Coordination chemistry of perhalogenated cyclopentadienes and alkynes, xxix. the reaction of ni(0) and pt(0) phosphane complexes with trichloroethene, hexachloro- and hexabromocyclopentadiene

Article abstract of DOI:10.5560/ZNB.2012-0087

Trichloroethene reacts with [Pt(PPh3)2(C2H4)] at first to the p complex [Pt(PPh3)2(h2-C2HCl3)] (1a), which isomerizes via the cis-isomer to the insoluble trans-[Pt(Cl)(h1-CH=CCl2)(PPh3)2] (2a). Both 1a and 2a react with PBu3 to the corresponding tributylp

Full text of DOI:10.5560/ZNB.2012-0087

Coordination Chemistry of Perhalogenated Cyclopentadienes and
Alkynes, XXIX. The Reaction of Ni(0) and Pt(0) Phosphane Complexes
with Trichloroethene, Hexachloro- and Hexabromocyclopentadiene
Karlheinz Su¨nkel, Stefanie Bernhartzeder and Uwe Birk
Department of Chemistry, Ludwig-Maximilians University Munich, Butenandtstr. 9, D-81377
Munich, Germany
Reprint requests to Prof. Dr. Karlheinz Su¨nkel. Fax: ++49 89 2180 77774.
E-mail: suenk@cup.uni-muenchen.de
Z. Naturforsch. 2012, 67b, 557 – 563 / DOI: 10.5560/ZNB.2012-0087
Received March 29, 2012
Dedicated to Professor Wolfgang Beck on the occasion of his 80th birthday
Trichloroethene reacts with [Pt(PPh3)2(C2H4)] at first to the π complex [Pt(PPh3)2(η2-C2HCl3)]
(1a), which isomerizes via the cis-isomer to the insoluble trans-[Pt(Cl)(η1-CH=CCl2)(PPh3)2] (2a).
Both 1a and 2a react with PBu3 to the corresponding tributylphosphane complexes 1b and 2b, re-
spectively. From the reactions of [Ni(PR3)2(C2H4)] (R = Me, Et, Bu) and C2HCl3 only the products
of oxidative addition trans-[Ni(Cl)(η1-CH=CCl2)(PR3)2] (3a – c) can be isolated. Hexachlorocy-
clopentadiene and hexabromocyclopentadiene react with [Pt(PPh3)2(C2H4)] or [Ni(PR3)2(C2H4)]
(R = Ph, Me) to give highly colored solutions.
Key words: Oxidative Addition, Platinum Phosphane Complexes, Nickel Phosphane Complexes,
Trichloroethene, Hexachlorocyclopentadiene
Introduction
[Pt(PPh3)2(C2H4)] to give the product of oxida-
tive C-Cl addition [7]. Beck et al. studied the re-
The reactions of chloro-olefins and chloroalkanes action of tetrachlorocyclopropene with the same
with [Pt(PPh3)4] and [Pt(PMePh2)4] were first stud- Pt(0) compound and could isolate an unexpected σ-
ied ca. fourty years ago [1]. These studies showed that (3-triphenylphosphonio)-propenyl complex resulting
while with tetrachloroethene a Pt(0) π complex could from a ring-opening reaction [8]. The reaction of
be isolated, trichloroethene or dichloroethene yielded 5,5-dibromo-1,2,3,4-tetraphenylcyclopentadiene with
only σ-vinyl complexes of Pt(II), and chloroalkanes [Ni(PEt3)4] led to [NiBr2(PEt3)2] and triethylphos-
like CHCl3 or CCl4 produced mainly [Pt(PPh3)2Cl2]. phonium tetraphenylcyclopentadienide [9]. Although
Later on, the reactivity of the formed α-chlorovinyl the coordination chemistry of hexachlorocyclopenta-
complexes was studied by Chisholm et al. [2] and diene apparently has not been studied in much de-
Otsuka et al. [3]. The oxidative addition of tetra- tail, its reactivity toward low-valent transition metal
chloroethene to Ni(0) phosphane complexes was ex- complex seems to be governed by highly reactive car-
amined by Wada et al. since 1979 [4], and the re- bene and radical intermediates, which in most cases
activity of σ-trichlorovinyl nickel complexes was allowed only the identification of organic products, but
studied by Muller et al. in 1985 [5]. The reactiv- no metal-containing species [10 – 13].
