.2(3).
5
2
δ = -30.8 ppm (3JP,F = 50 Hz, JF,F = 1.5 Hz, JPt,F = 616 Hz). The
fluorine atom in the β-position at the vinyl ligand gives rise to a
doublet of quartets with 195Pt satellites at δ = -101.9 ppm
In addition, the fluorido ligand in [Pt(PhC=CFPh)(F){κ2-(P,N)-
5
3
(4JP,F = 3.5 Hz, JF,F = 1.5 Hz, JPt,F = 278 Hz). LIFDI-MS data
reveal a peak at m/z 650 and 581 which can be assigned to the
[M]+ and [M-CF3]+ ion.
iPr2PC2H4NMe2}] (4) was replaced by
a methyl group on
treatment of 4 with MeLi yielding [Pt(PhC=CFPh)(Me){κ2-(P,N)-
iPr2PC2H4NMe2}] (7). The 31P{1H} NMR spectrum of 7 displays a
Irradiation of 8 over 12 h led to a β-F-elimination at the vinyl
doublet at δ = 50.2 ppm with JP,F = 4 Hz and 195Pt satellites
4
ligand
yielding
the
complex
[Pt(F)(CF3){κ2-(P,N)-
(1JPt,P = 1954 Hz). The β-fluoro vinyl ligand causes in the 19F{1H}
NMR spectrum a doublet with 195Pt satellites at δ = -104.9 ppm
(4JP,F = 4 Hz, 3JPt,F = 329 Hz). The presence of the methyl ligand
is evidenced by a doublet at δ = 1.03 ppm (3JP,H = 7 Hz) in the
1H NMR spectrum. The P,H-coupling constant confirms the trans
arrangement of the methyl ligand to the phosphorus atom of the
iPr2PC2H4NMe2 ligand.[98] The 195Pt satellites overlap in the 1D
spectrum with the signals for the isopropyl group, but a 1H,13C
HMQC spectrum reveals them to be 2JPt,H = 64 Hz.
iPr2PC2H4NMe2}] (9) and tolane.[25,110–113] The latter was
identified by GC-MS. Irradiation of a solution of complex 7 did
not result in the formation of a comparable metal fluorido
complex. Instead decomposition was observed. The 31P{1H}
NMR spectrum of
9 exhibits a doublet of quartet with
195Pt satellites at δ = 42.9 ppm (2JP,Ftrans = 157 Hz, JF,F = 7 Hz,
1JPt,P = 4178 Hz). In the 19F{1H} NMR spectrum the CF3 group
appears as a triplet at δ = -19.3 ppm, due to the similar P,F and
F,F coupling constants (3JP,F ≈ 3JF,F ≈ 7 Hz). The signal features
a Pt,F-coupling constant of 725 Hz. The metal-bound fluorido
ligand gives rise to a doublet of quartets at δ = -229.4 ppm with
3
The molecular structure of 7 was also determined by X-ray
diffraction studies (Figure 4). The unit cell of 7 contains two
independent molecules in the asymmetric unit, which exhibit
comparable bond lengths and angles. Therefore only one
molecule will be discussed. The platinum atom is coordinated in
a square-planar geometry by the phosphorus P(1) and nitrogen
N(1) atom of the iPr2PC2H4NMe2 ligand as well as by the C(11)
and C(12) atom of the methyl- and β-fluorovinyl ligand. The
Pt(1)−N(1) and Pt(1)−C(12) bond lengths are similar, whereas
the Pt(1)−P(1) of 2.2708(6) Å is slightly elongated compared to
the bond length in 3. The Pt(1)−C(11) bond length of 2.131(2) Å
is in good agreement with the one found for Pt−C = 2.112(3) Å in
195Pt satellites (2JP,Ftrans = 157 Hz, JF,F = 7 Hz, JPt,F = 165 Hz).
3
1
The P,F-coupling constant of 157 Hz indicates trans
a
arrangement of the fluorido ligand to the phosphorus atom of the
iPr2PC2H4NMe2 ligand. Note that neither for complex 7 nor for 8
a C−C coupling reaction by reductive elimination of a fluorinated
olefine was observed in the presence of tolane, although this
might be thermodynamically feasible.[101,102,104,105,114,115]
Formation of platinum(IV) fluorido complexes
the
complex
[Pt(CH3)(SEt)(dippe)]
(dippe = 1,2-
As mentioned above, there is some literature precedence on
C−F bond formation steps by reductive elimination at metal(IV)
fluorido complexes (M = Pd, Pt).[56,65–67] Therefore, the tolane
Bis(diisopropylphosphino)ethane).[98] As expected, the bite angle
P(1)-Pt(1)-N(1) of 7 with 84.55(6)° is smaller in comparison to
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complexes [Pt(L)(ƞ2-PhC≡CPh)] (1, 2) (L
=
κ2-(P,N)-
cyclometalated
product
[Pt(F)(κ2-(C,C)-bisphenyl)(PPP)]
iPr2PC3H6NMe2: 1, κ2-(P,N)-iPr2PC2H4NMe2: 2) were treated with
(PPP = bis(2-diphenylphosphinoethyl)phenylphosphine) under
HF elimination.
two equivalents of XeF2. The conversion resulted in the
formation
of
the
platinum(II)
vinyl
complexes
[Pt(PhC=CHPh)(F){L}] (L = 2-(P,N)-iPr2PC3H6NMe2: 10, κ2-
(P,N)-iPr2PC2H4NMe2: 11) as well as platinum(IV) complexes,
which we assign to be [Pt(F)2(o-C6H4CF=CPh)(L)] (L = κ2-(P,N)-
iPr2PC3H6NMe2: 12a/b,
κ2-(P,N)-iPr2PC2H4NMe2:
13a/b)
(Scheme 3). The latter are both generated as two isomers and
the complexes are not stable in solution. Reactivity studies show
no reductive elimination of fluorinated organic products.
Mechanistically, we propose a formal addition of two equiv. XeF2
at the starting compound to give [Pt(PhC=CFPh)(F)3{L}] (L = κ2-
(P,N)-iPr2PC3H6NMe2: 13a/b or κ2-(P,N)-iPr2PC2H4NMe2: 12a/b).
A subsequent C−H activation results in the orthometalated
products by concomitant HF elimination. The HF then converts
the unreacted starting material into the β-H-vinyl complexes
[Pt(PhC=CHPh)(F){L}] (10, 11) (L = κ2-(P,N)-iPr2PC3H6NMe2: 10,
κ2-(P,N)-iPr2PC2H4NMe2: 11). An independent reaction of [Pt(κ2-
(P,N)-iPr2PC2H4NMe2)(ƞ2-PhC≡CPh)]
(2)
with
Et3N∙3HF
confirmed this reactivity. The cyclometalation by aromatic C−H
activation has been demonstrated before at comparable
systems.[66,116] Thus, Gagné et al. described the reaction of
[Pt(2-bisphenyl)Ph(PPP)](BF4) with XeF2 to furnish the
Scheme 3. Formation of platinum(IV) fluorido complexes.
Figure 5. 19F{1H} NMR spectra and coupling constants (282 MHz) of 13a and 13b in CD2Cl2; the F,F- and P,F- coupling constants (Hz) are given as obtained from
the 19F{1H}-NMR and 31P{1H}-NMR spectra; the Pt,F-coupling constants are revealed in the 19F{1H} NMR spectra at 470 MHz. (See Supporting Information).
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The platinum(II) vinyl complexes [Pt(PhC=CHPh)(F){L}] (L = κ2-
(P,N)-iPr2PC3H6NMe2: 10, κ2-(P,N)-iPr2PC2H4NMe2: 11) show
comparable analytical data, and only 11 will be discussed. The
31P{1H} and the 19F{1H} NMR spectrum reveal each a doublet
with 195Pt satellites at δ = 33.2 ppm (2JP,Ftrans = 180 Hz,
The NMR spectra confirm that the molecular structure of each
isomer consist of two metal-bound fluorine atoms, one in the
cis- and one in the trans-position to the phosphorus atom. In
addition, 1H,13C-HMBC and 19F,13C-HMBC studies allowed
assignments of the configuration at the platinum centers. In the
1H,13C-HMBC spectrum of 13 the methyl protons bound at the
nitrogen moiety correlate with the carbon atom of an organyl
entity in the trans position (Figure 6). This can be considered to
be distinctive and similar correlations were observed for the
platinum(II) complexes 3-8. Thus, the resonances of the
prochiral methyl groups of the NMe2 moiety in 13a at
δ = 1.73 ppm and δ = 2.69 ppm correlate with a signal for an
aromatic carbon atom at δ = 127 ppm. The signals exhibit a
1JPt,P = 4560 Hz)
and
δ = 214.81
(2JP,Ftrans = 180 Hz,
1JPt,F = 276 Hz). The β-H atom causes a characteristic singlet
with 195Pt satellites in the 1H NMR spectrum at δ = 6.55 ppm
(3JPt,H = 78 Hz). The molecular structures of the isomers 12a/b
and 13a/b were deduced from their NMR spectra and LIFDI-
TOF-MS measurements. The NMR data for 12 and 13 are
comparable and only these for 13 will be discussed. Figure 5
shows the assignment of the P,F- and F,F-coupling constants in
13a/b to the suggested molecular structures. The 31P{1H} NMR
spectrum consist of two doublets of doublets at δ = 17.3 ppm
(13a) and δ = 20.4 ppm (13b) in a ratio of 1:0.3. The splitting
pattern of the signal of 13a are caused by the coupling of the
phosphorus atom to the fluorine atoms in the cis-position
(2JP,Fcis = 6 Hz) and in the trans-position (2JP,Ftrans = 160 Hz). The
1
Pt,C-coupling constant of JPt,C = 740 Hz. This suggests a trans
arrangement of orthometalated aromatic carbon atom and the
nitrogen atom of the iPr2PC2H4NMe2 ligand in the isomer 13a.
