Volatile methylplatinum complexes - Formation and reactions in anhydrous HF

Article abstract of DOI:10.1002/ejic.201201104

[(CO)₂Pt(CH₃)₂], [(PF₃) ₂Pt(CH₃)₂], and [(CF₃) ₂PC₂H₄P(CH₃)₂Pt(CH ₃)₂] [dfmpe = (CF_3<

Full text of DOI:10.1002/ejic.201201104

FULL PAPER
DOI:10.1002/ejic.201201104
Volatile Methylplatinum Complexes – Formation and
Reactions in Anhydrous HF
Roland Friedemann[a] and Konrad Seppelt*[a]
Keywords: Platinum / P ligands / HF reactions / Structure elucidation
[(CO)2Pt(CH3)2], [(PF3)2Pt(CH3)2], and [(CF3)2PC2H4P(CH3)2-
Pt(CH3)2] [dfmpe = (CF3)2PC2H4P(CF3)2] are obtained by li-
gand exchange reactions. The thermal stability of the com-
plexes increases in the given sequence, whereas their volati-
lity decreases. Demethylation reactions with anhydrous HF
cleave one methyl group. The addition of AsF5 and SbF5
often cleaves both methyl groups. The resulting L2Pt2+ com-
pounds are obtained in crystalline form with the correspond-
2–
ing [AsF6]–, [SbF6]–, [Sb2F11]–, and [B12F12
]
anions. Bridged
dimeric or trimeric platinum complexes are also formed.
lated.[4] We achieved its isolation by modification of a well-
known procedure, namely the reaction of a diene complex
with gaseous CO:
Introduction
There is a vast number of platinum(II) compounds
known that are stabilized by complex ligands. Platinum
complexes are also very important in many catalytic pro-
cesses. To mention just one example, (bipyrimidyl)plati-
num(II) in concentrated sulfuric acid catalyzes the oxi-
dation of methane to methanol.[1] This example shows that
platinum(II) complexed by the “weak” ligand sulfuric acid
is very reactive. Platinum(II) compounds with weakly basic
ligands are rare. PtF2, which should have PtII in a very ionic
environment, does not even exist! Possibly the compound
closest to having a naked Pt2+ ion is [Pt(H2O)4][SbF6]2,
which can only be prepared in a tedious way and is barely
stable at room temperature. Attempts to remove some or all
of the water molecules result in complete decomposition.[2]
One can try to obtain a partially stabilized PtII complex,
for example with two ligands L2Pt2+, which may be then
called “half naked” Pt2+. Here, the work by Roddick et al.,
who used the bidentate ligand (C2F5)2P–C2H4–P(C2F5)2 for
this purpose, should be mentioned.[3]
[(diene)Pt(CH3)2] + 2 CO Ǟ [(CO)2Pt(CH3)2].
The resulting [(CO)2Pt(CH3)2] is very volatile, which
hampered its isolation. In particular, the separation from
the commonly used dienes such as norbornadiene (nbd) or
cyclooctadiene (cod) proved to be impossible. Therefore, we
used 7-phenylnorbornadiene as the diene as it has a very
low vapor pressure.[5] For details of the starting compound
[C6H5–C7H7Pt(CH3)2] see the Experimental Section.
Pure [(CO)2Pt(CH3)2] thus obtained is a yellow crystal-
line solid with a m.p. of 5 °C that slowly decomposes above
0 °C. Its crystal structure is shown in Figure 1.
In the present work, we used CO, PF3, F2P(CH2)1,2PF2
and (CF3)2PC2H4P(CF3)2 (dfmpe) as protecting ligands.
The other ligands are two methyl groups, which should be
eliminated in HF solution as methane in the hope of gener-
ating L2Pt2+ complexes with very weakly coordinated
anions.
Results and Discussion
[(CO)2Pt(CH3)2] and Its Reactions
Figure 1. Crystal structure of [(CO)2Pt(CH3)2]2. ORTEP represen-
tation, 50% probability ellipsoids. The molecules pack in an almost
linear columnar structure with Pt–Pt distances of 338.0 pm.
[(CO)2Pt(CH3)2] has previously been identified in solu-
tion by NMR and IR spectroscopy but has not been iso-
[(CO)2Pt(CH3)2] reacts in anhydrous HF to result in the
[a] Freie Universität Berlin, Institut für Chemie und Biochemie,
Fabeckstraße 34-36, 14195 Berlin, Germany
Fax: +49-30-838-54289
cleavage of one Pt–CH3 bond:
HF
E-mail: seppelt@chemie.fu-berlin.de
[(CO)2Pt(CH3)2] Ǟ [(CO)2Pt(CH3)]+ + CH4
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Figure 2. Crystal structure of [(PF3)2Pt(CH3)2]. ORTEP representation, 50% probability ellipsoids. The three crystallographically indepen-
dent but otherwise identical molecules are shown. The columnar arrangement has Pt–Pt distances between 393.2 and 409.9 pm.
rav(Pt–C) = 210(1) pm, rav(Pt–P) = 220.1(5) pm, average C–Pt–C 84.0(5)°, average P–Pt–P 99.9(1)°.
The cation could only be identified by NMR spec-
troscopy in solution. It decomposes upon warming and also
after the addition of SbF5, which ought to give [SbF6]–- or
[Sb2F11]–-containing compounds.
Decomposition always produces finely divided Pt pow-
der. According to an X-ray powder analysis the average
crystal size is 50 nm.
[(PF3)2Pt(CH3)2] and Its Reactions
The preparation of [(PF3)2Pt(CH3)2] is completely analo-
gous to that of the carbonyl complex, except that PF3 is
used instead of CO. Again, it was necessary to start with
[(7-phenylnorbornadiene)Pt(CH3)2] to obtain a pure prod-
uct. [(PF3)2Pt(CH3)2] is a little less volatile but thermally
and chemically more stable. Its crystal structure is shown in
Figure 2. The spectroscopic data, especially the various
NMR spectroscopic data (see Figure 3 and the Experimen-
tal Section), are in accordance with the crystal structure.
Figure 3. 195Pt NMR spectrum of [(PF3)2Pt(CH3)2]; first-order
spectrum of a binominal triplet of septets of septets. Chemical shift
values are in ppm relative to K2PtCl6/H2O.
Figure 4. Crystal structures of [(PF3)PtCH3][BF4] (top) and [(PF3)2-
PtCH3][SbF6] (bottom). ORTEP representations, 50% probability
ellipsoids.
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The reaction of [(PF3)2Pt(CH3)2] with anhydrous HF can [(PF3)2Pt(CH3)][SbF6] are isolated below –35 °C. HF solu-
be interpreted by NMR spectroscopy, but no crystalline tions of these complexes show spectra similar to that of the
products can be isolated. There are two new products minor compound observed for [(PF3)2Pt(CH3)2] in HF.
formed in an intensity ratio of 2.9:1. The NMR spectra (31P,
The crystal structures of the two salts are shown in Fig-
19F, H) of the minor compound is very similar to that of ure 4. It is obvious that ionic formulations do not fully de-
the cation in [(PF3)2Pt(CH3)][BF4] or [(PF3)2Pt(CH3)][SbF6] scribe the structures; in fact, the compounds appear as ion
(see below). Here, the two PF3 groups are chemically and pairs with a close contact between the platinum atom and
magnetically no longer equivalent. The major compound one fluorine atom of the anions. The Pt–F distance is
has similar spectra, except that all lines are broadened. We 208(2) pm in the [BF4]– compound and 215.6(8) pm in the
1
–
assume this is due to a dimeric cation such as [(PF3)2(CH3)- [SbF6 ] compound. This shows clearly the more ionic char-
Pt–F–Pt(CH3)(PF3)2]+. It was not possible to crystallize any acter of [(PF3)2Pt(CH3)][SbF6] owing to the higher fluoride
of these compounds, and the platinum compounds decom- ion affinity (Lewis acidity) of SbF5 than BF3.
pose above –78 °C.