ity of some cyclic polyhaloolefins with Pt(0) was
Since on one hand, trichloroethene is a starting ma-
also studied in a few cases. Thus, reaction of 2,3- terial for the synthesis of dichloroethyne, the coordi-
dihalobicyclo[2.2.1.]hept-2-ene with [Pt(PPh3)3] af- nation chemistry of which was studied by us in some
forded π-alkene complexes which could be isomer- detail [14], and since on the other hand the special
ized to the corresponding σ-vinyl complexes by properties of the pentahalocyclopentadienyl ligand al-
heating [6]. Later on, Schubert reported the reac- lowed us to develop a fascinating coordination chem-
tion of 3,3-dichloro-1,2-diphenylcyclopropene with istry [15], we found it worthwhile to look at the reac-
c
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tions of trichloroethene and hexachloro- and hexabro-
mocyclopentadiene with Ni(0) and Pt(0) phosphane
complexes.
Results and Discussion
A toluene solution of [Pt(PPh3)2(C2H4)] was treated
with an excess of trichloroethene at room tempera-
ture. When the resulting solution was evaporated to
dryness and the residue taken up in dichloromethane,
a
31P NMR spectrum of this solution showed the
presence of two species in an approximate 4 : 1 ra-
tio. The spectroscopic data (see Experimental Sec-
tion) suggested that the major component is the
π-olefin complex [Pt(PPh3)2(η2-CHCl=CCl2) (1a),
while the minor compound is the σ-vinyl complex
cis-[Pt(Cl)(CH=CCl2)(PPh3)2] (2a0). From this solu-
tion a colorless precipitate began to form after ca. one
hour, and after several hours precipitation was com-
plete, and no signals could be seen in the NMR spec-
trum of the supernatant solution. The IR spectrum
of this insoluble colorless powder agreed well with
the data of trans-[Pt(Cl)(CH=CCl2)(PPh3)2] (2a) re-
ported by Kemmitt for the product of the reaction in
benzene at 105 ◦C. Treatment of the freshly prepared
NMR solution with PBu3 produced a new species
with NMR data indicative of a π complex, presum-
ably [Pt(PBu3)2(η2-CHCl=CCl2)] (1b). After stand-
ing for several hours the solution contained a new
species, now with data suggesting the formation of
trans-[Pt(Cl)(CH=CCl2)(PBu3)2] (2b). There was no
sign of formation of an intermediate cis-σ-vinyl com-
plex. The same spectrum of 2b could be obtained
after addition of PBu3 to the CH2Cl2 suspension of
2a, which led to complete dissolution of the solid
(Scheme 1).
The observations made here for the isomeriza-
tion process as well as for the phosphane substitu-
tion process are very similar to the ones made by
us for the corresponding reactions of dichloroethyne
with [Pt(PPh3)2(C2H4)], suggesting similar mecha-
Scheme 1. Synthesis and reactivity of platinum trichloro-
ethene complexes.
nisms [14]. It should also be mentioned that Kemmitt cept for R = Me, where a second species is present.
found strong solvent effects on the kinetics of the cor- (Scheme 2).
responding isomerization reaction of [Pt(PPh3)2(η2-
The regioselective addition of the (H)C–Cl bond
C2Cl4)] [16].
and not of the (Cl)C–Cl bond can be proven by a 1H-
Treatment of solutions of the in situ-generated coupled 13C NMR spectrum of 3c and is in agreement
[Ni(PR3)2(C2H4)] (R = Me, Et, Bu) with trichloro- with Muller’s observation with the corresponding PPh3
ethene apparently gives only the product of oxidative complex [17]. The NMR data of the second product in
trans-addition [Ni(Cl)(CH=CCl2)(PR3)2] (3a – c), ex- the reaction of the PMe3 complex, however, indicate
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559
istry [18] and were also observed in the reaction with
Fe(CO)5 [12]. The initially observed intense colors
hint on the formation of the C5Cl5 radical [19].
The reaction of [Pt(PPh3)2(C2H4)] with C5Cl6
yielded a green-blue solid. However, the FAB+-
MS spectra showed no chlorine-containing species
besides [Pt(PPh3)2Cl]+ and the usual fragments
of the [Pt(PPh3)2] unit, including e. g. [20],
[Pt(PPh3)(PPh2)]+. The 31P NMR spectrum
showed, besides signals of PPh3O, cis- and trans-
[Pt(PPh3)2Cl2], and [Pt(PPh3)2(CO3)] (most likely
an impurity in the starting ethylene complex),
only an AX spin system with signals at δ = 22.8
(d, JPP = 13 Hz, JPPt = 4079 Hz), and 26.5 (d,
JPP = 13 Hz, JPPt = 1710 Hz). The size of the PAPX
coupling constant suggests a cis-orientation of two
PPh3 ligands, and the values of J (P-Pt) hint on one
chloride and one carbon ligand (compare data of 2a0).