For the isomer 13b the 1H,13C-HMBC spectrum shows the cross
peaks connecting resonances for the prochiral methyl protons at
δ = 3.00 ppm and δ = 2.80 ppm with the α-vinyl carbon at
δ = 114 ppm; a value which is comparable with the data for the
2
corresponding P,F-coupling constants for 13b are JP,Fcis = 9 Hz
2
1
and JP,Ftrans = 160 Hz. The 195Pt satellites with JPt,P = 2848 Hz
other
platinum-β-fluorovinyl
complexes
like
[Pt(PhC=CFPh)(F){κ2-(P,N)-iPr2PC2H4NMe2}] (4).[71] Additional
information was provided by the 19F,13C-HMBC NMR spectrum.
For 13a the doublet of doublets of the α-vinyl-carbon atom
appears at δ = 104 ppm in the 13C domain (2JP,C = 6 Hz,
2JC,F = 22 Hz). The β-carbon atom give rise to a doublet of
doublet of doublets at δ = 157 ppm (J = 7 Hz, J = 28 Hz) with a
1
(13a) and JPt,P = 2860 Hz (13b) are in the typical range for
platinum(IV) complexes.[57,65,116] The β-F atoms in the 19F NMR
spectrum (Figure 5) generate two signals with a typical chemical
4
shift at δ = -114.1 ppm (4Jß- trans = 2.5 Hz, Jß- cis = 22 Hz,
F,F
F,F
3JPt,F = 197 Hz) (13a) and δ = -117.9 ppm (4Jß-
= 4 Hz,
trans
F,F
3JPt,F = 179 Hz) (13b) (the fluorine atoms in the trans-position to
the phosphorus atom are labeled Ftrans, whereas the fluorine
atoms in the cis-position to the phosphorus atom are labeled
Fcis). The resonances for the metal-bound fluorine atoms appear
1
C,F-coupling constant of JC,F = 265 Hz. A further signal for an
aromatic carbon atom appears at δ = 143 ppm (J = 7 Hz,
J = 30 Hz, J = 53 Hz). Comparable signals were found for the
Isomer 13b. LIFDI-MS spectrometry of 13 reveal peaks at m/z
618, 599, 580 which can be assigned to the [M]+ ion and the ions
[M-F]+, [M-2F]+.
as
a
doublet of doublets of doublets for 13a at
δ(Fcis) = -236.5 ppm (1JPt,F = 78 Hz) and δ(Ftrans) = -242.2 ppm
(1JPt,F = 110 Hz). For Fcis the pattern is caused by the coupling to
the phosphorus atom (2JP,Fcis = 6 Hz) and to the Ftrans
Reactivity of [Pt{κ2-(P,P)-Cy2PC2H4PCy2}(ƞ2-PhC≡CPh)] (14)
towards XeF2
(2JF
cis = 93 Hz) as well as to the β-F (4Jß- cis = 22 Hz). The
F,F
trans
,F
coupling constant of the Ftrans are 2JP,Ftrans = 160 Hz,
2JF
cis = 93 Hz and Jß- cis = 2.5 Hz. The resonances for the
4
It was shown in previous investigations that the platinum(0)
trans
,F
F,F
alkyne
complexes
[Pt(κ2-(P,N)-iPr2PC2H4NMe2)(ƞ2-
platinum bound fluorine atoms in 13b are δ(Fcis) = -221.5
(1JPt,F = 91 Hz) ppm and δ(Ftrans) = -237.2 (1JPt,F = 137 Hz) ppm
and the corresponding coupling constants are shown in Figure 5.
PhC≡CPh)] (2) and [Pt{κ2-(P,P)-Cy2PC2H4PCy2}(ƞ2-PhC≡CPh)]
(14) show
a different reactivity towards the electrophilic
fluorinating agent N-Fluorbenzensulfonimid (NFSI).[71] Therefore,
the complex [Pt{κ2-(P,P)-Cy2PC2H4PCy2}(ƞ2-PhC≡CPh)] (14)
was also treated with one equivalent XeF2 and the reaction was
monitored by NMR spectroscopy (Figure 7, Scheme 4).
1
In comparison to platinum(II)-fluorido species the JPt,F-coupling
constants for the metal-bound fluorine atoms in 13a/b are
considerable smaller.[116]
Scheme 4. Reaction of [Pt{κ2-(P,P)-Cy2PC2H4PCy2}(ƞ2-PhC≡CPh)] (14) with
XeF2.
Figure 6. Part of 1H,13C-HMBC NMR spectrum of 13a/b.
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Figure 8. ORTEP diagram of 15. Ellipsoids are drawn at the 50 % probability
level. The hydrogen atoms of the dcpe ligand and the FHF- anions are omitted
for clarity. Selected bond lengths [Å] and angles [°] of complex 15: Pt(1)-
P(1) 2.2152(5), O(1)-H(1) 0.8227, Pt(1)-P(2) 2.2057(5), F2-H2 1.35(4), Pt(1)-
O(1) 2.0646(14), H2-F1 0.95(4),
O(1)-Pt(1)-P(1) 99.11(5),
Pt(1)-O(1)-
H(1) 124.3, O(1)-Pt(1)-P(2) 173.90(5), F(1)-H(2)-F(2) 178.39, P(1)-Pt(1)-
P(2) 86.295(17).
Figure 7. 31P{1H} NMR spectrum of the reaction of [Pt{κ2-(P,P)-
Cy2PC2H4PCy2}(ƞ2-PhC≡CPh)] (14) with XeF2 in CD2Cl2,
1 h at -20°C
P,P-coupling constant appears to be rather small and couldn’t
be resolved.[124]
(bottom); 24 h at room temperature (top).
The signal at δ = 44.9 ppm with the larger P,F-coupling constant
2
1
of JP,Ftrans = 164 Hz and Pt,P-constant of JPt,P = 3933 Hz refers
to the phosphorus atom in the trans position to the fluorido
ligand, whereas the resonance at δ = 72.5 ppm with coupling
The NMR spectra of the reaction solution revealed the formation
of
[Pt(µ-OH){κ2-(P,P)-Cy2PC2H4PCy2}]2[FHF]2
(15)
and
[Pt(PhC=CFPh)(F){κ2-(P,P)-Cy2PC2H4PCy2}] (16) in a ratio of 1:4
even at low temperature. The binuclear complex 15 gives rise to
4
2
1
constants of JP,F = 45 Hz, JP,Fcis = 23 Hz and JPt,P = 2080 Hz
can be assigned to the phosphorus atom in cis position to the
fluorido ligand. In the 19F{1H} NMR spectrum a doublet of
doublets for the metal-bound fluorine atom appears at
a
singlet
with
platinum
satellites
at
δ = 61.0 ppm
(1JPt,P = 3452 Hz) in the 31P{1H} NMR spectrum (Figure 7) and a
1
broad singlet in the H NMR spectrum at δ = 6.07 ppm, which is
δ = -266.0 ppm with JP,Ftrans = 164 Hz, JP,Fcis = 23 Hz and 195Pt
satellites (1JPt,F = 210 Hz). Both the chemical shift as well as the
coupling constants are in good agreement with the data found
for other platinum fluorido compounds.[20,54,67,116] A doublet at
δ = -93.6 ppm with 195Pt satellites can be assigned to the
β-fluorine atom of the vinyl ligand (4JP,F = 45 Hz, 3JPt,F = 229 Hz).
Complex 16 is not stable in solution. By monitoring the reaction
solution by 31P{1H} NMR spectroscopy the transformation of 16
into two new complexes was observed. After 24 h at room
temperature the reaction mixture consisted of the platinum
difluorido complex [Pt(F)2{κ2-(P,P)-Cy2PC2H4PCy2}] (17), the
2
2
caused by the bridging µ-OH ligands. The data are comparable
with the one reported for binuclear platinum complexes [Pt(µ-
OH)(dppm)2]2(BF4)2
(dppm = 1,1-bis(diphenylphosphino)-
methane).[117] Presumably, 15 is generated from an intermediate
difluorido complex 17 by traces of water (see below). At room
temperature the FHF- anion exhibits
a broad singlet at
δ = 15.7 ppm in the 1H NMR spectrum, but no signal was
observed for the anion in the 19F NMR spectrum. Low
temperature NMR data of 15 at 233 K indeed reveal the
expected broad triplet with JHF ≈ 130 Hz in the 1H NMR spectrum
and the corresponding broad doublet at δ = -146.5 ppm in the
19F NMR spectrum.[118] The IR spectrum of 15 displays a broad
absorption band between 1600 cm-1 and 1800 cm-1, which is
compatible with a free bifluoride ion.[118–121]
orthometalated
Cy2PC2H4PCy2}]
Cy2PC2H4PCy2}]2[FHF]2 (15) in
product
(18)
[Pt(o-C6H4CF=CPh){κ2-(P,P)-
and
[Pt(µ-OH){κ2-(P,P)-
ratio of 2:2:1 (Figure 7,
a
Scheme 4). The concentration of 15 within the reaction
remained stable, which was proven by an external 31P standard.