After warming the [(PF3)2Pt(CH3)][SbF6] sample in HF
Upon addition of BF3 or SbF5, however, thermally un- and [SbF5], two new compounds were found that are stable
stable crystalline complexes of [(PF3)2Pt(CH3)][BF4] and at room temperature. The main product is [(PF3)2Pt]-
[SbF6]2 (see Figure 5). This compound is again best de-
scribed as an ion pair. Here the Pt–F distances come down
to 206.0(5) and 208.9(4) pm, which shows that the “half
naked” [(PF3)2Pt]2+ cation competes well in terms of fluor-
ide ion affinity with SbF5.
The high fluoride ion affinity of the [(PF3)2Pt]2+ ion also
explains the formation of a minor side product, which has
only been characterized by a single-crystal structure deter-
mination, namely the trimeric [(PF3)2PtF]3[SbF6]3·HF (see
Figure 5). The cation has Pt–F bond lengths (203–208 pm)
similar (or even shorter) than those of [(PF3)2Pt][SbF6]2.
[(F2PCH2)2Pt(CH3)2] and [(F2P)2CH2Pt(CH3)2]2
To arrive at more stable (fluorophosphane)dimethylplati-
num complexes, we checked the ligands F2PC2H4PF2 and
F2PCH2PF2. Both were prepared according to a literature
procedure from the corresponding chlorides.[6] The plati-
num precursor for the ligand exchange reaction is
[codPt(CH3)2].
[(F2PCH2)2Pt(CH3)2] is formed in solution and can be
identified by 1H, 13C, 19F, 31P, and 195Pt NMR spec-
troscopy. Concentration of such solution results in an insol-
uble material that is probably polymeric.
Figure 5. Crystal structures of [(PF3)2Pt][SbF6]2 (top) and of the
cation in [(PF3)2PtF]3[SbF6]3·HF (bottom). ORTEP representation,
50% probability ellipsoids.
Figure 6. Crystal structure of dinuclear [(PF2)2CH2Pt(CH3)2]2.
ORTEP representation, 50% probability ellipsoids. The intra- and
intermolecular Pt–Pt distances are 351.8 and 381.0 pm.
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The reaction of F2PCH2PF2 and [codPt(CH3)2] results in
a dinuclear complex (see Figure 6). This compound slowly
dissolves in HF at –50 °C with the evolution of gas. The
NMR spectra indicate the loss of one methyl group per
platinum atom and the nonequivalency of the two phos-
phorus atoms at each platinum center. Attempts to obtain
crystalline materials failed. The addition of BF3 or AsF5
provides colorless precipitates that are unstable above
–50 °C.
[(dfmpe)Pt(CH3)2] and Its Reactions
The ligand (CF3)2PC2H4P(CF3)2 (dfmpe) has been
prepared by
a modification of a known procedure
(Scheme 1).[7]
–
Figure 7. Crystal structure of [(dfmpe)Pt][AsF6]2·HF. One AsF6
anion is a complex ligand and the other is a discrete anion. ORTEP
representation, 50% probability plot. [(dfmpe)Pt][SbF6]2(HF)2 and
[(dfmpe)Pt][SbF6][Sb2F11](HF)3 have similar structures, except that
in the former there is one additional HF in the lattice, and in the
latter an exchange of the external [SbF6]– anion by the [Sb2F11]–
anion.
Scheme 1.
This is then treated with [codPt(CH3)2] to form the title
compound. The ligand (CF3)2PC2H4P(CF3)2 is very similar
to (C2F5)2PC2H4P(C2F5)2, which has been used by Roddick
et al.[3] The advantage of complexes that contain CF3
groups is that they form crystals of better quality as they
have a lower tendency for disorder. In the following, we will
abbreviate (CF3)2PCH2CH2P(CF3)2 as dfmpe, in analogy to
(C2F5)2PCH2CH2P(C2F5)2, which has been abbreviated as
dfepe by Roddick.[3] [(dfmpe)Pt(CH3)2] is thermally much
more stable than [(CO)2Pt(CH3)2] and [(PF3)2Pt(CH3)2]. It
can be sublimed at 80–90 °C/14 mbar.
This compound dissolves in anhydrous HF with the for-
mation of one new compound, which decomposes upon
warming to room temperature. In the 31P NMR spectrum,
the two phosphorus atoms are nonequivalent. It is, there-
fore, safe to assume that only one methyl group has been
cleaved.
Upon addition of AsF5 to such a solution, the second
methyl group is also cleaved, and the compound [(dfmpe)-
Pt](AsF6)2·HF is formed (see Figure 7).
Figure 8. Structure of the [(dfmpe)PtF]22+ ion. ORTEP representa-
tion, 50% probability plot. Counterions are ([AsF6]–)2 or [B12F12]2–·
HF (see below).
If the excess AsF5 is removed before the crystallization,
a dinuclear complex, [(dfmpe)PtF2Pt(dfmpe)][AsF6]2, is
formed (see Figure 8).
SbF5 acts similarly to AsF5; the first product [(dfmpe)-
Pt][SbF6]2·2HF differs only from the AsF6 compound in the
HF content (Figure 7). A larger excess of SbF5, to reach the
less basic Sb2F11 ion, results in the formation of [(dfmpe)-
Pt][SbF6]·[Sb2F11]·3HF, in which the coordination sphere
around Pt is now completed by [SbF6] and HF, and the
[Sb2F11] anion is separate from the cation. Coordination of
the [Sb2F11] anion to the platinum atom is only achieved if
the crystallization is done in the absence of HF (see Fig-
ure 9).
This complex is possibly the one with the least basic li-
gand so far, namely [Sb2F11], which is considered even less
basic than SbF6 and HF.
Figure 9. [(dfmpe)Pt][Sb2F11]+ complex. ORTEP representation,
50% probability plot. There are two independent molecules in the
The product distribution varies depending on the reac-
tion conditions, especially when SbF5 is used as the fluoride unit cell, which are essentially identical. Counterions are [Sb2F11]–.
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Physical Methods: NMR spectra were obtained with a JEOL multi-
nuclear 400 spectrometer; 1H: 399.656 MHz (external reference
TMS), 19F: 376.00 MHz (external reference CFCl3), 31P:
161.7 MHz (external reference H3PO4/H2O), 195Pt: 85.36 MHz (ex-
ternal reference K2PtCl6/H2O). Raman spectra were recorded with
a Bruker RFS 100 FT Raman spectrometer. IR spectra were re-
corded with a 5 SXC Nicolet FT spectrometer. Single crystals were
handled with the exclusion of moisture and at low temperatures in
a special device[11] and cut to an appropriate size if necessary, and
data were measured with a Bruker SMART CCD 1000 TU dif-
fractometer by using Mo-Kα irradiation, a graphite monochroma-
tor, a scan width of ω = 0.3°, and a measuring time of 20 s per
frame. A full sphere mostly up to 2θ = 61° was usually obtained
by 2400 frames. After semiempirical absorption corrections
(SADABS) by equalizing symmetry-equivalent reflections, the
SHELX programs were used for solution and refinements.[12] Ex-
perimental details are summarized in Tables 1, 2, 3, and 4. CCDC-
895923 {for [(CO)2Pt(CH3)2]}, -895924 {for [(PF3)2Pt(CH3)2]},
-895929 {for [(PF3)2PtCH3][BF4]}, -895925 {for [(PF3)2Pt-
CH3][SbF6]}, -895930 {for [(PF3)2Pt][SbF6]2}, -895928 {for [(PF3)6-
Pt3F3][SbF6]3·HF}, -895916 {for [CH2(PF2)2Pt(CH3)2]}, -895921
{for [C6H5C7H7Pt(CH3)2]}, -895918 {for [(dfmpe)Pt(CH3)2]},
-895926 {for [(dfmpe)PtHF][AsF6]2}, -895917 {for [(dfmpe)PtF]2-
[(AsF6)]2(HF)2}, -895920 {for [(dfmpe)PtHF][SbF6]·2HF}, -895919
{for [(dfmpe)PtHF][SbF6]·[Sb2F11]·HF}, -895927 {for [(dfmpe)Pt]-
[Sb2F11]2}, -895922 {for [(dfmpe)Pt]2[Sb2F11]2}, and -895915 {for
[(dfmpe)PtF]2[B12F12](HF)2} contain the supplementary crystallo-
graphic 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.