When the reaction was carried out in an NMR tube,
Scheme 2. Reaction of [Ni(PR3)2(C2H4)] with trichloro-
ethene.
that the alternative C–Cl bond can also undergo oxida- high field signals at δ < −60 ppm appeared which
tive addition. are indicative of the formation of an orthometallated
The reaction of hexachlorocyclopentadiene with PPh3 ligand [21]. Such a ligand might decompose via
Ni(0) complexes [Ni(PR3)2(C2H4)] yielded no iden- [Pt(PPh3)(PPh2)(C6H5)] in CH2Cl2 with formation
tifiable nickel compounds, as was reported for the of cis-[Pt(PPh3)2(Cl)(C6H5)], the trans isomer of
corresponding reaction of the PEt3 ethylene com- which has been reported [22]. From the NMR tube
plex [13]. Mass spectral examination of the products solutions some colorless crystals precipitated, which
showed all members of the series C5nCl4n−(1,2,3) for were shown by X-ray crystallography to be a new
n = 1 – 4 as well as C5Cl6, C5Cl5, C10Cl10, and C10Cl8. modification of trans-[Pt(PPh3)2Cl2] (see Fig. 1 and
These fragments are quite common in C5Cl6 chem- discussion below).
Fig. 1. ORTEP-III view of trans-[Pt(PPh3)2Cl2]
(displacement ellipsoids are at the 30% probabil-
ity level; the H atoms are drawn as spheres with
arbitrary radii).
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K. Su¨nkel et al. · Coordination Chemistry of Perhalogenated Cyclopentadienes and Alkynes
The reaction of C5Br6 with [Pt(PPh3)2(C2H4)] pro- were commercial products and used without further purifi-
cation. [Pt(PPh3)2(C2H4)], [Ni(PR3)2Cl2] and C5Br6 were
prepared according to literature procedures [28 – 30]
duced again an intensely colored solution from which
a beige solid precipitated, which was isolated and ex-
amined. The FAB+-MS spectrum showed the same
fragments as the product of the C5Cl6 reaction in
addition to [Pt(PPh3)2Br]+. The 31P NMR spectrum
showed signals due to PPh3O, cis-[Pt(PPh3)2Br2] and
cis-[Pt(PPh3)2(Br)(Cl)], which were identified by com-
parison with literature data [23]. About the origin
of the chlorido ligand can only be speculated. An
impurity in the starting ethylene complex seems to
be the most plausible source. The reaction solution
yielded after evaporation a dark brown solid. Its
FAB+-MS spectrum showed the presence of the dimer
[Pt(PPh3)(Br)(µ-Br)]2 and its fragments [24] together
with two fragments apparently containing the (C5Br5)
group [Pt(PPh3)n(C5Br5)]+ with m/e = 1179 (n = 2)
Reaction of [Pt(PPh3)2(C2H4)] with trichloroethene
A solution of 130 mg [Pt(PPh3)2(C2H4)] in 5 mL toluene
was treated with ca. 0.12 mL C2HCl3 and then stirred for
90 min at r. t. Evaporation of the solvent in vacuo produced
a colorless powder, which was dissolved in CH2Cl2 and ex-
amined by 31P NMR: 1a: δ = 22.0 (d, 2JPP = 23 Hz, 1JPtP
=
2
1
3262 Hz), 17.1 (d, JPP = 23 Hz, JPtP = 3120 Hz). 2a0:
δ = 12.4 (d, 2JPP = 27 Hz, 1JPtP = 1952 Hz), 10.7 (d, 2JPP
=
1
27 Hz, JPtP = 4131 Hz). This solution was stirred for 3 h
at r. t. to produce a colorless precipitate which was isolated
and identified by its IR spectrum (νPtC=C = 1550 cm−1) as
2a. A freshly prepared CH2Cl2 solution of 1a was treated
with several drops of PBu3. A relatively broad 31P NMR
signal at δ = 0.2 (1JPtP = 3127 Hz) indicated the forma-
and 917 (n = 1). The 31P NMR spectrum exhibited be- tion of 1b, but was gradually replaced by another singlet at
δ = 7.2 (1JPtP = 2581 Hz), which was also observed when
sides the signal of PPh3O those of both cis- and trans-
the CH2Cl2 suspension of 2a was treated with several drops
of PBu3: 2b. Evaporation of the solution to dryness and dis-
solution of the residue in CDCl3 allowed the measurement of
the 1H NMR spectrum. Besides the signals due to free PPh3
and free and/or complexed PBu3 only a triplet at δ = 5.52
(3JHP = 2 Hz, 2JHPt = 32 Hz) could be observed.