Similarly as found for compound 8, the generation of complex
[Pt(F)2{κ2-(P,P)-Cy2PC2H4PCy2}] (17) can be explained by a β-F-
elimination resulting in diphenylacetylene as organic product,
which was detected by GC-MS measurements. The formation of
Crystals suitable for an X-ray analysis were formed in a PFA
tube from a thf or CH2Cl2 solution (Figure 8). Each platinum
center exhibits a square-planar coordination geometry. The
Pt(1)−O(1) = 2.0646(14) Å is shortened compared to the one in
the
literature
known
complex
(BArF = B[3,5-C6H3-(CF3)2]4 ,
The
[Pt(µ-OH){κ2-(P,P)-
-
Cy2PC2H4PCy2}]2[BArF]2
[Pt(o-C6H4CF=CPh){κ2-(P,P)-Cy2PC2H4PCy2}]
(18)
might
Pt(1)−O(1) = 2.147(5) Å).[122]
bond
lengths
thermodynamically be favored because of the HF elimination.[66]
Complex 17 was characterized by NMR spectroscopy in solution.
The 31P{1H} NMR and 19F{1H} NMR spectrum show signals at
F(2)−H(2) = 1.35(4) Å and H(2)−F(1) = 0.95(4) Å confirm an
asymmetrical arrangement of the atoms in the bifluoride anion.
There is an interaction between the OH group and the FHF
anion, although the distance H1∙∙∙F2 = 1.835 Å is slightly longer
than in the complex [(cod)3Rh3(µ-OH)2]FHF.[123] The F−F
distance of 2.301 Å is comparable with the one for [(PdMe)2{µ-
ĸ2(P,P)-Ph2PCH2PPh2}2(µ-F)][FHF].[118]
δ = 57.0 ppm
(1JPt,P = 3815 Hz)
and
δ = -233.6 ppm
(1JPt,F = 346 Hz) which are of higher order and can be simulated
as parts of AA’XX’/AA’MXX’ spin systems (A = 31P, X = 19F,
M = 195Pt; Figure 9). The analytical data of 17 are also in good
agreement with the one found for [Pt(F)2(dppp)] (dppp = 1,3-
bis(diphenylphosphino)propane).[67] A reaction of 17 with water
yielded immediately the binuclear hydroxo complex 15. This
might explain the above mentioned formation of 15 in the
presence of adventitious water.
The 31P{1H} NMR spectrum of [Pt(PhC=CFPh)(F){κ2-(P,P)-
Cy2PC2H4PCy2}] (16) shows two signals with a doublet and a
doublet of doublets pattern with 195Pt satellites for the
inequivalent phosphorus atoms of the dcpe ligand
(dcpe = 1,2-Bis(dicyclohexylphosphino)ethane) (Figure 7). The
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The reaction of [Pt{κ2-(P,P)-Cy2PC2H4PCy2}(ƞ2-PhC≡CPh)] (14)
with two equivalents XeF2 yielded several fluorinated organic
products as well as tolane and [Pt(µ-OH){κ2-(P,P)-
Cy2PC2H4PCy2}]2[FHF]2 (15) as the only metal containing
product (Scheme 5). Note, that the cyclometalated complex
[Pt(o-C6H4CF=CPh){κ2-(P,P)-Cy2PC2H4PCy2}] (18) was not
observed in the reaction with two equivalents XeF2. The organic
products were separated by hexane extraction from 15. The
fluorinated products 1,1,2,2-tetrafluoro-1,2-diphenylethane, (Z)-
1,2-difluoro-1,2-diphenylethene
and
(E)-1,2-difluoro-1,2-
diphenylethene were formed in a ratio of 1:3.5:2.5 according to
the 19F NMR spectrum. Note that these fluorinated products can
also be synthesized from tolane as starting material on using
gaseous F2 conditions under low temperatures or by reaction
with XeF2.[125–129]
Figure 9. 19F{1H} NMR spectrum of [Pt(F)2{κ2-(P,P)-Cy2PC2H4PCy2}] (17),
simulated (bottom); observed (top). The following coupling constants were
used for the simulation: JPt,P = 3842 Hz, JPt,F = 323.51 Hz, JP,P = 74.94 Hz,
JP,Fcis = 3.91 Hz, JP,Ftrans = 174.48 Hz, JF,F = 2 Hz.
LIFDI-MS data of complex [Pt(o-C6H4CF=CPh){κ2-(P,P)-
Cy2PC2H4PCy2}] (18) reveal a peak at m/z 813 which can be
assigned to the [M]+ ion. The 31P{1H} NMR spectrum exhibits two
signals for the inequivalent phosphorus atoms of the dcpe ligand.
Scheme 5. Reaction of [Pt{κ2-(P,P)-Cy2PC2H4PCy2}(ƞ2-PhC≡CPh)] (14) with 2
equiv. XeF2.
4
One doublet of doublets at δ = 62.6 ppm with JP,F = 28 Hz and
195Pt satellites (1JPt,P = 2184 Hz) and a doublet at δ = 61.7 ppm
with 195Pt satellites (1JPt,P = 1927 Hz). The P,P-coupling constant
of JP,P = 3 Hz is fairly small, but not unusual for platinum bound
phosphorus atoms in a mutual cis position to each other.[71,124]
Further proof for the identity of 18 was given by X-ray
crystallography. Colorless crystals were obtained by slow
evaporation of a saturated hexane solution of 18 (Figure 10).
The platinum center adopts a square planar geometry by the
phosphorus atoms P(1) and P(2) of the dcpe ligand as well as
the C(33) and C(36) atoms. The Pt(1)−P(1) and Pt(1)−P(2) bond
length and the bite angle are similar to the one known for other
platinum(II) complexes with dcpe ligand.[124]
Scheme 6. Proposed mechanism for the reaction of [Pt{κ2-(P,P)-
Cy2PC2H4PCy2}(ƞ2-PhC≡CPh)] (14) with 2 equiv. XeF2.
Mechanistically, we assume that in a first step the fluorido
complex [Pt(PhC=CFPh)(F){κ2-(P,P)-Cy2PC2H4PCy2}] (16) is
formed after a reaction of the platinum alkyne complex 14 with
XeF2 (Scheme 6). Then a formal β-F-elimination might occur to
yield the platinum difluorido complex 17 and tolane. An
alternative pathway for the generation of 17 could be the
reaction of 14 with XeF2 under dissociation of tolane. The latter
can react with XeF2 without any metal species involved to yield
Figure 10. ORTEP diagram of 18. Ellipsoids are drawn at the 50 % probability
level. The hydrogen atoms are omitted for clarity. Selected bond lengths [Å]
and angles [°] of complex 18: Pt(1)-P(1) 2.3098(15), C(33)-C(34) 1.343(10),
Pt(1)-P(2) 2.3001(15), C(34)-C(35) 1.448(9), Pt(1)-C(33) 2.106(6), C(35)-
C(36) 1.406(9),
Pt(1)-C(36) 2.088(6),
C(34)-F(1) 1.380(7),
P(1)-Pt(1)-
P(2) 85.73(5), C(33)-Pt(1)-C(36) 80.5(2), P(1)-Pt(1)-C(33) 95.98(18), C(33)-
C(34)-F(1) 122.6(6), P(2)-Pt(1)-C(36) 97.86(17), C(35)-C(34)-F(1) 115.2(6).
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perfluorinated 1,1,2,2-tetrafluoro-1,2-diphenylethane, which was
chromatograph (Agilent 19091S-433 Hewlett-Packard) equipped with an
Agilent 5973 Network mass selective detector at 70 eV. For all
photochemical experiments a L.O.T. Oriel 150 W Xarc lamp was used.
The microanalyses were obtained using a Euro EA HEKAtech elemental
analyzer. Structure determination of complexes 3, 6, 7, 15, 18. The data
collections were performed with a BRUKER D8 VENTURE area detector,
Mo-Kα radiation (λ = 0.71073 Å). Multi-scan absorption corrections
implemented in SADABS[131] were applied to the data. The structures
were solved by intrinsic phasing method (SHELXT-2013)[132] and refined
by full-matrix least square procedures based on F2 with all measured
reflections (SHELXL-2013)[132] with anisotropic temperature factors for all
non-hydrogen atoms. All hydrogen atoms were added geometrically and
refined using a riding model.
confirmed by an independent reaction.[128] Alternatively 16 can
convert with additional XeF2 into
a platinum(IV) fluorido
intermediate. Fast C−F reductive elimination steps then give the
fluorinated olefins and [Pt(F)2{κ2-(P,P)-Cy2PC2H4PCy2}] (17). The
platinum(II)-difluoridocomplex 17 reacts with traces of water to
yield 15. The generation of an isomer of 16 with both phenyl
groups in a cis-position at the double bond was not observed,
possibly because of fast tolane elimination. However in the
presence of an excess XeF2 it might be trapped and finally (Z)-
1,2-difluoro-1,2-diphenylethene can be furnished.