ion acceptor. For example, after long reaction times be-
tween [(dfmpe)Pt(CH3)2] and SbF5, small amounts of the
dihydridodiplatinum complex [(dfmpe)PtH2Pt(dfmpe)]-
[Sb2F11]2 are formed. Similar complexes have been de-
scribed before, both as dicationic complexes such as here[8]
and as neutral complexes.[9] In this dinuclear compound,
the separation between the platinum atoms is now 260 pm,
in contrast to the distances in the fluorine-bridged dinuclear
and trinuclear complexes, so that a Pt–Pt interaction can be
discussed (see Figure 10).
2+
Figure 10. Structure of the [(dfmpe)PtH]2 ion; the counterion
[Sb2F11]– is not shown. ORTEP representation, 50% probability
plot.
Chemicals: AsF5, CsF, and CO were from laboratory stock. Anhy-
One attempt has been made to arrive at cationic com- drous HF was distilled from 98% technical HF, by using a stainless
steel vacuum line, into a stainless steel cylinder containing BiF5
(ca. 10 g) to remove any water as [H3O]+[BiF6]–. Cl2PCH2PCl2 was
purchased from Acros Chemicals, and Cl2PCH2CH2PCl2 was pur-
chased from abcr Co, Germany. SbF5 was distilled twice in vacuo
to remove any oxyfluorides and HF. It was only used if its viscosity
was high at room temperature. PF3 is commercially available but
is prohibitively expensive. We prepared it by a simple procedure
published recently.[13] A 300 mL stainless steel autoclave was filled
with commercial PCl3 (30 g, 218 mmol), and HF (13.8 g, 0.7 mol)
was then condensed into it. The mixture was heated at 80 °C for
24 h, during which time the pressure increased to about 100 bar.
After cooling to room temperature, the gaseous products were
blown through a water container and –78 and –160 °C cold traps.
With a single wash, all of the HCl and excess HF were completely
absorbed by the water. The PF3 from the –160 °C cold trap was
condensed at –196 °C into a metal storage cylinder. The product
was free of PCl2F, PFCl2, HCl, and HF. Yield 18.7 g (97%).
[codPt(CH3)2],[14] 7-phenylnorbornadiene,[5] 1,2-bis(difluorophos-
plexes with a completely different weakly coordinating
anion, namely [B12F12]2–, by salt metathesis (see Figure 8).
Under these conditions, a dimeric platinum complex with
two fluorine bridges is formed and is similar to one of the
products in the [AsF6]– series.
Conclusions
The molecules [(CO)2Pt(CH3)2] and [(PF3)2Pt(CH3)2]
present highly volatile small platinum complexes. Owing to
their instability, their use in further synthetic chemistry is
rather limited. Reactions with the cyclic compound
[(dfmpe)Pt(CH3)2] are more successful. In no case has it
been possible to arrive at a platinum centre that is so weakly
coordinated that it would react with elemental xenon, as
has been shown with AuI, AuII, AuIII, and HgII centers.[10]
This would demand different anions and should not be
tried in the presence of anhydrous HF. Reactions in the
presence of HF and xenon always lead to HF bound to Pt.
phanyl)ethane,[6] 1,2-bis(difluorophosphanyl)methane,[6] 1,2-bis(di-
[16]
phenoxyphosphanyl)ethane,[15] and Cs2-closo-B12F12
were pre-
pared according to literature procedures.
Dichlorido(7-phenylnorbornadiene)platinum(II): Potassium tetra-
chloroplatinate(II) (3.76 g, 9.06 mmol) was dissolved in a warm
solution of water, acetic acid, and hydrochloric acid, and 7-phenyl-
norbornadiene (3.05 g, 18.1 mmol) was added. The red mixture was
heated under reflux for 30 min. The solution became colorless, and
a yellow solid precipitated. The solid was removed by filtration at
room temperature, washed with water and ethanol, and dried in
high vacuum. Yield 3.65 g (89%). 1H NMR ([D8]THF): δ = 3.53
Experimental Section
General: The handling of hydrolytically sensitive compounds was
performed in a glove box with pH2O Ͻ 1 ppm and pO2 = 1 ppm.
Reactions with anhydrous HF were performed by its distillation
into PFA tubes (PFA = perfluorovinylether tetrafluoroethylene co-
polymer) by using a stainless steel vacuum line.
2
(s, 1 H), 4.77 (m, 2 H), 5.25 (m, JH,Pt = 69 Hz, 2 H), 5.47 (m,
2JH,Pt = 69 Hz, 2 H), 7.20–7.42 (m, 5 H) ppm. IR: ν = 3067 (w),
˜
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Table 1. Crystal parameters, data collection, and refinement details for the single-crystal X-ray determinations of [(CO)2Pt(CH3)2], [(PF3)2-
Pt(CH3)2], [(PF3)2Pt(CH3)][BF4], and [(PF3)2Pt(CH3)][SbF6].
[(CO)2Pt(CH3)2]
[(PF3)2Pt(CH3)2]
[(PF3)2Pt(CH3)][BF4]
[(PF3)2Pt(CH3)][SbF6]
Empirical formula
M
Crystal system
Space group
a [pm]
b [pm]
c [pm]
C4H6O2Pt
281.2
orthorhombic
Pbca
1302.8(7)
675.5(4)
1446.5(9)
90
C2H6F6P2Pt
401.1
monoclinic
P21/c
1379.2(5)
826.3(3)
2371.8(10)
90
CH3BF10P2Pt
472.9
monoclinic
P21/m
736.1(2)
792.3(2)
834.1(2)
90
CH3F12P2PtSb
621.8
orthorhombic
P212121
892.7(1)
893.3(1)
1514.0(2)
90
α [°]
β [°]
γ [°]
90
90
1273.0
8
2.934
106.67(1)
90
2589.5
12
3.087
16.66
0.3ϫ0.2ϫ0.05
colorless
7869
0.0310
307
0.0405, 0.1067
–
104.97(2)
90
487.2
90
90
1207.4
4
3.421
14.20
0.05ϫ0.04ϫ0.04
colorless
3259
–
157
0.0556, 0.1435
0.466
Vϫ106[pm3]
Z
2
Dcalcd. [Mgm3]
μ [mm–1]
Crystal size [mm]
Color
3.223
14.84
0.05ϫ0.05ϫ0.01
colorless
1752
0.1134
89
21.94
0.4ϫ0.05ϫ0.01
yellow
1946
0.0857
66
0.0450, 0.1266
–
Independent data
Rint
Parameters
R1, wR2
0.0727, 0.1909
–
Flack parameter
Table 2. Crystal parameters, data collection, and refinement details for the single-crystal X-ray determinations of [(PF3)2Pt][SbF6]2, [(PF3)6-
Pt3F3][SbF6]3·HF, [CH2(PF2)2Pt[CH3]2]2, and [(dfmpe)Pt[CH3]2].