[Pt(PPh3)2Br2] [25] together with a very-low-intensity
AMX (or two AA’XX’) system(s) with JPP = 5 Hz and
JPPt = 2740 and 2460 Hz. The small value of J (P-P)
hints on a long range coupling, and therefore we assign
these signals to the dimeric complexes cis- and trans-
[Pt(PPh3)(Br)(µ-Br)]2, the NMR data of which appar-
ently have not been reported. However, for the anal-
Reaction of [Ni(PMe3)2(C2H4)] with trichloroethene
0
ogous chlorido-complexes (cis and trans) JPP = 5 Hz
has been reported [26].
A red solution of [NiCl2(PMe3)2] (570 mg, 2.0 mmol) in
5 mL thf was treated under C2H4 with an excess of zinc pow-
der for 30 min. The yellow solution was filtered, cooled to
−30 ◦C and treated with ca. 0.1 mL C2HCl3. After warm-
ing to ambient temperature a black suspension had formed.
Evaporation to dryness was followed by column chromatog-
raphy on silica gel. A yellow band formed, which was
collected, eluted with Et2O and evaporated in vacuo. The
residue was examined by NMR spectroscopy in C6D6 solu-
tion. – 1H NMR: δ = 6.16 (1H), 5.29 (1H), 1.08 (18H), 0.96
(18H) (broad signals). – 31P NMR: δ = −12.8 s, −13.4 s
Crystal structure determination of
trans-[Pt(PPh3)2Cl2]
The structure of a triclinic modification of trans-
dichloridobis(triphenylphosphine) platinum was re-
ported in 1999 [27]. The orthorhombic modification
that we obtained crystallizes with two molecules of
CH2Cl2 per formula unit, in space group Pcab. Simi-
lar to the triclinic form, the platinum atom also resides
on an inversion center. The bond parameters around Pt
are very similar to those in the triclinic modification:
(relative intensities 1 : 1). – 13C NMR: δ = 150.4 (t, JCP
=
42 Hz), 144.7 (t, J = 41 Hz), 118.3 (t, J = 8 Hz), 102.7 (t,
J = 7 Hz), 12.8 (t, J = 14 Hz), 12.2 (t, J = 14 Hz).
After standing for several days at r. t. a precipitate formed
in the NMR tube, and the 31P NMR spectrum showed a de-
crease in intensity of the signal at −12.8 ppm. Column
chromatography of this solution on alumina, using Et2O as
eluent, produced a yellow band, from which, after dissolu-
tion and concentration in vacuo on cooling to −78 ◦C or-
˚
Pt–Cl 2.3086(7) vs. 2.2997(11) A; Pt–P 2.3095(7◦) vs.
˚
2.3163(11) A, and Cl–Pt–P 86.62(3) and 93.38(3) vs.
87.88(4) and 92.12(4)◦.
Experimental Section
The reactions were performed under N2 or Ar, using stan- ange crystals of 3a0 could be obtained. – 1H NMR (CDCl3):
dard Schlenk techniques. Solvents were purified by standard δ = 6.11 (“t”, JHP = 6 Hz, 1H), 1.35 (“t”, JHP = 4 Hz, 18H)
procedures, saturated with N2 or Ar and stored over molec- 31P NMR (CDCl3): δ = −13.1 s. – C8H19Cl3P2Ni: calcd.
ular sieves. Trichloroethene and hexachlorocyclopentadiene C 27.96, H 5.57; found C 28.95, H 6.16.