Conclusions
Synthesis of [Pt(PhC=CFPh)(F){κ2-(P,N)-iPr2PC3H6NMe2}] (3)[71]
In conclusion, we described electrophilic outer-sphere
fluorination reactions at platinum(0) alkyne complexes with XeF2
resulting in the formation of the fluoride fluorovinyl complexes
[Pt(PhC=CFPh)(F){L}] (3, 4) (L = κ2-(P,N)-iPr2PC3H6NMe2: 3, κ2-
(P,N)-iPr2PC2H4NMe2: 4). Examples for the isolation of
compounds bearing a fluorinated ligand after outer-sphere
fluorination are extremely scarce.[70,71,78,130] Derivatization and
reactivity studies at 4 did not result in any C-C coupling
reactions. However, photolysis of [Pt(PhC=CFPh)(CF3){κ2-(P,N)-
iPr2PC2H4NMe2}] (8) induced a β-fluorine elimination to yield
[Pt(F)(CF3){κ2-(P,N)-iPr2PC2H4NMe2}] (9) and the alkyne.[25,110–
A CH2Cl2 solution (1 mL) of the complex [Pt{κ2-(P,N)-iPr2PC3H6NMe2}(ƞ2-
PhC≡CPh)] (1) (58 mg, 0.10 mmol) was cannulated to a CH2Cl2 solution
(1 mL) of XeF2 (17 mg, 0.10 mmol) in a PFA tube at T = -30°C. The
yellow reaction mixture was slowly warmed up to room temperature and
stirred for 1h. The solvent was reduced to 1 mL and an excess hexane
(6 mL) was added resulting in a product precipitation. The supernatant
was filtered off, the solid was washed three times with hexane (1 mL) and
dried
in
vacuum.
The
complex
[Pt(PhC=CFPh)(F){κ2-(P,N)-
iPr2PC3H6NMe2}] (3) was isolated as colorless solid. Yield 51 mg (82%).
1H NMR (500.1 MHz, CD2Cl2, 298 K): δ=8.49 (d, 3J(H,H)=8 Hz, 2H, CHar),
7.69 (d, 3J(H,H)=8 Hz, 2H, CHar), 7.35-7.21 (m, 5H, CHar), 7.09 (t,
3J(H,H)=7 Hz, 1H, CHar), 2.91 (s, br, 3H, N(CH3)2), 2.85 (s, br, 3H,
N(CH3)2), 2.53 (m, 2H, CH2N(CH3)2), 1.73-1.63 (m, 4H, PCH(CH3)2, CH2),
1.48 (m, 1H, CH2PiPr2), 1.13 (m, 1H, CH2PiPr2), 0.87 (dd, 3J(P,H)=15 Hz,
3J(H,H)=7 Hz, 3H, PCH(CH3)2), 0.79 (dd, 3J(P,H)=13 Hz, 3J(H,H)=7 Hz,
3H, PCH(CH3)2), 0.69 (dd, 3J(P,H)=17 Hz, 3J(H,H)=7 Hz, 3H, PCH(CH3)2),
0.54 (dd, 3J(P,H)=17 Hz, 3J(H,H)=7 Hz, 3H, PCH(CH3)2) ppm;
13C{1H} NMR (125.67 MHz, CD2Cl2, 298 K): δ=147.3 (dd, J=7 Hz,
1J(C,F)=248 Hz, CF), 145.7 (d, J=7 Hz, ipso-C), 136.6 (dd, J=2 Hz,
J=34 Hz, ipso-C), 130.3 (d + sat, J=2 Hz, 1J(Pt,C)=28 Hz, Car), 129.5 (t,
J=5 Hz, Car), 127.7 (s, Car), 127.5 (s, Car), 127.3 (s, Car), 125.0 (s, Car),
105.0 (dd + sat, J=2 Hz, J=10 Hz, 1J(Pt,C)=940 Hz, C=CF), 65.6 (s,
J=4 Hz CH2N(CH3)2), 50.5 (d, J=10 Hz, N(CH3)2), 49.3 (d, J=11 Hz,
N(CH3)2), 27.0 (dd + sat, J=2 Hz, J=40 Hz, 1J(Pt,C)=60 Hz, PCH(CH3)2),
24.1 (s + sat, 1J(Pt,C)=51 Hz, CH2), 23.4 (dd + sat, J=1 Hz, J=39 Hz,
1J(Pt,C)=60 Hz, PCH(CH3)2), 16.4 (dd, J=2 Hz, J=32 Hz, CH2PiPr2), 18.8
(d + sat, 2J(P,C)=5 Hz, 1J(Pt,C)=43 Hz, PCH(CH3)2), 17.0 (s+sat,
1J(Pt,C)=36 Hz, PCH(CH3)2), 16.8 (s, PCH(CH3)2), 15.6 (d+sat, J=5 Hz,
1J(Pt,C)=43 Hz, PCH(CH3)2) ppm; 19F{1H} NMR (300.1 MHz, CD2Cl2,
298 K): δ=-91.9 (d+sat, 4J(F,F)=3 Hz, 3J(Pt,F)=260 Hz), -206.9 (dd+sat,
113]
Further investigations focused on the formation of fluorido
species by oxidation reactions with an excess XeF2. In the case
of the platinum(0)-alkyne complexes, bearing a P,N donating
ligand the formation of orthometalated platinum(IV) difluorido
complexes was observed. The reaction pattern confirms the
assumption that fluoride complexes might be able to induce C-H
activation steps.[29,66,68,116] However, fluorination of [Pt{κ2-(P,P)-
Cy2PC2H4PCy2}(ƞ2-PhC≡CPh)] (14) with two equivalents XeF2
resulted
in
the
generation
of
[Pt(µ-OH){κ2-(P,P)-
Cy2PC2H4PCy2}]2[FHF]2 (15) and fluorinated olefins, possibly by
C−F reductive elimination from a Pt(IV) intermediate.
Experimental Section
The synthetic work was carried out on a Schlenk line or in a glove box in
an atmosphere of argon. Tetrahydrofurane and hexane as well as
[D6]benzene, [D8]toluene and [D8]tetrahydrofuran were purified by
distillation from Na/K and stored under argon over molecular sieves.
MeOH was stored under molecular sieve. Dichlormethane and
[D2]dichloromethane were purified by distillation from CaH2 and stored
under argon. [Pt{L}(ƞ2-PhC≡CPh)] (L: κ2-(P,N)-iPr2PC3H6NMe2, κ2-(P,N)-
iPr2PC2H4NMe2, κ2-(P,P)-Cy2PC2H4PCy2 and complex 4 were prepared
according to the literature.[71] NaBF4, MeLi, AgF, MeOH, Me3SiCF3 were
obtained from Aldrich and were used without further purification. XeF2
was also obtained from Aldrich but was sublimed before use. The NMR
spectra were recorded at 300 K on a Bruker Avance 500, a Bruker
Avance 400, a Bruker DPX 300 or a Bruker Avance III 300 NMR
spectrometer. The 1H NMR chemical shifts were referenced to residual
C6D5H at δ 7.15 ppm, [D7]toluene at δ 2.09 ppm, CDHCl2 at δ 5.32 ppm
and C4D7HO at δ 1.72 ppm and 3.58 ppm. The 19F NMR spectra were
referenced to external CFCl3 at δ 0.0 ppm and the 31P{1H} NMR spectra
to external H3PO4 at δ 0.0 ppm. Infrared spectra were recorded on a
Bruker Vertex 70 spectrometer which was equipped with a diamond ATR
unit. Mass spectra were measured on a Micromass Q-Tof-2 instrument
equipped with a Linden LIFDI source (Linden CMS GmbH) or on an
Agilent Technologies 6210 Time-of-Flight LC-MS instrument (ESI). GC-
MS spectra were measured on an Agilent 6890N gas-phase
4J(F,F)=3 Hz,
2J(P,Ftrans)=179 Hz,
CD2Cl2,
1J(Pt,F)=156 Hz)
298 K): δ=6.6
ppm;
(d+sat,
31P{1H} NMR (202.4 MHz,
2J(P,Ftrans)=179 Hz, 1J(Pt,P)=4369 Hz) ppm; LIFDI-TOF-MS (THF): m/z:
614 [M]+; elemental analysis calcd (%) for C25H36F2NPPt: C 48.85, H 5.90,
N 2.28, found C 48.80, H 5.78, N 1.99.
Synthesis of [Pt(PhC=CFPh)(F){κ2-(P,N)-iPr2PC2H4NMe2}] (4)[71]
A CH2Cl2 solution (1 mL) of the complex [Pt{κ2-(P,N)-iPr2PC2H4NMe2}(ƞ2-
PhC≡CPh)] (2) (67 mg, 0.12 mmol) was cannulated to a CH2Cl2 solution
(1 mL) of XeF2 (20 mg, 0.12 mmol) in a PFA tube at T = -30°C. The
yellow reaction mixture was slowly warmed up to room temperature and
stirred for 1h. The solvent was reduced to 1 mL and an excess hexane
(6 mL) was added resulting in a product precipitation. The supernatant
was filtered off, the solid was washed three times with hexane (1 mL) and
dried
in
vacuum.