[(PF3)2Pt][SbF6]2
[(PF3)6Pt3F3][SbF6]3·HF
[CH2(PF2)2Pt[CH3]2]2
[(dfmpe)Pt[CH3]2]
Empirical formula
M
Crystal system
Space group
a [pm]
b [pm]
c [pm]
F18P2PtSb
842.5
monoclinic
P21/n
832.3(1)
1251.6(1)
1427.3(2)
90
94.91(1)
90
F40P6Pt3Sb
1896.34
monoclinic
P21/n
1148.5(1)
1393.9(1)
2037.0(2)
90
90.5(1)
90
3260.8
4
3.863
15.80
0.3ϫ0.05ϫ0.05
colorless
7289
0.0620
470
C6H16F8P4Pt2
754.25
C4H10F12P2Pt
591.2
Tetragonal
P42
979.7(1)
979.7(1)
849.7(2)
90
90
90
850
2
2.407
8.91
0.3ϫ0.2ϫ0.1
Colorless
2493
0.0284
107
triclinic
¯
P1
773.4(2)
883.9(2)
1329.7(3)
77.68(1)
83.54(1)
65.20(1)
805.8
α [°]
β [°]
γ [°]
Vϫ106 [pm3]
Z
1481.4
4
3.778
2
Dcalcd. [Mgm3]
μ [mm–1]
Crystal size [mm]
Color
3.109
17.80
0.15ϫ0.15ϫ0.06
colorless
4776
0.0265
186
0.0219, 0.0531
–
13.44
0.4ϫ0.4ϫ0.2
colorless
5321
–
209
0.0498, 0.1329
–
Independent data
Rint
Parameters
R1, wR2
0.0734, 0.1916
–
0.0239, 0.0657
0.243
Flack parameter
3050 (w), 2894 (vw), 1730 (w), 1596 (w), 1496 (w), 1448 (w), 1394
was slowly added to the mixture. A cold saturated ammonium
(w), 1340 (w), 1293 (m), 1228 (w), 1198 (w), 1163 (w), 1141 (w), chloride solution (5 mL) was added within 2 h. After warming the
1078 (w), 1032 (w), 975 (m), 932 (w), 908 (w), 883 (w), 861 (w), mixture to room temperature, the phases were separated. The aque-
844 (w), 831 (w), 817 (w), 789 (w), 741 (s), 698 (s), 647 (w), 622
ous phase was washed three times with diethyl ether. The combined
organic phases were dried with sodium sulfate, which was removed
(w), 608 (w) cm–1. Raman: ν = 83 (s), 211 (w), 151 (m), 211 (w),
˜
244 (w), 266 (w), 322 (w), 334 (w), 572 (w), 883 (w), 941 (w), 1004 by filtration, and the solvent was removed. The resulting brown
(w), 1029 (w), 1078 (w), 1140 (w), 1157 (w), 1191 (w), 1228 (w), residue was dissolved in pentane, and – after cooling the solution
1418 (w), 1582 (w ), 1602 (w), 3034 (w), 3050 (w), 3059 (w), 3066
to –80 °C – a yellow solid was obtained. Single crystals were ob-
(w), 3076 (w) cm–1. MS (EI, 190 °C): m/z = 434 [M]+·, 398 [M – tained by slow evaporation of the pentane at room temperature.
HCl]+·, 168 [Ph-nbd]+·, 167 [Ph2CH]+·, 165 [C13H9]+·.
Yield 1.1 g (81%). H NMR (CDCl3): δ = 0.77 (s, JH,Pt = 90 Hz,
1
2
2
3 H), 0.81 (s, JH,Pt = 90 Hz, 3 H), 3.39 (s, 1 H), 4.28 (m, 2 H),
2
2
Dimethyl(7-phenylnorbornadiene)platinum(II): Dichlorido(7-phen- 4.84 (m, JH,Pt = 38 Hz, 2 H), 5.15 (m, JH,Pt = 40 Hz, 2 H), 7.04
ylnorbornadiene)platinum(II) (1.5 g, 3.45 mmol) was dissolved in
diethyl ether (25 mL) at 0 °C, and methyllithium (5.4 mL, 1.6 m)
(m, 2 H), 7.17–7.30 (m, 3 H) ppm. 13C{1H} NMR: δ = 6.5 (s, 1JPt,C
1
2
= 809 Hz), 6.7 (s, JPt,C = 812 Hz), 53.3 (s, JPt,C = 39 Hz), 86.0 (s,
Eur. J. Inorg. Chem. 2013, 1197–1206
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Table 3. Crystal parameters, data collection, and refinement details for the single-crystal X-ray determinations of [(dfmpe)PtHF][AsF6]2,
[(dfmpe)PtHF][SbF6]2HF, [(dfmpe)PtHF][SbF6]·[Sb2F11](HF)2, and [(dfmpe)PtF]2[AsF6]2(HF)2.
[(dfmpe)PtHF][AsF6]2 [(dfmpe)PtHF][SbF6]2HF [(dfmpe)PtHF][SbF6]·[Sb2F11](HF)2 [(dfmpe)PtF]2[AsF6]2(HF)2
Empirical formula C6H5As2F25P2Pt
C6H4F26P2PtSb2
1070.6
monoclinic
Cc
1611.5(2)
1302.9(2)
1100.0(2)
90
90.142
90
2309.6
4
C6H7F32P2PtSb3
1306.4
monoclinic
P21/n
1189.6(3)
1711.2(4)
1372.8(3)
90
101.801(4)
90
2730.2
4
3.174
8.37
C12H10AsF40P4Pt2
1576.1
M
954.0
monoclinic
Cc
1008.4(2)
1520.6(3)
1494.6(3)
90
Crystal system
Space group
a [pm]
b [pm]
c [pm]
triclinic
¯
P1
969.8(3)
987.7(3)
1072.4(3)
83.64(1)
84.79(1)
65.33(1)
926.6
α [°]
β [°]
γ [°]
106.76(1)
90
2194.5
4
2.903
9.74
Vϫ106 [pm3]
Z
1
Dcalcd. [Mgm3]
3.079
8.71
2.824
9.70
μ [mm–1]
Crystal size [mm] 0.4ϫ0.05ϫ0.05
Color yellow
Independent data 5791
0.3ϫ0.3ϫ0.2
yellow
5328
0.0330
334
0.0228, 0.0507
0.0
0.3ϫ0.2ϫ0.03
light yellow
7271
0.0481
398
0.0442, 0.1202
–
0.1ϫ0.1ϫ0.1
yellow
5503
0.0341
272
0.0356, 0.0871
–
Rint
Parameters
R1, wR2
0.0249
337
0.202, 0.0435
0.169
Flack parameter
Table 4. Crystal parameters, data collection, and refinement details for the single-crystal X-ray determinations of [(dfmpe)Pt][Sb2F11]2,
[(dfmpe)PtH]2[Sb2F11]2, (dfmpe)[PtF]2[B12F12](HF)2, and [C6H5C7H7Pt(CH3)2].