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Reaction of [Ni(PEt3)2(C2H4)] with trichloroethene
Reaction of C5Cl6 with [Ni(PMe3)2(C2H4)]
A mixture of [NiCl2(PMe3)2] (0.29 g, 1.03 mmol),
a small amount of zinc powder and C5Cl6 (0.17 mL,
1.06 mmol) was treated under an atmosphere of ethene with
tetrahydrofuran (1.5 mL). Immediately a violet color devel-
oped. After stirring for 15 min the mixture was given on top
of a short silica gel column and chromatographed using Et2O
as eluent. A red fraction was obtained which was evapo-
A solution of [NiCl2(PEt3)2] (630 mg, 1.70 mmol) in
10 mL toluene was treated with sodium dust (300 mg,
13 mmol) under C2H4 for 20 h, filtered and cooled to
−78 ◦C. After addition of 0.17 mL C2HCl3 (1.70 mmol) the
reaction mixture was warmed to ambient temperature within
two hours. Evaporation of the solvent in vacuo was followed
by chromatography on Al2O3 using Et2O as eluent. A yellow
band developed, which was collected. Evaporation in vacuo
produced 3b as a yellow oil (350 mg, 47% yield). Careful re-
crystallization from pentane at −30 ◦C gave 3b as large red
crystals. – 1H NMR (CDCl3): δ = 5.23 (t, J = 3 Hz, 1H),
1.71 (m, 12H), 1.24 (m, 18H). – 31P NMR (CDCl3): δ = 13.5
(s). – 13C NMR (CDCl3): δ = 143.4 (t, J = 39 Hz) 103.6 (t,
J = 7 Hz), 13.7 (“t”, J = 13 Hz), 7.9 (s). – C14H31Cl3NiP2:
calcd. C 39.43, H 7.33; found C 39.99, H 7.44.
rated to dryness. Yield: 0.19 g of a red-brown solid. The 31
P
NMR spectrum in CDCl3 showed only a weak, very broad
absorption at ca. δ = 60 ppm. – MS (DEI): m/e = 473.6
(C10Cl10), 403.7 (C10Cl8), 331.8 (C10Cl6), 308.7 (C5Cl7),
271.8 (C5Cl6), 236.8 (100%, C5Cl5), 202.9 (C5Cl4), 166.9
(C5Cl3), 140.9 (C3Cl3), 129.9 (C5Cl2), 95.0 (C5Cl), 60.0
(C5); in addition, at very weak intensity, the complete series
C5nCl4n−(1,2,3) with n = 2,3,4,5.
Reaction of C5Cl6 with [Pt(PPh3)2(C2H4)]
Reaction of [Ni(PBu3)2(C2H4)] with trichloroethene
A solution of [Pt(PPh3)2(C2H4)] (360 mg, 0.48 mmol)
in toluene (10 mL) was treated at −40 ◦C with C5Cl6
(0.43 mL, 2.68 mmol). After keeping the reaction mixture
at −78 ◦C for 16 h the precipitate was isolated by fil-
tration, washed three times with 20 mL portions of pen-
tane and dried in vacuo. Yield: 0.14 g of a green-blue
solid. – MS ((+)-FAB): m/e = 755.4 (PtP2C36H30Cl), 735.4
(PtP2C36H31O), 719.4 (PtP2C36H30), 642.3 (PtP2C30H25),
455.2 (PtPC18H14), 378.1 (PtPC12H8), 279.3 (PC18H15O),
262.3 (PC18H15) plus numerous very weak unidentified
A solution of [NiCl2(PBu3)2] (800 mg, 1.50 mmol)
in 10 mL toluene was stirred with 230 mg sodium dust
(10.0 mmol) under C2H4 for 20 h, then cooled to −78 ◦C and
treated with 0.15 mL C2HCl3 (1.50 mmol). Stirring was con-
tinued for 15 min at this temperature and then for 90 min at
r. t. After evaporation of the solvent in vacuo the residue was
taken up in a small amount of pentane and chromatographed
on silica gel. Elution with Et2O produced a yellow band
from which after evaporation in vacuo a yellow oil could be
isolated: 3c. Recrystallization from MeOH at −78 ◦C gave
a yellow flocculent precipitate, which was isolated. How-
ever, upon warming to r. t. the compound melted again. –
1H NMR (C6D6): δ = 5.25 (t, J = 3 Hz, 1H), 1.54 (m, 24H),
1.34 (m, 12H), 0.86 (“t”, 18H). – 31P NMR (C6D6): δ =
peaks. – 31P NMR (109.3 MHz, in CH2Cl2): δ = 8.2 (JPPt
3700 Hz, [Pt(PPh3)2CO3], impurity in the starting mate-
=
rial), 15.6 (JPPt = 3680 Hz, cis-[Pt(PPh3)2Cl2]), 22.1 (JPPt
2640 Hz, trans-[Pt(PPh3)2Cl2]), 22.8 (d, JPP = 13 Hz, JPPt
=
=
4079 Hz), 26.5 (d, JPP = 13 Hz, JPPt = 1710 Hz), 29.0
(PPh3O). From the NMR tube a few colorless crystals pre-
cipitated, which were used for a crystal structure determina-
tion (see below).