The
complex
[Pt(PhC=CFPh)(F){κ2-(P,N)-
iPr2PC2H4NMe2}] (4) was isolated as colorless solid. Yield 56 mg
(80%).1H NMR (500.1 MHz, CD2Cl2, 298 K): δ=8.44 (d, J(H,H)=7 Hz, 2H,
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CHar), 7.54 (d, 3J(H,H)=7 Hz, 2H, CHar), 7.31 (t, 3J(H,H)=7 Hz, 2H, CHar),
7.26-7.21 (m, 3H, CHar), 7.07 (t, 3J(H,H)=7 Hz, 1H, CHar), 2.82 (s, br, 3H,
N(CH3)2), 2.71 (s, br, 3H, N(CH3)2), 2.49 (m, 2H, CH2N(CH3)2), 1.80 (m,
1H, PCH(CH3)2), 1.64 (m, 2H, CH2PiPr2, PCH(CH3)2), 1.40 (m, 1H,
CH2PiPr2), 0.91 (dd, 3J(P,H)=16 Hz, 3J(H,H)=7 Hz, 3H, PCH(CH3)2),
0.85 (dd, 3J(P,H)= 16 Hz, 3J(H,H)=7 Hz, 3H, PCH(CH3)2), 0.61 (dd,
3J(P,H)=16 Hz, 3J(H,H)=7 Hz, 3H, PCH(CH3)2), 0.47 (dd, 3J(P,H)=16 Hz,
3J(H,H)=7 Hz, 3H, PCH(CH3)2) ppm; 13C{1H} NMR (125.67 MHz, CD2Cl2,
298 K): δ = 147.5 (dd, J=6 Hz, 1J(C,F)=248 Hz, β-CF), 145.7 (d, J=7 Hz,
ipso-C), 138.7 (dd, J=2 Hz, J=30 Hz, ipso-C), 129.7 (d + sat, J=2 Hz,
1J(Pt,C)=26 Hz, Car), 128.8 (t, J=5 Hz, Car), 127.5 (s, Car), 127.6 (s, Car)
127.4 (s, Car), 124.8 (s, Car), 106.8 (dd+sat, J=2 Hz, J=9 Hz,
1J(Pt,C)=940 Hz, C=CF), 63.7 (s + sat, 1J(Pt,C)=45 Hz CH2N(CH3)2),
48.5 (d, J=5 Hz, N(CH3)2), 50.0 (d, J=5 Hz, N(CH3)2), 24.2 (dd+sat,
J=2 Hz, J=37 Hz, 1J(Pt,C)= 60 Hz, PCH(CH3)2), 21.7 (dd + sat, J=2 Hz,
PCH(CH3)2), 0.90 (dd, 3J(P,H)=15 Hz, 3J(H,H)=7 Hz, 3H, PCH(CH3)2)
ppm; 19F{1H} NMR (282.4 MHz, [D8]THF, 298 K): δ=91.3 (d+sat,
4J(P,F)=3 Hz, 3J(Pt,F)=150 Hz, β-F), 154.2 (s, 4F, BF4) ppm;
31P{1H} NMR (121.5 MHz, [D8]THF, 298 K): δ=49.91 (d+sat, 4J(P,F)=3 Hz,
1J(Pt,P)=3347 Hz) ppm; IR (ATR): 푣̃(CO) = 2125 cm-1.
Synthesis of [Pt(PhC=CFPh)(Me){κ2-(P,N)-iPr2PC2H4NMe2}] (7)
The complex [Pt(PhC=CFPh)(F){κ2-(P,N)-iPr2PC2H4NMe2}] (4) (53 mg,
0.09 mmol) was dissolved in Et2O (3 mL) and the solution was cooled to
T = -30°C. MeLi (66 µL, 11 mmol, 1.6 M) was added and the suspension
was warmed up. At 0°C the solution was quenched with MeOH (0.5 mL)
and the solvent was removed in vacuum at room temperature. The
remaining solid was extracted with toluene (3x5 mL). The extract was
dried under vacuum resulting in [Pt(PhC=CFPh)(Me){κ2-(P,N)-
iPr2PC2H4NMe2}] (7) as a light yellow powder. Yield 32 mg (60%).
1H NMR (400.1 MHz, C6D6, 298 K): δ=9.10 (d, 3J(H,H)=8 Hz, 2H, CHar),
7.83-7.80 (m, 2H, CHar), 7.32 (t, 3J(H,H)=8 Hz, 2H, CHar), 7.25 (t, 2H,
CHar), 7.20-7.17 (m, 1H, CHar), 7.07-7.03 (m, 1H, CHar), 2.26 (s+sat,
3J(Pt,H)=21 Hz, 3H, N(CH3)2), 2.03 (s+sat, 3J(Pt,H)=21Hz, 3H, N(CH3)2),
1.78 (m, 2H, CH2N(CH3)2), 1.57 (m, 2H, PCH(CH3)2), 1.03 (d+sat,
3J(P,H)=7 Hz, 2J(Pt,H)=64 Hz, PtCH3), 0.85 (m, 2H, CH2PiPr2), 0.90 (dd,
3J(P,H)=15 Hz, 3J(H,H)=7 Hz, 3H, PCH(CH3)2), 0.77 (dd, 3J(P,H)=16 Hz,
3J(H,H)=7 Hz, 3H, PCH(CH3)2) 0.48 (m, 6H, PCH(CH3)2) ppm;
13C{1H} NMR (100.61 MHz, C6D6, 298 K): δ=148.3 (dd, J=2 Hz, J=9 Hz,
ipso-C), 143.5 (dd, J=4 Hz, 1J(C,F)= 238 Hz, β-CF), 137.8 (dd, J=1 Hz,
J=33 Hz, ipso-C), 130.0 (d+sat, J=1 Hz, J(Pt,C)=46 Hz, Car), 127.3 (d,
J=2 Hz, Car), 127.2 (s, Car), 127.1 (s, Car), 125.5 (s, Car), 124.4 (s, Car),
114.3 (d+sat, 2J(P,C)=10 Hz, 1J(Pt,C)=1032 Hz, C=CF), 67.6 (d, J=7 Hz
CH2N(CH3)2), 50.4 (s, N(CH3)2), 49.1 (s, N(CH3)2), 24.4 (d+sat, J=23 Hz,
2J(Pt,C)=30 Hz, PCH(CH3)2), 21.7 (d + sat, J=22 Hz, 2J(Pt,C)=28 Hz,
PCH(CH3)2), 18.6 (d, J=19 Hz, CH2PiPr2), 18.3 (d, J=6 Hz, PCH(CH3)2),
18.2 (d, J=6 Hz, PCH(CH3)2), 17.0 (d, J=4 Hz, PCH(CH3)2), 15.9 (d,
J=7 Hz, PCH(CH3)2), 9.9 (d+sat, 2J(P,C)=99 Hz, 1J(Pt,C)= 672 Hz,
PtCH3) ppm; 19F{1H} NMR (282.4 MHz, C6D6, 298 K): δ=104.9 (d+sat,
4J(P,F)=4 Hz, 3J(Pt,F)=329 Hz) ppm; 31P{1H} NMR (121.5 MHz, C6D6,
298 K): δ=50.2 (d+sat, 4J(P,F)=4 Hz, 1J(Pt,P)=1954 Hz) ppm; elemental
analysis calcd (%) for C25H37FNPPt: C 50.33, H 6.25, N, 2.35; found
C 50.73, H 6.40, N 2.24.
1
J=37 Hz, J(Pt,C)=60 Hz, PCH(CH3)2), 20.9 (d, J=32 Hz, CH2PiPr2), 18.1
(s, PCH(CH3)2), 17.1 (s + sat, 1J(Pt,C)=25 Hz, PCH(CH3)2), 16.3 (s
PCH(CH3)2), 15.6 (d + sat, J=5 Hz, 1J(Pt,C)=42 Hz PCH(CH3)2) ppm;
19F{1H} NMR (470.5 MHz, CD2Cl2, 298 K): δ=94.9 (d + sat, 4J(F,F)=5 Hz,
3J(Pt,F)=268 Hz, β-F), 217.4 (dd + sat, 4J(F,F)=5 Hz, 2J(P,Ftrans)=176 Hz,
1J(Pt,F)=228 Hz) ppm; 31P{1H} NMR (202.4 MHz, CD2Cl2, 298 K): δ=32.8
(d + sat, 2J(P,Ftrans)=176 Hz, 1J(Pt,P)=4384 Hz) ppm; elemental analysis
calcd (%) for C24H34F2NPPt: C 48.00, H 5.71, N 2.33, found C 47.75,
H 5.66, N 2.04.
Synthesis of [Pt(PhC=CFPh)(thf){κ2-(P,N)-iPr2PC2H4NMe2}]BF4 (5)
The complex [Pt(PhC=CFPh)(F){κ2-(P,N)-iPr2PC2H4NMe2}] (4) (19 mg,
0.03 mmol) was dissolved in thf (2 mL) and NaBF4 (7 mg, 0.06 mmol)
was added. The reaction mixture was stirred for 12 h at room
temperature and a white precipitate formed. The supernatant was filtered
over a plug of celite (1 cm) and the filtrate was dried under vacuum. The
complex [Pt(PhC=CFPh){κ2-(P,N)-iPr2PC2H4NMe2}]BF4 (5) was isolated
as a light yellow powder. Yield 15 mg (71%). 1H NMR (400.1 MHz,
[D8]THF, 298 K): δ=8.37 (d, J(H,H)=8 Hz, 1H, CHar), 7.48 (d,
J(H,H)=8 Hz, 1H, CHar), 7.35-7.02 (m, 8H, CHar), 3.61 (m, 4H, thf),
2.82 (s, br, 3H, N(CH3)2), 2.73 (s, br, 3H, N(CH3)2), 1.77 (m, 4H, thf),
2.76-2.61 (m, 2H, CH2N(CH3)2), 1.92 (m, 1H, CH2PiPr2), 1.66 (m, 1H,
CH2PiPr2), 1.62 (m, 1H, PCH(CH3)2, 1.24 (m, 1H, PCH(CH3)2, 0.88 (m,
6H,
19F{1H} NMR (282.4 MHz,
3J(Pt,F)=235 Hz,
β-F),
31P{1H} NMR (121.5 MHz,
PCH(CH3)2),
0.61 (m,
[D8]THF,
153.6
[D8]THF,
6H,
298 K):
(s,
PCH(CH3)2)
ppm;
(s+sat,
ppm;
Synthesis of [Pt(PhC=CFPh)(CF3){κ2-(P,N)-iPr2PC2H4NMe2}] (8)
δ=92.5
4F,
BF4)
298 K):
δ=34.54
(s+sat,
The complex [Pt(PhC=CFPh)(F){κ2-(P,N)-iPr2PC2H4NMe2}] (70 mg,
0.12 mmol) and AgF (68 mg, 0.47 mmol) were dissolved in thf (2 mL)
under exclusion of light. After addition of Me3SiCF3 (116 µL, 0.23 mmol,
2 M) the reaction mixture was sonicated for 1.5 h. The mixture was
filtered through a plug of celite and the filtrate was concentrated to
dryness. The residue was washed with benzene (3x1 mL) and dried
1J(Pt,P)=4716 Hz) ppm. elemental analysis calcd (%) for C24H34BF5NPPt:
C 43.13, H 5.13, N 2.10; found C 43.14, H 5.36, N 1.84.
Formation of [Pt(PhC=CFPh)(CO){κ2-(P,N)-iPr2PC2H4NMe2}]BF4 (6)
The complex [Pt(PhC=CFPh)(thf){κ2-(P,N)-iPr2PC2H4NMe2}]BF4 (5) was
dissolved in thf-d8 (0.6 mL) in a Young NMR tube. The solution was
cooled to 77 K. The NMR tube was degassed in vacuo and was
pressurized with gaseous CO to 1 atm. The solution was slowly allowed
to warm up to room temperature while the color turned from yellow to
light green. A complete conversion was monitored by NMR spectroscopy.
After 12 h crystals were formed in the NMR tube. The supernatant was
filtered of and the crystals were dried under vacuum. With these crystals
X-ray analysis, NMR and IR spectroscopy were done. Bringing the
reaction solution to dryness led to the generation of the starting material.
1H NMR (300.1 MHz, [D8]THF, 298 K): δ=8.25 (d, 3J(H,H)=7 Hz, 2H,
CHar), 7.54-7.48 (m, 4H, CHar), 7.41 (t, 3J(H,H)=7 Hz, 1H, CHar), 7.31 (t,
3J(H,H)=7 Hz, 2H, CHar), 7.19 (t, 3J(H,H)= 7 Hz, 1H, CHar), 2.91 (s, br, 3H,
N(CH3)2), 2.79 (s, br, 3H, N(CH3)2), 2.33 (m, 2H, CH2N(CH3)2), 2.04 (m,
2H, CH2PiPr2), 1.82 (m, 1H, PCH(CH3)2), 1.64 (m, 1H, PCH(CH3)2),
1.25 (m, 6H, PCH(CH3)2), 0.97 (dd, 3J(P,H)=16 Hz, 3J(H,H)=7 Hz, 3H,
under
vacuum
resulting
in
[Pt(PhC=CFPh)(CF3){κ2-(P,N)-
iPr2PC2H4NMe2}] (8) as a colorless solid. Yield 54 mg (71%). 1H NMR
(300.1 MHz, [D8]THF, 298 K): δ=8.61 (d, 3J(H,H)=7 Hz, 2H, CHar), 7.56-
7.52 (m, 2H, CHar), 7.22 (t, 3J(H,H)=7 Hz, 2H, CHar), 7.15-7.10 (m, 3H,
CHar), ), 7.00-6.95 (m, 1H, CHar), 2.89 (s+sat, 3J(Pt,H)=18 Hz, 3H,
N(CH3)2), 2.81 (s+sat, 3J(Pt,H)=18 Hz, 3H, N(CH3)2), 2.64 (m, 2H,
CH2N(CH3)2), 2.04 (m, 1H, PCH(CH3)2), 1.57 (m, 3H, CH2PiPr2,
PCH(CH3)2), 0.99 (dd, 3J(P,H)=15 Hz, 3J(H,H)=7 Hz, 3H, PCH(CH3)2),
0.85 (m, 6H, PCH(CH3)2), 0.62 (dd, 3J(P,H)=15 Hz, 3J(H,H)=7 Hz, 3H,
PCH(CH3)2) ppm; 13C{1H} NMR (100.6 MHz, [D8]THF, 298 K): δ=146.8
(dd, J=1.5 Hz, J=8 Hz, ipso-C), 145.4 (dd, J=3 Hz, 1J(C,F)=242 Hz, β-
CF), 137.8 (dd, J=1 Hz, J=34 Hz, ipso-C), 131.0 (d+sat, J=2.5 Hz,
J(Pt,C)= 44 Hz, Car), 127.6 (d, J=3 Hz, Car), 127.2 (m, Car), 126.4 (s, Car),
124.9 (s+sat, J(Pt,C)=11 Hz, Car), 106.8 (m, C=CF, Pt satellites were not
observed), 67.6 (s, CH2N(CH3)2), 51.7 (s, N(CH3)2), 51.2 (s, N(CH3)2),
25.1 (d, J=25 Hz, PCH(CH3)2), 22.2 (d, J=27 Hz, PCH(CH3)2), 19.7 (d,
This article is protected by copyright. All rights reserved.

10.1002/chem.201700403
Chemistry - A European Journal
FULL PAPER
J=23 Hz, CH2PiPr2), 18.5 (d, J=4 Hz, PCH(CH3)2), 17.7 (d, J=4 Hz,
PCH(CH3)2), 16.7 (d, J=1 Hz, PCH(CH3)2), 15.4 (d, J=7 Hz, PCH(CH3)2)
ppm. The resonance for the CF3 group was not detected.
2J(Fcis,Ftrans)=100 Hz, Fcis
298 K): δ=-3.08 (d+sat, 2J(P,Ftrans)=169 Hz, 1J(Pt,P)=2865 Hz) ppm,
LIFDI-TOF-MS (THF): m/z: 613 [M-F]+.
)
ppm; 31P{1H} NMR (121.5 MHz, CD2Cl2,
19F{1H} NMR (282.4 MHz,
[D8]THF,
298 K):
δ=30.8
(dd+sat,
3J(P,F)=50 Hz, 5J(F,F)=1.5 Hz, 2J(Pt,F)=616 Hz, 3F, CF3), 101.9
(dq+sat, 4J(P,F)=3.5 Hz, 5J(F,F)=1.5 Hz, 3J(Pt,F)=278 Hz) ppm,
Selected spectroscopic data for [Pt(F)2(o-C6H4CF=CPh){κ2-(P,N)-
iPr2PC3H6NMe2}] (12b): 19F{1H} NMR (282.4 MHz, CD2Cl2, 298 K):
δ=119.4 (d+sat, 4J(Ftrans,β-F)=2 Hz, 3J(Pt,β-F)=181 Hz, β-F), 214.6
(dd+sat, 2J(P,Fcis)=5 Hz, 2J(Fcis,Ftrans)=107 Hz, 1J(Pt,Fcis)=106 Hz, Fcis),
229.3 (ddd, 4J(Ftrans,β-F)=2 Hz, 2J(Fcis,Ftrans)=106 Hz, 2J(P,Ftrans)=169 Hz,
Ftrans) ppm; 31P{1H} NMR (121.5 MHz, CD2Cl2, 298 K): δ=2.62 (dd+sat,
2J(P,Fcis)=5 Hz, 2J(P,Ftrans)=169 Hz, 1J(Pt,P)=2830 Hz) ppm, LIFDI-TOF-
MS (THF): m/z: 613 [M-F]+.
31P{1H} NMR (121.5 MHz,
[D8]THF,
298 K):
δ=41.3
(qd+sat,
3J(P,F)=50 Hz, 4J(P,F)=3.5 Hz, 1J(Pt,P)=2245 Hz) ppm, LIFDI-TOF-MS
(THF): m/z: 650 [M]+; elemental analysis calcd (%) for C25H34F4NPPt:
C 46.15, H, 5.27, N 2.15; found C 46.45, H 5.26, N 1.96.