[(dfmpe)Pt][Sb2F11]2
[(dfmpe)PtH]2[Sb2F11]2
(dfmpe)[PtF]2[B12F12](HF)2
[C6H5C7H7Pt(CH3)2]
Empirical formula
M
Crystal system
Space group
a [pm]
b [pm]
c [pm]
C6H4F34P2PtSb4
1466.1
C12H10F46P4Pt2Sb4
C12H10B12F40P4Pt2
1557.9
monoclinic
P21/n
1106.6(2)
1369.3(3)
1382.9(3)
90
91.75(1)
90
2094.3
2
2.470
7.01
C15H18Pt
393.48
monoclinic
P21/c
1104.9(4)
653.6(2)
1747.7(6)
90
103.12(1)
90
1229.3
4
2.126
11.38
2029.3
monoclinic
P21/n
1008.4(3)
2094.2(5)
1048.1(2)
90
98.93(1)
90
2186.52
2
3.082
9.17
0.1ϫ0.03ϫ0.03
orange
6215
triclinic
¯
P1
1274.3(7)
1469.1(8)
1711.2(7)
77.08(5)
69.94(5)
89.94(4)
2922.9
α [°]
β [°]
γ [°]
Vϫ106 [pm3]
Z
4
Dcalcd. [Mgm3]
μ [mm–1]
Crystal size [mm–1]
Color
3.332
8.75
0.2ϫ0.1ϫ0.05
light yellow
14023
0.3ϫ0.2ϫ0.1
colorless
6384
0.3ϫ0.05ϫ0.01
light yellow
3424
Independent data
Rint
0.0533
–
0.0240
0.0442
Parameters
R1, wR2
850
313
330
147
0.0719, 0.2053
0.0558, 0.1661
0.0198, 0.0483
0.0264, 0.0915
3
1
1JPt,C = 48 Hz), 87.3 (s, JPt,C = 44 Hz), 88.3 (s, JPt,C = 48 Hz),
cis-Dicarbonyldimethylplatinum(II): [PtMe2(Ph-nbd)] (490 mg,
1.25 mmol) and dimethyl ether (5 mL) were added into a glass ves-
sel equipped with a Teflon valve, and carbon monoxide (3.1 mmol)
was condensed at –196 °C into the mixture. The contents were
warmed to room temperature, and a clear solution formed. A trap-
126.8 (s), 128.0 (s), 128.4 (s) ppm. 195Pt{1H} NMR: δ = –3551 (s,
1JPt,C = 812 Hz) ppm. IR: ν = 3080 (vw), 3056 (w), 3018 (w), 2919
˜
(w), 2863 (w), 2781 (w), 1596 (w), 1575 (w), 1495 (w), 1441 (w),
1300 (w), 1260 (w), 1170 (w), 1089 (m), 1073 (m), 1030 (w), 937 (w),
812 (w), 757 (w), 726 (s), 694 (s), 645 (m), 572 (m) cm–1. Raman: ν to-trap condensation in vacuo (–15, –78, and –196 °C) gave the title
˜
= 83 (s), 143 (m), 163 (m), 184 (m), 236 (m), 256 (w), 531 (w), 554
(w), 574 (m), 619 (w), 647 (w), 859 (w), 899 (w), 920 (w), 937 (w),
991 (w), 1003 (m), 1031 (w), 1041 (w), 1089 (w), 1135 (w), 1155
compound in high purity in the –78 °C trap. Yield 250 mg (71%).
Single crystals were obtained by slow cooling of a dichloromethane
solution to –80 °C. M.p. 5 °C. 1H NMR (CD2Cl2): δ = 0.88 (s,
(w), 1170 (w), 1197 (w), 1209 (w), 1228 (w), 1289 (w), 1305 (w), 2JH,Pt
= δ = =
78 Hz) ppm. 13C{1H} NMR: –2.1 (1JC,Pt
1340 (w), 1436 (w), 1457 (w), 1580 (w), 1602 (w), 2868 (w), 2905
(w), 3001 (w), 3010 (w), 3038 (w), 3061 (w), 3078 (w) cm–1. MS
(EI, 50 °C): m/z = 393.3 [M]+·, 168 [Ph-nbd]+·, 167 [Ph2CH]+·, 165
[C13H9]+·.
592 Hz),178.2 (1JC,Pt = 908 Hz) ppm. 195Pt NMR: δ = –4255 (sept,
1
2JPt,H = 77 Hz) ppm. 195Pt{1H} NMR: δ = –4255 (s, JPt,C = 904,
1JPt,C = 591 Hz) ppm. IR (gas): ν = 462 (m), 2044 (w), 2079 (vs),
˜
2121 (vs), 2128 (vs), 2830 (w), 2907 (m), 2968 (m) cm–1. Raman: ν
˜
Eur. J. Inorg. Chem. 2013, 1197–1206
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= 83 (s), 117 (m), 287 (w), 411 (m), 460 (w), 544 (m), 561 (m), 1232 two-chamber 4 mm PFA tube, and antimony pentafluoride
(w), 1418 (w), 2063 (w), 2118 (w), 2821 (w), 2896 (w), 2960 (w) (250 mg, 1.2 mmol) was added to the other part. aHF (0.5 mL) was
cm–1. MS (EI, 30 °C): m/z = 281 [M]+·, 266 [M – CH3]+, 251 [M –
condensed into the part of the tube containing the platinum com-
plex. At –78 °C, a colorless solution formed within 1 h with the
evolution of gas. The gas was removed under vacuum, and the con-
tents of the two parts of the tube were combined. A colorless pre-
cipitate immediately formed and dissolved completely at –35 °C.
The tube was sealed, and slow cooling of the solution to –80 °C
afforded crystals. 1H NMR (aHF, –35 °C): δ = 0.8 (br. m) ppm.
2 CH3]+, 238 [M – CH3 – CO]+, 209 [PtCH2]+.
cis-Dicarbonyldimethylplatinum(II) in Anhydrous HF (aHF):
[PtMe2(CO)2] (80 mg, 0.28 mmol) and aHF (0.5 mL) were con-
densed into a 4 mm PFA tube at –196 °C. At –80 °C, the complex
dissolved with the evolution of gas, and a yellow solution formed.
1
The gas was removed under vacuum, and the tube was sealed. H
1
2
19F NMR (aHF, –35 °C): δ = –40.8 (d, JF,P = 1440, JF,Pt
=
NMR (aHF, –80 °C): δ = 0.83 (br. s, 2JH,Pt = 60 Hz) ppm. 13C{1H}
1
2
312 Hz), –31.8 (d, JF,P = 1260, JF,Pt = 1430 Hz), –94.4 (br.),
1
1
NMR: δ = –17.6 (s, JC,Pt = 319 Hz), 161.9 (s, JC,Pt = 1780 Hz),
–120.7 (br.), –143.4 (br.) ppm. 31P NMR (aHF, –35 °C): δ = 47.9
172.1 (s, JC,Pt = 866 Hz) ppm. 195Pt{1H} NMR: δ = –4273 (s)
1
1
1
2
1
(qd, JP,Pt = 12390, JP,F = 1260, JP,P = 56 Hz), 155.6 (qd, JP,F
=
ppm. At room temperature, the solution turns brown within
10 min. Warming the solution to 50 °C for 5 h quantitatively pro-
duces nanocrystalline platinum.
1
2
1430, JP,Pt = 3740, JP,P = 55 Hz) ppm.