3
6.4 (s). – 13C NMR (C6D6): δ = 143.7 (dt, JCP = 39 Hz,
2JCH = 21 Hz), 103.5 (dt, 2JCP = 6 Hz, 1JCH = 190 Hz); 26.6
(s), 24.9 (“t”, JCP = 6 Hz), 21.7 (“t”, JCP = 13 Hz), 14.0 (s)
(PCH2CH2CH2CH3). – C26H55Cl3P2Ni (%): calcd. C 52.51,
H 9.32; found C 50.08, H 9.27.
Reaction of C5Br6 with [Pt(PPh3)2(C2H4)]
A solution of [Pt(PPh3)2(C2H4)] (360 mg, 0.48 mmol) in
toluene (10 mL) was treated at −25 ◦C with C5Br6 (270 mg,
0.50 mmol). Under continuous stirring the temperature
Reaction of C5Cl6 with [Ni(PPh3)2(C2H4)]
A suspension of [Ni(PPh3)2(C2H4)] (412 mg, 0.67 mmol) was raised to ambient within 16 h. The precipitate was
in toluene (10 mL) was treated at −78 ◦C with C5Cl6 isolated by filtration, washed with two 10 mL portions
(1.0 mL, 6.2 mmol) with stirring. The temperature raised to of toluene and dried in vacuo. Yield: 0.21 g of a beige
ambient overnight. The obtained dark-brown suspension was solid. – MS ((+)-FAB): m/e = 799.1 (PtP2C36H30Br),
centrifuged and the supernatant discarded. The residue was 755.2 (PtP2C36H31Cl, from impurity in the starting ma-
washed three times with 20 mL portions of hexane, dried terial), 734.3 (PtP2C36H30O), 718.3 (PtP2C36H29), 455.2
and extracted with 20 mL methanol. Evaporation of the ex- (PtPC18H15), 378.1 (PtPC12H10), 279.2 (PC18H16O).
tract left a light-green paramagnetic powder (228 mg). The
IR spectrum showed bands which are attributable to the PPh3 JPP = 14 Hz, cis-Pt(PPh3)2BrCl), 15.0 (JPPt = 3630 Hz,
–
31P NMR (109.4 MHz, in CH2Cl2): δ = 14.0 (d,
ligand.
cis-Pt(PPh3)2Br2), 16.4 (d, JPP = 14 Hz, JPPt = 3680 Hz,
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K. Su¨nkel et al. · Coordination Chemistry of Perhalogenated Cyclopentadienes and Alkynes
cis-Pt(PPh3)2BrCl), 29.4 (PPh3O). The filtrate was evap- Table 1. Crystal data for trans-[Pt(PPh3)2Cl2].
orated to dryness. Yield: 0.47 g of a dark-brown solid. –
Empirical formula
Formula weight
Crystal size, mm3
Crystal system
C36H30Cl2P2Pt · 2CH2Cl2
MS ((+)-FAB): m/e = 1257.2 (Pt2P2C36H30Br4+Na),
1234.8 (Pt2P2C36H30Br4), 1179 (PtP2C36H30C5Br5),
1154.0 (Pt2P2C36H30Br3), 1074.0 (Pt2P2C36H30Br2),
960.38
0.09 × 0.07 × 0.05
orthorhombic
Pcab
Space group
993.1
(Pt2P2C36H29Br),
917
(PtPC18H15C5Br5),
Unit cell dimensions
799.2 (PtP2C36H30Br), 755.9 (PtP2C36H31Cl), 718.3
(PtP2C36H29), 557.3 (P2C36H31O2), 537.9 (PtPC18H15Br),
456.1 (PtPC18H16), 279.2 (PC18H16O, 100%). – 31P
NMR (109.4 MHz, in C6D6): δ = 7.9 (d, JPP = 5 Hz,
JPPt = 2740 Hz), 9.4 (d, JPP = 5 Hz, JPPt = 2460 Hz), 15.8
(JPPt = 3572 Hz, cis-[Pt(PPh3)2Br2]), 21.2 (JPPt = 2560 Hz,
trans-[Pt(PPh3)2Br2]), 28.0 (br, PPh3O).