Synthesis of [Pt(F)(CF3){κ2-(P,N)-iPr2PC2H4NMe2}] (9)
The complex [Pt(PhC=CFPh)(CF3){κ2-(P,N)-iPr2PC2H4NMe2}] (8) (15 mg,
0.02 mmol) was dissolved in thf-d8. After irradiation for 12 h a quantitative
formation of [Pt(F)(CF3){κ2-(P,N)-iPr2PC2H4NMe2}] was observed by
NMR spectroscopy. 1H NMR (400.1 MHz, [D8]THF, 298 K): δ=2.69-
2.62 (m, 2H, CH2N(CH3)2), 2.61 (s+sat, 3J(Pt,H)=10 Hz, 6H, N(CH3)2),
2.24-2.17 (m, 2H, PCH(CH3)2), 1.88-1.84 (m, 2H, CH2PiPr2), 1.26 (dd,
J(P,H)=17 Hz, J(H,H)=7 Hz, 6H, PCH(CH3)2), 1.21 (dd, J(P,H)=15 Hz,
J(H,H)=7 Hz, 6H, PCH(CH3)2) ppm; 13C{1H} NMR (75.5 MHz, [D8]THF,
298 K): δ=64.0 (s+sat, 2J(Pt,C)=42 Hz, CH2N(CH3)2), 48.6 (d, J=7 Hz,
N(CH3)2), 24.0 (dd, J=37 Hz, J=2 Hz, PCH(CH3)2), 21.3 (d, J=33 Hz,
CH2PiPr2), 19.2 (s+sat, 3J(Pt,C)=22 Hz, PCH(CH3)2), 17.8 (s+sat,
3J(Pt,C)=34 Hz, PCH(CH3)2) ppm. The resonance for the CF3 group was
not detected. 19F{1H} NMR (282.4 MHz, [D8]THF, 298 K): δ=-19.3 (t+sat,
3J(P,F)=3J(F,F)=7 Hz, 2J(Pt,F)=725 Hz, 3F, CF3), -229.4 (dq+sat,
Reaction of [Pt{κ2-(P,N)-iPr2PC2H4NMe2}(ƞ2-PhC≡CPh)] (2) with two
equivalents of XeF2
A CH2Cl2 solution (1 mL) of the complex [Pt{κ2-(P,N)-iPr2PC2H4NMe2}(ƞ2-
PhC≡CPh)] (2) (50 mg, 0.08 mmol) was added to a CH2Cl2 solution
(1 mL) of XeF2 (30 mg, 0.17 mmol) in a PFA tube at T = -30°C. The
yellow reaction mixture was slowly warmed up to room temperature and
stirred for 1h. The solvent was reduced to 1 mL and an excess hexane
(6 mL) was added resulting in a product precipitation. The supernatant
was filtered off and the filtrate was dried under reduced pressure. NMR
spectroscopic
measurements
confirm
the
formation
The remaining
of
[Pt(PhC=CHPh)(F){κ2-(P,N)-iPr2PC2H4NMe2}] (11).
residue was washed three times with hexane (1 mL) and dried in vacuum.
The NMR spectrum revealed the formation of the isomers [Pt(F)2(o-
C6H4CF=CPh){κ2-(P,N)-iPr2PC2H4NMe2}] (13a/b) in a ratio of 1:0.3. Yield
35 mg (71%).
2J(P,F)=157 Hz,
3J(F,F)=7 Hz,
1J(Pt,F)=165 Hz,
298 K): δ=42.9
PtF)
ppm;
(dq+sat,
31P{1H} NMR (121.5 MHz,
[D8]THF,
2J(P,F)=157 Hz, 3J(F,F)=7 Hz, 1J(Pt,P)=4178 Hz) ppm; LIFDI-TOF-MS
(THF): m/z: 453 [M-F]+, 403 [M-CF3]+.
Spectroscopic
data
for
[Pt(PhC=CHPh)(F){κ2-(P,N)-
iPr2PC2H4NMe2}] (11): 1H NMR (400.1 MHz, CD2Cl2, 298 K): δ=7.29-
7.25 (m, 2H, CHar), 7.16-7.10 (m, 2H, CHar), 7.06-7.01 (m, 1H, CHar),
6.99-6.96 (m, 2H, CHar), 6.93-6.90 (m, 1H, CHar), 6.87-6.84 (m, 2H, CHar),
6.55 (s+sat, 3J(Pt,H)=78 Hz, 1H, β-H), 2.66 (s+sat, 3J(Pt,H)=10 Hz, 6H,
N(CH3)2), 2.52 (m, 2H, CH2N(CH3)2), 2.04 (m, 2H, PCH(CH3)2), 1.67 (m,
2H, CH2PiPr2), 1.18 (dd, 3J(P,H)=15 Hz, 3J(H,H)=6 Hz, 6H, PCH(CH3)2),
1.07 (dd, 3J(P,H)=16 Hz, 3J(H,H)=7 Hz, 6H, PCH(CH3)2) ppm;
13C{1H} NMR (125.67 MHz, CD2Cl2, 298 K): δ=149.4 (s, ipso-C), 140.4 (d,
J=2 Hz, ipso-C), 137.7 (d, J=8 Hz, α-C), 132.4 (d, J=5 Hz, β-CH), 128.8
(s, Car), 128.7 (s, Car), 127.9 (s, Car), 127.7 (s, Car), 124.6 (s, Car), 124.7
(s, Car), 63.1 (s+sat, 2J(Pt,C)=49 Hz CH2N(CH3)2), 48.8 (s, N(CH3)2),
48.7 (s, N(CH3)2), 29.9 (d, J=37 Hz, PCH(CH3)2), 21.0 (d, J=37 Hz,
PCH(CH3)2), 21.3 (d, J=32 Hz, CH2PiPr2), 18.2 (d+sat, J=1 Hz,
PCH(CH3)2), 18.3 (d+sat, J=1 Hz, PCH(CH3)2), 17.5 (d+sat, J=1 Hz,
Reaction of [Pt{κ2-(P,N)-iPr2PC3H6NMe2}(ƞ2-PhC≡CPh)] (1) with two
equivalents of XeF2
A CH2Cl2 solution (1 mL) of the complex [Pt{κ2-(P,N)-iPr2PC3H6NMe2}(ƞ2-
PhC≡CPh)] (1) (70 mg, 0.12 mmol) was cannulated to a CH2Cl2 solution
(1 mL) of XeF2 (41 mg, 0.24 mmol) in a PFA tube at T = -30°C. The
yellow reaction mixture was slowly warmed up to room temperature and
stirred for 1h. The solvent was reduced to 1 mL and an excess hexane
(6 mL) was added resulting in a product precipitation. The supernatant
was filtered off and the filtrate was dried under reduced pressure. NMR
spectroscopic
measurements
confirm
the
formation
The remaining
of
[Pt(PhC=CHPh)(F){κ2-(P,N)-iPr2PC3H6NMe2}] (10).
residue was washed three times with hexane (1 mL) and dried in vacuum.
The NMR spectrum revealed the formation of the isomers [Pt(F)2(o-
C6H4CF=CPh){κ2-(P,N)-iPr2PC3H6NMe2}] (12a/b) in a ratio of 0.5:1. Yield
49 mg (65%).
PCH(CH3)2),
17.4
(d+sat,
CD2Cl2,
J=1 Hz,
298 K):
PCH(CH3)2)
δ=214.8
ppm;
19F{1H} NMR (282.4 MHz,
(d+sat,
2J(P,Ftrans)=180 Hz, 1J(Pt,F)=276 Hz) ppm; 31P{1H} NMR (121.5 MHz,
CD2Cl2, 298 K): δ=33.2 (d+sat, 2J(P,Ftrans)=180 Hz, 1J(Pt,P)=4560 Hz)
ppm.
Spectroscopic
data
for
[Pt(PhC=CHPh)(F){κ2-(P,N)-
iPr2PC3H6NMe2}] (10):1H NMR (300.1 MHz, CD2Cl2, 298 K): δ= 7.84-7.25
(m, 4H, CHar), 7.01-6.73 (m, 6H, CHar), 6.57 (s+sat, 1H, 3J(Pt,H)=70 Hz,
Spectroscopic data for [Pt(F)2(o-C6H4CF=CPh){κ2-(P,N)-iPr2PC2H4NMe2}]
(13a): 1H,13C-HMBC-NMR (400.1 MHz/75.5 MHz, CD2Cl2): δ=2.7/127
β-H),
2.95-0.69
(m,
br,
CD2Cl2,
κ2-(P,N)-iPr2PC3H6NMe2}]
298 K): δ=204.4
ppm,
(d+sat,
19F{1H} NMR (282.4 MHz,
(s/s+sat,
1J(Pt,C)=720 Hz,
1J(Pt,C)=720 Hz,
N(CH3)2/Car),
N(CH3)2/Car).
1.7/127
(s/s+sat,
2J(P,Ftrans)=182 Hz, 1J(Pt,F)=215 Hz) ppm; 31P{1H} NMR (161.9 MHz,
CD2Cl2, 298 K): δ=9.64 (d+sat, 2J(P,Ftrans)=182 Hz, 1J(Pt,P)=4580 Hz)
ppm, LIFDI-TOF-MS (THF): m/z: 595 [M-H]+.
19F,13C-HMBC-
NMR (282.4 MHz/75.5 MHz, CD2Cl2): δ=-114/158 (ddd/s, J=7 Hz,
J=28 Hz, 1J(C,F)=265 Hz, C=CF), -114/143 (ddd/s, J=7 Hz, J=30 Hz,
J=53 Hz, Car), -114/127 (dd/s, J=12 Hz, J=22 Hz, Car trans to
N), -114/104 (dd/s, 2J(P,C)=6 Hz, 2J(C,F)=22 Hz, C=CF) ppm.
19F{1H} NMR (282.4 MHz, CD2Cl2, 298 K): δ=114.1 (dd+sat, 4J(Ftrans,β-
F)=2.5, 4J(Fcis,β-F)=22 Hz, 3J(Pt,β-F)=197 Hz, β-F), 236.5 (ddd+sat,
Selected spectroscopic data for [Pt(F)2(o-C6H4CF=CPh){κ2-(P,N)-
iPr2PC3H6NMe2}] (12a): 19F{1H} NMR (282.4 MHz, CD2Cl2, 298 K):
δ=112.7 (dd+sat, 4J(Ftrans,β-F)=3 Hz, 4J(Fcis,β-F)=22 Hz 3J(Pt,β-
F)=189 Hz, β-F), 231.3 (ddd, 4J(Ftrans,β-F)=3 Hz, 2J(Fcis,Ftrans)=100 Hz,
2J(P,Ftrans)=169 Hz, Ftrans), 238.5 (dd, br, 4J(Fcis,β-F)=22 Hz,
4
2
1
2J(P,Fcis)=6 Hz, J(Fcis,β-F)=22 Hz, J(Fcis,Ftrans)=93 Hz, J(Pt,Fcis)=78 Hz,
Fcis), -242.2 (ddd+sat, 2J(P,Ftrans)=158 Hz, 2J(Fcis,Ftrans)=93 Hz, 4J(Ftrans,β-
F)=2.5, 1J(Pt,Ftrans)=110 Hz, Ftrans) ppm. The Pt,F coupling constants
This article is protected by copyright. All rights reserved.

10.1002/chem.201700403
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were determined from 19F{1H} NMR spectra recorded at 470 MHz.
Spectroscopic data for [Pt(o-C6H4CF=CPh){κ2-(P,P)-Cy2PC2H4PCy2}]
(18): 1H NMR (300.1 MHz, [D8]THF, 298 K): δ = 7.43 (dd+sat,
J(P,H)=7 Hz, J(H,H)=7 Hz, J(Pt,H)=54 Hz, 1H, CHar), 7.27-7.22 (m, 2H,
CHar), 7.10-7.01 (m, 2H, CHar), 6.79-6.71 (m, 2H, CHar), 6.62-6.60 (m, 2H,
CHar), 2.39-2.30 (m, 4H, CH), 2.03 (m, 3H, CH2), 1.82-1.64 (m, 19H,
CH2), 1.37-1.27 (m, 8H, CH2), 1.23-1.04 (m, 14H, CH2) ppm;
31P{1H} NMR (121.5 MHz,
CD2Cl2,
298 K):
δ=17.33
(dd+sat,
2J(P,Fcis)=6 Hz, 2J(P,Ftrans)=160 Hz, 1J(Pt,P)=2848 Hz) ppm, LIFDI-TOF-
MS (THF): m/z: 618 [M]+, 599 [M-F]+, 580 [M-F2]+.
Spectroscopic data for [Pt(F)2(o-C6H4CF=CPh){κ2-(P,N)-iPr2PC2H4NMe2}]
(13b): 1H,13C-HMBC-NMR (400.1 MHz/75.5 MHz, CD2Cl2): δ=3.0/114
19F{1H} NMR (282.4 MHz,
4J(P,F)=28 Hz, 3J(Pt,F)=337 Hz)
[D8]THF,
298 K):
ppm;
δ=108.4
(d+sat,
,
2.8/114 (s/s, N(CH3)2/CVinyl) ppm.19F,13C-HMBC-
31P{1H} NMR (121.9 MHz,
(s/s, N(CH3)2)/Cvinyl
[D8]THF, 298 K): δ=62.6 (dd+sat, 4J(P,F)=28 Hz, 2J(P,P)=3 Hz,
1J(Pt,P)=2184 Hz), 61.7 (d+sat, 2J(P,P)=3 Hz, 1J(Pt,P)=1927 Hz) ppm;
LIFDI-TOF-MS (THF): m/z: 813 [M]+.
NMR (282.4 MHz/75.5 MHz, CD2Cl2): δ=-118/157 (ddd/s, J=7 Hz,
J=28 Hz, 1J(C,F)=265 Hz, C=CF), -118/145 (dd/s, J=7 Hz, J=30 Hz,
Car), -118/130 (d/s, J=7 Hz, Car), -118/114 (d/s, J(P,C)=9 Hz, C=CF trans
to N) ppm. 19F{1H} NMR (282.4 MHz, CD2Cl2, 298 K): δ=117.9 (d+sat,
4J(Ftrans,β-F)=4 Hz,
3J(Pt,β-F)=179 Hz,
β-F),
221.5
(dd+sat,
Reaction of [Pt{κ2-(P,P)-Cy2PC2H4PCy2}(ƞ2-PhC≡CPh)] (14) with two
equiv. XeF2
2J(P,Fcis)=9 Hz, 2J(Fcis,Ftrans)=99 Hz, 1J(Pt,Fcis)=91 Hz, Fcis), 237.2
(ddd+sat, 2J(P,Ftrans)=160 Hz, 2J(Fcis,Ftrans)=99 Hz, 4J(Ftrans,β-F)=4 Hz,
1J(Pt,Ftrans)=137 Hz, Ftrans
determined from 19F{1H} NMR spectra recorded at 470 MHz.
31P{1H} NMR (121.5 MHz,
CD2Cl2, 298 K): δ=20.36 (dd+sat,
2J(P,Fcis)=9 Hz, 2J(P,Ftrans)=160 Hz, 1J(Pt,P)=2860 Hz) ppm; LIFDI-TOF-
MS (THF): m/z: 618 [M]+, 599 [M-F]+, 580 [M-F2]+.
) ppm. The Pt,F coupling constants were
A CH2Cl2 solution (2 mL) of the complex [Pt{κ2-(P,P)-Cy2PC2H4PCy2}(ƞ2-
PhC≡CPh)] (14) (52 mg, 0.06 mmol) was cannulated to a CH2Cl2 solution
(1 mL) of XeF2 (22 mg, 0.12 mmol) in a PFA tube at -30°C. The yellow
reaction mixture was slowly warmed up to room temperature and stirred
for 1h. The solvent was reduced to 1 mL and an excess hexane (6 mL)
was added resulting in a product precipitation. The supernatant was
filtered off and the filtrate was dried under reduced pressure. NMR
spectroscopic measurements confirm the formation of 1,1,2,2-
Tetrafluoro-1,2-diphenylethane, (Z)-1,2-Difluoro-1,2-diphenylethene and
(E)-1,2-Difluoro-1,2-diphenylethene in a ratio of 1:3.5:2.5.[128,129] The
remaining residue was washed three times with hexane (1 mL) and dried
in vacuum. The NMR spectrum revealed the formation of [Pt(µ-OH){κ2-
(P,P)-Cy2PC2H4PCy2}]2[FHF]2 (15). The sample contained small
amounds of 17, which could not be separated.
Reaction of [Pt{κ2-(P,P)-Cy2PC2H4PCy2}(ƞ2-PhC≡CPh)] (14) with XeF2
A CH2Cl2 solution (2 mL) of the complex [Pt{κ2-(P,P)-Cy2PC2H4PCy2}(ƞ2-
PhC≡CPh)] (14) (68 mg, 0.09 mmol) was cannulated to a CH2Cl2 solution
(1 mL) of XeF2 (14 mg, 0.09 mmol) in a PFA tube at T = -30°C. The
yellow reaction mixture was slowly warmed up to room temperature and
stirred for 1h. The solvent was reduced to 1 mL and an excess hexane
(6 mL) was added resulting in a product precipitation. The hexane
solution which contains diphenylacetylene was filtered off. The remaining
solid was washed three times with hexane (1 mL), dried under vacuum,
and was dissolved in CD2Cl2. The freshly prepared solution consisted of
Acknowledgements
[Pt(µ-OH){κ2-(P,P)-Cy2PC2H4PCy2}]2[FHF]2 (15)
and
[Pt(PhC=CFPh)(F){κ2-(P,P)-Cy2PC2H4PCy2}] (16) in a ratio of 1:4 The
CD2Cl2 solution was monitored by NMR spectroscopy after one day. The
complex [Pt(PhC=CFPh)(F){κ2-(P,P)-Cy2PC2H4PCy2}] (16) was not
We gratefully acknowledge support from the research training group
“Fluorine as
a
Key Element” funded by the Deutsche
present
anymore.
The
amount
of
[Pt(µ-OH){κ2-(P,P)-
Forschungsgemeinschaft. We would like to thank L. Berg for assistance
with experiments and Dr. L. Zámostná and C. Berg for NMR
measurements.
Cy2PC2H4PCy2}]2[FHF]2 (15) did not change, which was checked on
using an external 31P standard (P(p-C6H5F)3). The NMR spectrum
revealed the presence of [Pt(µ-OH){κ2-(P,P)-Cy2PC2H4PCy2}]2[FHF]2 (15),
[Pt(F)2{κ2-(P,P)-y2PC2H4PCy2}] (17) and [Pt(o-C6H4CF=CPh){κ2-(P,P)-
Cy2PC2H4PCy2}] (18) in a ratio of 1:2:2.
Keywords: electrophilic fluorination • platinum complexes •
fluorido complexes
Spectroscopic data for [Pt(µ-OH){κ2-(P,P)-Cy2PC2H4PCy2}]2[FHF]2 (15):
1H NMR (300.1 MHz, CD2Cl2, 273 K): δ=15.82 (t, br, 1J(H,F)=130 Hz,
FHF), 6.07 (br, s, 2H, µ-OH), 2.53-1.25 (m, 96H, CH, CH2) ppm;
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CD2Cl2,
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293 K):
δ=233.6
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This article is protected by copyright. All rights reserved.

10.1002/chem.201700403
Chemistry - A European Journal
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The Versatile Behaviour of Platinum
Alkyne Complexes Towards XeF2:
Formation of Fluorovinyl and
Fluorido Complexes
Electrophilic fluorination with XeF2 occurs at platinum bound alkyne ligands to
yield platinum(II)-β-fluorovinyl-fluorido compounds. An excess of XeF2 gives access
to platinum(IV)-fluorido-complexes, but can also lead to fluorinated olefins.
This article is protected by copyright. All rights reserved.