Bis(trifluorophosphane)platinum(II) Bis(hexafluoridoantimonate): A
reaction mixture as described above was warmed to room tempera-
ture, and a second gas evolution occurred. The compounds
[Pt(PF3)2][SbF6]2 and (possibly) [PtMe(PF3)3]+ formed in a ratio of
3:2. [Pt(PF3)2][SbF6]2 crystallized after slow cooling of the solution
to –30 °C. Recrystallization of [Pt(PF3)2][SbF6]2 in aHF produced
cis-Dimethylbis(trifluorophosphane)platinum(II): [PtMe2(Ph-nbd)]
(827 mg, 2.10 mmol) was added into a glass vessel equipped with a
Teflon valve. Dimethyl ether (ca. 5 mL) and phosphorus trifluoride
(500 mg, 5.7 mmol) were condensed into the vessel at –196 °C. The
mixture was warmed to room temperature, and a clear yellow solu-
tion formed. After 1 h, fractional condensation through –10, –78,
and –196 °C cold traps afforded the pure title compound in the
–78 °C trap. Yield 750 mg (89%). M.p. –54 °C. 1H NMR (CD2Cl2):
some [Pt(PF3)2F]3[SbF6]3·HF. Yield of [Pt(PF3)2][SbF6]2: 20 mg
1
(20%). [Pt(PF3)2][SbF6]2: 19F NMR (aHF): δ = –33.5 (d, JF,P
=
1300, JF,Pt = 827 Hz) ppm. 31P NMR (aHF): δ = 8.5 (q, br, JP,Pt
= 8640, JP,F = 1310 Hz) ppm. Raman: ν = 83 (s), 119 (w), 218
2
1
1
3
2
δ = 0.99 (t, JH,P = 22, JH,Pt = 74 Hz) ppm. 31P NMR: δ = 125.3
˜
(q, JP,F = 1380, JP,Pt = 3300 Hz) ppm. 19F NMR: δ = –34.6 (m)
1
1
(w), 232 (m), 281 (m), 300 (w), 390 (w), 411 (w), 560 (w), 587 (w),
1
649 (s), 985 (m), 1047 (w) cm–1. [PtMe(PF3)3]+: H NMR (aHF):
ppm. 13C{1H} NMR: δ = 1.2 (d m, JC,P = 151, JC,Pt = 564 Hz)
2
1
3
2
δ = 1.06 (q, JH,P = 8, JH,Pt = 53 Hz) ppm. 19F NMR (aHF): δ =
ppm. 195Pt NMR: δ = 4704 (tseptsept, JPt,P = 3270, JPt,F = 292,
1
2
1
2
2JPt,H = 77 Hz) ppm. IR (gas): ν = 515 (s), 528 (m), 547 (w), 877
–33.1 (d, JF,P = 1400, JF,Pt = 285 Hz, 3 F), –41.1 (m, 6 F) ppm.
˜
31P NMR (aHF): δ = 122.4 (qt, JP,F = 1400, JP,P = 78, JP,Pt
=
1
2
1
(vs), 907 (vs), 919 (vs), 926 (vs), 1217 (w), 2827 (w), 2910 (w), 2971
(w) cm–1. Raman: ν = 83 (s), 96 (s), 225 (m), 236 (m), 297 (w), 389
3640 Hz, 1 P), 96.5 (m, 2 P) ppm.
˜
(w), 527 (m), 550 (s), 626 (w), 741(w), 864 (w), 922 (w), 1211 (w),
1234 (w), 1428 (w), 2820 (w), 2902 (w), 2958 (w) cm–1. MS (EI,
30 °C): m/z = 401 [M]+·, 386 [M – CH3]+, 371 [M – 2 CH3]+, 298
[M – CH3 – PF3]+, 283 [M – 2 CH3 – PF3]+, 209 [PtCH2]+, 88
[PF3]+·. HRMS: calcd. for [M]+· 399.9476; found 399.9487.
[1,2-Bis(difluorophosphanyl)ethane]dimethylplatinum(II): 1,2-Bis(di-
fluorphosphanyl)ethane (150 mg, 0.9 mmol) and (cyclooctadiene)-
dimethylplatinum(II) (300 mg, 0.9 mmol) were separately dissolved
in diethyl ether (5 mL). The phosphane solution was added slowly
under vigorous stirring to the other solution, and a colorless solid
formed. Contact with air, too high concentration or cooling re-
sulted in the formation of an insoluble yellow solid. The reaction
cis-Dimethylbis(trifluorophosphane)platinum(II) in aHF: A 4 mm
PFA tube was filled with [PtMe2(PF3)2] (100 mg, 0.25 mmol), and
aHF (0.5 mL) was condensed into it. At –78 °C, the platinum com-
plex reacted within 1 h to result in a colorless solution and the
evolution of gas. The gas was removed under vacuum, and the tube
was sealed. 1H NMR (aHF, –80 °C): δ = 0.8 (br. m) ppm. 31P NMR
1
can also be performed in dichloromethane or tetrahydrofuran. H
3
2
NMR (CD2Cl2): δ = 0.73 (t, JH,P = 9, JH,Pt = 68 Hz), 2.28 (m)
ppm. 31P NMR (CD2Cl2): δ = 206.4 (t, JP,F = 1160, JP,Pt
=
1
1
2640 Hz) ppm. 19F NMR (CD2Cl2): δ = –74.8 (d, JF,P = 1160,
1
1
1
2JF,Pt = 193 Hz) ppm. 13C{1H} NMR (CD2Cl2): δ = 0.1 (d, JC,P
2
(aHF, –80 °C): major product: δ = 59.9 (br. q, JP,Pt = 9970, JP,F
1
1
= 127, 1JC,Pt = 540 Hz), 26.7 (m) ppm. 195Pt{19F} NMR (CD2Cl2):
= 1290 Hz), 145.5 (br. q, JP,Pt = 3350, JP,F = 1430 Hz); minor
product: δ = 65.7 (qd, JP,Pt = 9970, JP,F = 1260, JP,P = 55 Hz),
1
1
2
1
2
δ = 4528 (t, JPt,P = 2650, JPt,H = 66 Hz) ppm.
137.8 (qd, JP,Pt = 3370, JP,F = 1430, JP,P = 55 Hz) ppm. 19F
NMR (aHF, –80 °C): major product: δ = –42.3 (br. d, 1JF,P = 1440,
2JF,Pt = 271 Hz), –33.8 (br. d, 1JF,P = 1250, 2JF,Pt = 1240 Hz); minor
product: δ = –40.7 (d, 1JF,P = 1430, 2JF,Pt = 269 Hz), –34.7 (d, 1JF,P
1
1
2
Bis{bis(difluorophosphanyl)methane]dimethylplatinum(II)}: (Cyclo-
octadiene)dimethylplatinum(II) (510 mg, 1.5 mmol) was added to
an ampoule with a valve. At –196 °C, dichloromethane (ca. 10 mL)
and bis(difluorophosphanyl)methane (240 mg, 1.6 mmol) were
condensed into the ampoule. The valve was closed, and the am-
poule was warmed to room temperature. A milky suspension
formed. A clear solution was obtained by carefully warming of the
suspension to 50 °C. Upon cooling of the solution to 5 °C, yellow
crystals formed. The crystals were dried in high vacuum. Yield
2
= 1260, JF,Pt = 1160 Hz) ppm.
Methylbis(trifluorophosphane)platinum(II) Tetrafluoridoborate: Into
the colorless solution described above, boron trifluoride (0.3 mmol)
was condensed at –78 °C. A colorless precipitate formed immedi-
ately. The excess BF3 was removed under vacuum, and the tube
was sealed. At –60 °C, the solid dissolved, and a yellow solution
formed that slowly turned brown. Slow cooling of the solution to
1
3
2
400 mg (70%). H NMR (CDCl3): δ = 0.80 (t, JH,P = 10, JH,Pt
=
69 Hz), 3.11 (br. s) ppm. 31P NMR (CDCl3): δ = 192.6 (m) ppm.
19F NMR (CDCl3): δ = –60.6 (m), –74.7 (m) ppm. 13C{1H} NMR
1
–80 °C afforded crystals. NMR (aHF, –60 °C): H NMR: δ = 0.9
1
1
(br. m) ppm. 31P NMR: δ = 49.5 (qd, JP,Pt = 12140, JP,F = 1250,
(CD2Cl2, 50 °C): δ = 0.1 (d, JC,P = 130, 1JC,Pt = 560 Hz), 45.3 (m)
2
2JP,P = 56 Hz), 154.1 (qd, 1JP,F = 1440, 1JP,Pt = 3680, 2JP,P = 56 Hz)
ppm. 195Pt{1H} NMR (CD2Cl2, 50 °C): δ = 4427 (tquint, JPt,P
=
1
ppm. 19F NMR: δ = –41.3 (d, JF,P = 1440, JF,Pt = 306 Hz), –32.5
1
2
2
2770, JPt,F = 183 Hz) ppm. IR: ν = 708 (s), 774 (s), 841 (s), 893
˜
1
2
(d, JF,P = 1260, JF,Pt = 1400 Hz) ppm.