˚
a, A
8.0273(2)
˚
b, A
20.1801(3)
23.0606(4)
3735.63(13)
4
1.71
4.3
˚
c, A
3
˚
Volume, A
Z
Density (calculated), g cm−3
Absorption coefficient, mm−1
F(000), e
1888
θ range for data collection, deg
hkl ranges
Reflections collected / unique / Rint
Completeness to θ = 25.36◦, %
Absorption correction
3.24 – 25.36
±9,±24,±27
42311 / 3416 / 0.0394
99.9
semi-empirical from
equivalents
0.766 / 0.695
3416 / 215
0.0219 / 0.0507
0.0324/ 0.0572
1.106
X-Ray structure determination
An X-ray quality single crystal was mounted on a glass
fiber and cooled to 173(3) K for the measurements. The data
were collected on a Nonius KappaCCD diffractometer using
˚
Max. / min. transmission
Data / ref. parameters
Final R1/wR2 indices [I > 2σ(I)]
Final R1/wR2 indices (all data)
Goodness-of-fit on F2
MoKα radiation (λ = 0.71073 A, graded multilayer X-ray
optics). A multi-scan absorption correction was applied using
the program SADABS [31a]. The structure was solved with
SIR97 [31b] as implemented in the WINGX software pack-
age [31c]. Refinement (full-matrix least-squares on F2) was
carried out with SHELXL-97 [31d], also as implemented in
WINGX. Molecular graphics: ORTEP-III [31e]. For crystal-
lographic data and numbers pertinent to data collection and
structure refinement see Table 1.
Extinction coefficient
Largest diff. peak / hole, e A
0.00049(7)
0.752 / −0.629
−3
˚
of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data request/cif.
CCDC 873325 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free
[1] a) W. J. Bland, R. D. W. Kemmitt, J. Chem. Soc. (A),
1968, 1278; b) B. F. G. Johnson, J. Lewis, J. D. Jones,
K. A. Taylor, J. Chem. Soc., Dalton Trans. 1974, 34.
[2] a) R. A. Bell, M. H. Chisholm, D. A. Couch, L. A.
[8] E. Leidl, M. Steimann, K. Su¨nkel, W. Beck, Eur.
J. Solid State Inorg. Chem. 1991, 28, 841.
[9] J. J. Eisch, Y. Qian, M. Singh, J. Organomet. Chem.
1996, 512, 207.
Rankel, Inorg. Chem. 1977, 16, 677; b) R. A. Bell, [10] C. G. Krespan, J. Org. Chem. 1975, 40, 261.
M. H. Chisholm, Inorg. Chem. 1977, 16, 698. [11] C. Moberg, Acta Chem. Scand. 1978, B32, 149.
[3] T. Yoshida, T. Okano, S. Otsuka, J. Chem. Soc., Dalton [12] M. K. Chaudhuri, Ind. J. Chem. 1980, 19A, 125.
Trans. 1976, 993.
[13] D. R. Fahey, J. F. Mahan, J. Amer. Chem. Soc. 1977, 99,
[4] a) K. Oguro, M. Wada, N. Sonoda, J. Organomet.
2501.
Chem. 1979, 165, C10; b) M. Wada, K. Nishiwaki, J. [14] a) K. Su¨nkel, U. Birk, Polyhedron 1999, 18 3187; b)
Chem. Soc., Dalton Trans. 1983, 1841, and refs. cited
therein.
[5] J. M. Coronas, G. Muller, M. Rocamora, C. Miravitlles,
X. Solans, J. Chem. Soc., Dalton Trans. 1985, 2333.
K. Su¨nkel, U. Birk, Polyhedron 1997, 16, 3333; c)
K. Su¨nkel, U. Birk, C. Robl, Organometallics 1994, 13,
1679.
[15] K. Su¨nkel, Chem. Ber./Recl. 1997, 130, 1721.
[6] P. G. Gassman, I. Gennick Cesa, Organometallics [16] W. J. Bland, J. Burgess, R. D. W. Kemmitt, J. Organo-
1984, 3, 119. met. Chem. 1968, 15, 217.
[7] C. Mu¨ller, U. Schubert J. Organomet. Chem. 1991, [17] M. Anton, G. Muller, J. Sales, Trans. Met. Chem. 1983,
405, C1. 8, 79.
Unauthenticated
Download Date | 6/9/17 11:35 AM

K. Su¨nkel et al. · Coordination Chemistry of Perhalogenated Cyclopentadienes and Alkynes
563
[18] a) E. A. Stemmler, R. A. Hites, Anal. Chem. 1985, 57, [29] a) M. A. A. Beg, H. C. Clark, Can. J. Chem. 1961, 39,
684; b) K. Yu. Amsharov, M. Jansen, Carbon 2007, 45,
117.
595; b) R. C. Cass, G. E. Coates, R. G. Hayter, J. Chem.
Soc. 1955, 4007.
[19] F. Graf, Hs. H. Gu¨nthard, Chem. Phys. Lett. 1971, 8, [30] K. Su¨nkel, C. Stramm, M. Lang, W. Kempinger, J. Hof-
395; ibid. 1970, 7, 25.
mann, Inorg. Chim. Acta 1998, 269, 111.
[20] R. Bertani, P. Traldi, Inorg. Chim. Acta 1987 134, 123.
[21] a) M. A. Bennett, T. Dirnberger, D. C. R. Hockless,
E. Wenger, A. C. Willis, J. Chem. Soc., Dalton
Trans. 1998, 271; b) M. A. Bennett, S. K. Barghava,
S. H. Priver, A. C. Willis, Eur. J. Inorg. Chem. 2008,
3467; c) M. A. Bennett, S. K. Barghava, J. Mes-
selha¨user, S. H. Prive´r, L. L. Welling, A. C. Willis, J.
Chem. Soc., Dalton Trans. 2007, 3158; d) M. A. Ben-
nett, S. K. Barghava, M. Ke, A. C. Willis, J. Chem
Soc., Dalton Trans. 2000, 3537.
[31] a) G. M. Sheldrick, SADABS (version 2), Program
for Empirical Absorption Correction of Area Detector
Data, University of Go¨ttingen, Go¨ttingen (Germany)
2001; b) A. Altomare, M. C. Burla, M. Camalli, G. L.
Cascarano, C. Giacovazzo, A. Guagliardi, A. G. G. Mo-
literni, G. Polidori, R. Spagna, SIR97, A New Tool
for Crystal Structure Determination and Refinement;
see: A. Altomare, M. C. Burla, M. Camalli, G. L. Cas-
carano, C. Giacovazzo, A. Guagliardi, A. G. G. Mo-
literni, G. Polidori, R. Spagna, J. Appl. Crystallogr.
1999, 32, 115; c) L. J. Farrugia, WINGX, A MS-
Windows System of Programs for Solving, Refining
and Analysing Single Crystal X-ray Diffraction Data
for Small Molecules, University of Glasgow, Glas-
gow, Scotland (UK) 2005. See also: L. J. Farrugia, J.
Appl. Crystallogr. 1999, 32, 837; d) G. M. Sheldrick,
SHELXL-97, Program for the Refinement of Crystal
Structures, University of Go¨ttingen, Go¨ttingen (Ger-
many) 1997. See also: G. M. Sheldrick, Acta Crys-
tallogr. 2008, A64, 112; e) C. K. Johnson, M. N. Bur-
nett, ORTEP-III (version 1.0.2), Rep. ORNL-6895, Oak
Ridge National Laboratory, Oak Ridge, TN (USA)
1996. Windows version: L. J. Farrugia, University of
Glasgow, Glasgow, Scotland (UK) 1999. See also:
L. J. Farrugia, J. Appl. Crystallogr. 1997, 30, 565.
[22] L. Rigamonti, C. Manassero, M. Rusconi, M. Man-
assero, A. Pasini, J. Chem. Soc., Dalton Trans. 2009,
1206.
[23] L. Rigamonti, A. Forni, M. Manassero, C. Manassero,
A. Pasini, Inorg. Chem. 2010, 49, 123.
[24] T. L. Gilchrist, F. J. Graveling, C. W. Rees, Chem. Com-
mun. 1968, 821.
[25] L. Rigamonti, M. Rusconi, C. Manassero, M. Ma-
nassero, A. Pasini, Inorg. Chim. Acta 2010, 363,
3498.
[26] N. M. Boag, M. S. Ravetz, J. Chem. Soc., Dalton Trans.
1995, 3473.
[27] M. H. Johansson, St. Otto, Acta Crystallogr. 2000, C56,
e12.
[28] U. Nagel, Chem. Ber. 1982, 115, 1998.
Unauthenticated
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