(m), 1065 (w), 1139 (m), 1216 (w), 1347 (m), 1424 (w), 2814 (w),
Methylbis(trifluorophosphane)platinum(II) Hexafluoridoantimonate: 2899 (m), 2957 (w) cm–1. Raman: ν = 83 (s), 99 (w), 119 (vw), 158
˜
[PtMe2(PF3)2] (50 mg, 0.13 mmol) was added into one part of a
(w), 223 (w), 243 (m), 272 (m), 417 (vw), 433 (w), 518 (m), 532 (s),
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FULL PAPER
708 (vw), 720 (vw), 770 (vw), 796 (vw), 807 (vw), 841 (vw), 882
(vw), 895 (vw), 1066 (vw), 1147 (vw), 1204 (vw), 1228 (vw), 1346
(vw), 2812 (vw), 2899 (w), 2956 (vw) cm–1. MS (EI, 30 °C): m/z =
739 [M – CH3]+, 709 [M – CH3 – HF]+. HRMS: calcd. for [M –
CH3]+ 738.9125; found 738.9102.
–196 °C. At –78 °C, the colorless compound dissolved, gas evolved,
and a yellow solution formed. The gas was removed under vacuum,
1
and the PFA tube was sealed. H NMR (–70 °C): δ = 2.11 (br. m),
3.36 (br. m), 3.64 (br. m) ppm. 19F NMR (–70 °C): major product:
2
3
2
3
δ = –57.5 (d, JF,P = 88, JF,Pt = 70 Hz), –59.7 (d, JF,P = 97, JF,Pt
= 93 Hz); minor product: –57.5 (d, 2JF,P = 88, 3JF,Pt = 70 Hz) ppm.
Bis{[bis(difluorophosphanyl)methane]dimethylplatinum(II)} in aHF:
Bis{[bis(difluorophosphanyl)methane]dimethylplatinum(II)} (120 mg,
0.16 mmol) and aHF (0.5 mL) were combined in a 4 mm PFA tube.
The platinum complex dissolved at –50 °C within 1 h to form a
yellow solution. The evolved gas was removed under vacuum, and
the tube was sealed. 1H NMR (aHF, –60 °C): δ = 1.87 (br. m, 3
H), 4.04–4.44 (m, 2 H) ppm. 31P NMR (aHF, –60 °C): δ = 126.2
31P{19F} NMR (–70 °C): major product δ = 78.0 (s, JP,Pt
=
1
1
1
1580 Hz), 53.0 (s, JP,Pt = 5600 Hz); minor product: 74.3 (s, JP,Pt
= 1580 Hz), 56.2 (s, JP,Pt = 5300 Hz) ppm. 13C{1H,19F} NMR
1
(–70 °C): δ = 15.2 (m), 22.7 (m), 19.2 (m), 124.5 (m) ppm.
1
195Pt{19F} NMR (–70 °C): major product: δ = –4373 (dd, JPt,P
=
1
1
1580, JPt,P = 5500 Hz); minor product: –4400 (dd, JPt,P = 1560,
1JPt,P = 5600 Hz), –4536 (dd, JPt,P = 1570, JPt,P = 5300 Hz) ppm.
1
1
1
(m, JP,Pt = 7.6 kHz), 211.7 (m) ppm. 19F NMR (aHF, –60 °C): δ
= –81.5 (m), –72.2 (m), –61.7 (m), –50.1 (m) ppm. 13C{1H} NMR
(aHF, –60 °C): δ = 9 (br. m), 45 (br. m) ppm. 195Pt{1H,19F} NMR
(aHF, –60 °C): δ = –4120 (m, br) ppm.
{1,2-Bis[bis(trifluoromethyl)phosphanyl]ethane}(hydrogen fluoride)-
platinum(II) Bis(hexafluoridoarsenate) {[(dfmpe)PtHF][AsF6]2}:
Into the solution described above that had been kept at –78 °C,
arsenic pentafluoride (ca. 0.5 mmol) was condensed at –196 °C.
The tube was sealed and warmed to –78 °C. A yellow precipitate
formed that dissolved at –20 °C. Slow cooling of the solution to
–80 °C afforded yellow crystals.
1,2-Bis[bis(trifluoromethyl)phosphanyl]ethane (dfmpe): Cesium
fluoride (0.50 g, 3.3 mmol) and 1,2-bis(diphenoxyphosphanyl)eth-
ane (5.00 g, 10.8 mmol) were added to a 100 mL glass vessel
equipped with a Teflon valve, and diethyl ether (10 mL) was added.
CF3Si(CH3)3 (10.0 mL, 67.5 mmol) was then carefully added. The
vessel was closed, and the contents were stirred slowly for 24 h.
The surface of the CsF quickly turned brown, and finally the whole
suspension became brown. All volatiles including the product were
distilled in vacuo. Yield 1.67 g (42%) in 12.8 g of solution accord-
Bis{1,2-bis[bis(trifluoromethyl)phosphanyl]ethane}di-μ-fluoridodi-
platinum(II) Bis(hexafluoridoarsenate) {[(dfmpe)PtF2Pt(dfmpe)]-
[AsF6]2}: 1,2-{Bis[bis(trifluoromethyl)phosphanyl]ethane}dimethyl-
platinum(II) (49 mg, 0.083 mmol) was treated with aHF (0.2 mL)
at –78 °C in a PFA tube. The gas that formed was removed under
vacuum, and arsenic pentafluoride (50 mL, 600 mbar, 20 °C) was
condensed into the mixture. After warming the mixture to –20 °C,
the excess AsF5 was pumped off, and the tube was sealed. Storage
of the mixture at –30 °C overnight produced a yellow solid that
dissolved only at 40 °C. Slow cooling of the solution to room tem-
perature afforded yellow crystals.
1
1
ing to the H and 19F NMR spectra. H NMR: δ = 2.29–2.31 (m)
ppm. 31P NMR: δ = –1.5 to –4.5 (m) ppm. 31P{19F} NMR: δ =
–2.9 (s) ppm. 13C{1H,19F} NMR: δ = 14.4, 128.2 (dd, JC,P = 9,
1
2JC,P = 10 Hz) ppm. 19F{31P} NMR: δ = –55.2 (s) ppm. 19F NMR:
δ = –56.3 (m) ppm.
{1,2-Bis[bis(trifluoromethyl)phosphanyl]ethane}dimethylplatinum(II)
{[(dfmpe)Pt(CH3)2]}: (Cyclooctadiene)dimethylplatinum(II) (1.53 g,
4.60 mmol) was added to a solution of 1,2-bis[bis(trifluoromethyl)-
phosphanyl]ethane (1.67 g, 4.58 mmol) in diethyl ether (12.8 g, see
above). After 20 h, the solvent was removed under vacuum. The
remaining brown oil was dissolved in perfluorohexane at 50 °C.
Only a little of the brown oil remained undissolved. A large part
of the perfluorohexane was removed under vacuum, and a colorless
solid precipitated. This was sublimed at 80–90 °C/14 mbar. Yield
{1,2-Bis[bis(trifluoromethyl)phosphanyl]ethane}platinum(II)
(hexafluoridoantimonate) {[(dfmpe)Pt][SbF6]2}: {1,2-Bis[bis(tri-
fluoromethyl)phosphanyl]ethane}dimethylplatinum(II) (330 mg,
Bis-
0.56 mmol) and antimony pentafluoride (300 mg,1.4 mmol) were
added to a 4 mm o.d. PFA tube. aHF (ca. 0.4 mL) was condensed
into the mixture at –196 °C. At –78 °C, vigorous gas evolution oc-
curred, and a yellow solid precipitated from the yellow solution.
The solid dissolved at –20 °C, at which point NMR spectra were
measured (see below). Slow cooling of the solution to –100 °C re-
1
1.08 g (40%). M.p. 65–67 °C. H NMR ([D6]acetone): δ = 1.15 (t,
–
sulted in the formation of yellow crystals of [(dfmpe)Pt]2+(SbF6 )
3JH,P = 8, 2JH,Pt = 80 Hz), 2.87 (d, 2JH,P = 13, 3JH,Pt = 13 Hz) ppm.
1
2
3
2·2HF. H NMR (–20 °C): δ = 3.40 (m) ppm. 19F NMR (–20 °C):
19F NMR ([D6]acetone): δ = –59.1 (d, JF,P = 75, JF,Pt = 20 Hz)
2
3
ppm. 31P{19F} NMR ([D6]acetone): δ = 68.0 (t, 2JP,H = 13, 1JP,Pt
=
δ = –55.7 (d, JF,P = 114, JF,Pt = 45 Hz), –128.6 (br. s) ppm.
2
31P{19F} NMR (–20 °C): δ = 59.7 (s, JP,Pt = 4700 Hz) ppm. 31P
NMR (–20 °C): δ = 59.6 (septsept, JP,F = 115, JP,F = 14, JP,Pt
1
1430 Hz) ppm. 31P NMR ([D6]acetone): δ = 64.9 (sept, JP,F = 75,
2
5
1
1JP,Pt = 1430 Hz) ppm. 13C{1H} NMR ([D6]acetone): δ = 1.9 (m,
=
1
2
4700 Hz) ppm. 13C{1H,19F} NMR (–20 °C): δ = 19.5 (m), 117.0
(m) ppm. 195Pt{19F} NMR (–20 °C): δ = –4360 (t, 1JPt,P = 4700 Hz)
ppm. The following three compounds were obtained in low yields
and are considered to have formed from accidental crystallizations.
1JC,Pt = 314 Hz), 20.8 (dd, JC,P = 20, JC,P = 19 Hz), 122.2 (dq
and fine structure, JC,P = 55, JC,F = 320 Hz) ppm. 195Pt{19F}
1
1
NMR ([D6]acetone): δ = –4514 (tsept, 1JPt,P = 1470, 2JPt,H = 78 Hz)
ppm. IR: ν = 529 (m), 561 (st), 631 (w), 663 (m), 703 (m), 751 (w),
˜
814 (m), 880 (w), 904 (w), 972 (w), 1027 (w), 1086 (st), 1119 (st),
1141 (st), 1184 (st), 1262 (w), 1287 (w), 1318 (w), 1413 (w), 2814
{1,2-Bis[bis(trifluoromethyl)phosphanyl]ethane}(trihydrogen
trifluoride)platinum(II) Hexafluoridoantimonate Undecafluoridodi-
antimonate {[(dfmpe)Pt][SbF6][Sb2F11]·3HF}: The same procedure
as described above with an SbF5/Pt complex ratio of 8:1 (rather
than 2.4:1) resulted in the title compound.
(w), 2901 (w), 2976 (w) cm–1. Raman: ν = 176 (55), 195 (15), 218
˜
(70), 250 (5), 272 (15), 285 (30), 351 (5), 371 (20), 409 (2), 464 (10),
507 (10), 540 (100), 704 (10), 749 (30), 982 (2), 1145 (5), 1194 (15),
1220 (5), 1413 (5), 2811 (2), 2902 (5), 2924 (5), 2974 (10) cm–1. MS
(EI, 40 °C): m/z = 575.9 [M – Me]+, 560.8 [M – 2 Me]+, 491.8 [M –
2 Me – CF3]+·, 441.7 [M – 2 Me – C2F5]+·. HRMS: calcd. for [M –
Me]+ 575.94794; found 575.94812.
{1,2-Bis[bis(trifluoromethyl)phosphanyl]ethane}platinum(II) Bis(un-
decafluoridodiantimonate) {[(dfmpe)Pt][Sb2F11]2}: At –196 °C, a
thick-walled glass ampoule of 2 mm inner diameter was filled with
{1,2-bis[bis(trifluoromethyl)phosphanyl]ethane}platinum(II) bis-
Reaction of {1,2-Bis[bis(trifluoromethyl)phosphanyl]ethane}dimeth- (hexafluoridoantimonate) (23 mg, 0.022 mmol) and antimony
ylplatinum(II) {[(dfmpe)Pt(CH3)2]} with aHF: {1,2-Bis[bis(trifluoro-
methyl)phosphanyl]ethane}dimethylplatinum(II) (0.1 g, 0.2 mmol)
was treated with aHF (0.15 mL) in a 4 mm o.d. PFA tube at
pentafluoride (700 mg, 3.2 mmol). Xenon (6 mmol ) was condensed
into the mixture at –196 °C and the ampoule was sealed. Antimony
pentafluoride and xenon mixed at 0 °C as a colorless solution, but
Eur. J. Inorg. Chem. 2013, 1197–1206
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
[2] K. Seppelt, Z. Anorg. Allg. Chem. 2010, 636, 2391–2393.
the platinum complex remained undissolved. The ampoule was
kept in an ultrasound bath at 0 °C for 20 min. At 40 °C, a homo-
geneous yellow solution formed. The mixture was stored at 5 °C
for 1 month, and colorless single crystals formed.
[3] B. L. Bennett, J. Birnbaum, D. M. Roddick, Polyhedron 1995,
14, 187–195; J. F. Houlis, D. M. Roddick, J. Am. Chem. Soc.
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Bis{1,2-bis[bis(trifluoromethyl)phosphanyl]ethane}di-μ-hydridodipla-
tinum(II) Bis(undecafluoridodiantimonate) {[(dfmpe)PtH2Pt-
(dfmpe)][Sb2F11]2}: The same reaction as described above but per-
formed in a PFA tube in the presence of HF (600 mg, 30 mmol)
and kept solely at –30 °C produced the title compound as orange
crystals.
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1639.
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platinum(II)
Dodecafluoridododecaboranate
{[(dfmpe)PtF2Pt-
(dfmpe)][B12H12]·HF}:
{1,2-Bis[bis(trifluoromethyl)phosphanyl]-
ethane}platinum(II) bis(hexafluoridoantimonate) (40 mg, 40 nmol)
and cesium dodecafluoridododecaboranate (50 mg, 80 mmol) were
added to a 4 mm o.d. PFA tube, aHF (1.5 mL) was condensed in,
and the tube was sealed. After the solution was warmed to room
temp., the supernatant colorless liquid was separated from the in-
soluble remainder and cooled slowly to –80 °C. Two types of color-
less crystals formed: cubic-shaped CsSbF6 and needle-shaped plati-
num dodecafluoridododecaboranate. 19F NMR (aHF): δ = –54.5
(br. m, 24 F), –267 (br. m, 12 F) ppm. Crystal structure details are
summarized in Tables 1, 2, 3 and 4.
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Acknowledgments
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This work was supported by the graduate school “Fluorine as a
Key Element” funded by the Deutsche Forschungsgemeinschaft.
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[1] R. A. Periana, D. J. Taube, S. Gamble, H. Taube, T. Satoh, H.
Received: September 18, 2012
Fuji, Science 1998, 280, 560–564.
Published Online: December 14, 2012
Eur. J. Inorg. Chem. 2013, 1197–1206
1206
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim