Mono- Or diplatinum complexes containing a π-conjugated pentadiynyl ligand

Article abstract of DOI:10.1002/ejic.200901191

The reaction of pentadiynyl halides XCH₂C≡CC≡CPh (1) with equimolar amounts of Pt(C₂H₄)(PPh₃) ₂ in C₆D₆ produced cis-(PPh₃) ₂PtX(η¹-CH₂C≡CC≡CPh) (cis-2) as a kinetic product. Complex cis-2 isomerized to trans-(PPh₃) ₂PtX(η^:lCH₂C≡CC≡CPh) (trans-2) or trans-(PPh₃)₂PtX[η¹-C(C≡ CPh)=C=CH₂] (trans-3) under some reaction conditions. In contrast to the reaction of Pt(C₂H₄)(PPh₃)₂, treatment of 1 with Pt(PPh₃)₄ generated, cationic platinacyclobutene [(PPh₃J₂Pt(η²-CH ₂C(PPh₃)=C(C=CPh)}]⁺Cl^- (5) together with cis-2 and trans-2. Moreover, 2 equiv. of Pt(C₂H ₄)(PPh₃)₂ and 1 provided eta;¹, η²-coordinated diplatinum complex cis-(PPh₃) ₂-PtCl[η¹- CH₂C≡C((PPh ₃)₂Pt(η²-C≡CPh)] (7) and/or metallacyclobutene diplatinum complex (PPh₃)₂Pt[η ²-CH₂C[(PPh₃)₂PtCl}=C(C≡CPh)J (8). The coordination modes of these complexes depend, on the ratio of pentadiynyl halide, Pt, and PPh₃, as well as temperature and the nature of the solvents. Protonolysis of metallacyclobutene complexes 5 and 8 with HCl gave [cis-(PPh₃)₂PtCl{η¹- C(C≡CPh)=C(PPh₃)CH₃}]⁺Cl^- (9) and [(PPh₃)₂Pt(η³-CH₂{cis- (PPh₃)₂PtCl}CCH(C≡CPh)}]⁺Cl^- (10). Single-crystal X-ray diffraction analysis of 12 showed η³- and η¹-coordination structure.

Full text of DOI:10.1002/ejic.200901191

FULL PAPER
DOI: 10.1002/ejic.200901191
Mono- or Diplatinum Complexes Containing a π-Conjugated Pentadiynyl
Ligand
Ken Tsutsumi,*[a] Hayato Sakai,[a] Kazuyuki Sakonaka,[a] Tomomi Yabukami,[a]
Yoshiteru Takahashi,[a] Yuzo Nakagai,[a] Tsumoru Morimoto,[a] Kenji Tabata,[b] and
Kiyomi Kakiuchi*[a]
Keywords: Platinum / Pentadiynyl ligands / Bimetallic compounds / Coordination modes / Solvent effects
The reaction of pentadiynyl halides XCH2CϵCCϵCPh (1)
with equimolar amounts of Pt(C2H4)(PPh3)2 in C6D6 produced
cis-(PPh3)2PtX(η1-CH2CϵCCϵCPh) (cis-2) as a kinetic prod-
uct. Complex cis-2 isomerized to trans-(PPh3)2PtX(η1-
CH2CϵCCϵCPh) (trans-2) or trans-(PPh3)2PtX[η1-C(Cϵ
CPh)=C=CH2] (trans-3) under some reaction conditions. In
contrast to the reaction of Pt(C2H4)(PPh3)2, treatment of 1
with Pt(PPh3)4 generatedcationicplatinacyclobutene [(PPh3)2-
Pt{η2-CH2C(PPh3)=C(CϵCPh)}]+Cl– (5) together with cis-2
PtCl[η1- CH2CϵC{(PPh3)2Pt(η2-CϵCPh)}] (7) and/or metalla-
cyclobutene diplatinum complex (PPh3)2Pt[η2-CH2C{(PPh3)2-
PtCl}=C(CϵCPh)] (8). The coordination modes of these com-
plexes depend on the ratio of pentadiynyl halide, Pt, and
PPh3, as well as temperature and the nature of the solvents.
Protonolysis of metallacyclobutene complexes 5 and 8 with
HCl gave [cis-(PPh3)2PtCl{η1-C(CϵCPh)=C(PPh3)CH3}]+Cl–
(9) and [(PPh3)2Pt{η3-CH2{cis-(PPh3)2PtCl}CCH(CϵCPh)}]+-
Cl– (10). Single-crystal X-ray diffraction analysis of 12
and trans-2. Moreover, 2 equiv. of Pt(C2H4)(PPh3)2 and 1 pro- showed η3- and η1-coordination structure.
vided η1,η2-coordinated diplatinum complex cis-(PPh3)2-
modes AЈ–CЈ are generated from the reaction of propargyl
Introduction
halides with palladium(0)- or platinum(0)-triphenylphos-
phane complexes (Figure 1).[4–6] In some cases, the oxidat-
ive addition of Pd0(PPh3)n or Pt0(PPh3)2 to the correspond-
ing propargyl or allenyl halides gives cationic or neutral η3-
propargyl/allenyl palladium and/or platinum complexes DЈ
and EЈ.[7,8] Although various propargyl/allenyl palladium
and platinum complexes have been widely investigated,
metal complexes containing pentadiynyl ligand have been
limited to Mo and Fe complexes bearing η1-pentadiynyl li-
gand (type A), with the exception of Pd complexes.[9] In an
extension of these studies, we disclose here the synthesis of
mono- or diplatinum complexes from simple reactions of
pentadiynyl halide with Pt0 and PPh3, and we discuss the
coordination structures of the obtained platinum complexes
and their stability under various reaction conditions.
Currently, there is increasing interest in highly π-conju-
gated carbon-rich compounds, such as polyyne, polyene–
polyyne, and cumulene, because of their potentially wide
applications in synthetic chemistry and materials science.[1]
Although the elucidation of transition-metal complexes
bearing expanded π-conjugated hydrocarbons promises new
insights, little is understood about such complexes com-
pared to metal complexes bearing a propargyl/allenyl unit
as the shortest polyyne/cumulene.[2]
We have reported the synthesis of mono- and dinuclear
palladium complexes containing a pentadiynyl unit.[3] The
reaction of pentadiynyl halide with a (triphenylphosphan-
yl)palladium(0) complex produces monopalladium com-
plexes η1-pentadiynylpalladium A, η1-(penta-1,2-dien-4-yn-
3-yl)palladium B, and dinuclear complex C, revealing the
unique µ-η3-coordination of the Pd–Pd unit to three carbon
atoms (Scheme 1). These complexes can be yielded selec-
tively by treating pentadiynyl halide with Pd0 and PPh3 in
a suitable ratio. Palladium and/or platinum complexes con-
taining a propargyl/allenyl unit with similar coordination
[a] Graduate School of Materials Science, Nara Instituted of
Science and Technology (NAIST),
8916-5 Takayama, Ikoma, Nara 630-0101, Japan
Fax: +81-743-72-6089
E-mail: tsutsumi@ms.naist.jp
kakiuchi@ms.naist.jp
[b] Department of Applied Chemistry, Faculty of Engineering,
University of Miyazaki,
1-1 Gakuen Kibanadai-Nishi, Miyazaki 889-2155, Japan
Scheme 1. Reaction of pentadiynyl halides with Pd0 and PPh3.
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K. Tsutsumi, K. Kakiuchi et al.
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propargyl- and η1-allenylplatinum complexes.[11,12] In ad-
dition, Kurosawa and Ogoshi reported that Pt(PPh3)4 accel-
erates the propargyl–allenyl isomerization reaction through
an intermolecular redox transmetalation process; thus, a
similar reaction was tested for complex cis-2b.[12] When cis-
2b was heated in the presence of 0.1 equiv. of Pt(PPh3)4 at
70 °C, trans-(PPh3)2PtBr[η1-C(CϵCPh)=C=CH2] (trans-
3b) was formed along with trans-2b (Scheme 3). The 1H
NMR spectrum of trans-3b shows a triplet signal for the
methylene protons at low field (δ = 3.28 ppm) with a
smaller coupling constant (JHP = 4.0 Hz) compared to
those of complexes 2. Further isomerization to (PPh3)2-
PtBr[η1-C(Ph)=C=C=C=CH2] (4b) was not observed even
under the reaction conditions. It is possible that the steric
repulsion between the Ph group bonding to the terminal
acetylene and PPh3 prevent isomerization to 4b. This be-
havior is similar to that of the corresponding palladium an-
alogues.[3]
Figure 1. Structure of the propargyl/allenyl palladium and/or plati-
num complexes.
Results and Discussion
Reaction of Pentadiynyl Halides 1 with Pt(C2H4)(PPh3)2
In the reaction of pentadiynyl halide 1a or 1b (X = Cl,
Br) with equimolar amounts of Pt(C2H4)(PPh3)2 in C6D6
at room temperature, cis-(PPh3)2PtX(η1-CH2CϵCCϵCPh)
(cis-2a or cis-2b) was obtained as a sole product (Scheme 2).
1
Each complex shows a H NMR resonance of the methyl-
ene protons at δ = 2.64 ppm or δ = 2.79 ppm as a doublet
of doublets on the basis of two phosphanes (JHP = 9.2,
6.1 Hz or JHP = 9.2, 6.7 Hz) with 195Pt satellites (JHPt
=
73.3 Hz or JHPt = 77.6 Hz), which indicates the η1-pen-
tadiynyl structure with a cis arrangement of phosphane li-
gands on the Pt atom. In the 31P NMR spectra, two doublet
signals of these complexes also support the cis structure
[cis-2a: δ = 18.2 (d, JPP = 16.7 Hz), 21.2 (d, JPP
=
16.7 Hz) ppm; cis-2b: δ = 18.4 (d, JPP = 16.8 Hz), 19.1 (d,
JPP = 16.8 Hz) ppm]. Elemental analyses of these complexes
showed the expected composition.
Scheme 3. Isomerization reaction of cis-2b.
Reaction of Pentadiynyl Halide 1a with Pt(PPh3)4
The reaction of 1a with Pt(PPh3)4 in C6D6 gave a mixture
of cis-2a and trans-2a (Scheme 4). Excess amounts of PPh3
may accelerate the cis–trans isomerization of the geometry
around platinum. Interestingly, a similar reaction was con-
ducted in CDCl3 to give the phosphane adduct platina-
Scheme 2. Reaction of XCH2CϵCCϵCPh (1) with Pt(C2H4)-
(PPh3)2.
cyclobutene
complex
[(PPh3)2Pt{η2-CH2C(PPh3)=C-
1
(CϵCPh)}]+Cl– (5) in 90% yield. In the H NMR spectra,
Heating of cis-2a or cis-2b to 50 °C in C6D6 produced the resonance of methylene protons was found upfield (δ
trans-(PPh3)2PtX(η1-CH2CϵCCϵCPh) (trans-2a or trans- –0.05 ppm) with a 195Pt satellite (JHPt = 83.7 Hz). The 31P
1
2b). In the H NMR spectrum, a signal attributed to the NMR spectroscopic data, δ = 4.1 (dd, JPP = 26.9, 26.1 Hz),
methylene protons appears at δ = 1.64 ppm or δ = 1.72 ppm 21.0 (dd, JPP = 26.1, 9.3 Hz), and 22.3 (dd, JPP = 26.9,
as a triplet. Other platinum complexes with metal shifted 9.3 Hz) ppm, indicate that three phosphane ligands exist in
on
a
pentadiynyl ligand, such as, (PPh3)2PtX[η1- one cis and two anti arrangements as shown in Scheme 4.
C(CϵCPh)=C=CH2], were not generated by prolonged The phosphorus attached to carbon indicates smaller values
heating. It turns out that cis-2a and cis-2b are kinetically for the 195Pt satellite (JPPt = 606.6 Hz) compared to the
preferred over trans-2a and trans-2b, which are similarly phosphorus ligands attached to platinum (JPPt = 2521.3,
preferred in the case of propargylplatinum complexes.[6,10]
2169.6 Hz). These spectral features are almost similar to
Although chloride complex cis-2a required 24 h for cis– those of the other metallacyclobutene analogues.[13] In [D7]-
trans isomerization, bromide analogue cis-2b isomerized to dmf, 5 was generated together with cis-2a and trans-2a.
trans-2b within 1 h. The order of the reaction rates (Br Ͼ However, 5 was not observed in [D8]thf, similarly to the
Cl) is similar to that of the mutual isomerization of η1- reaction in C6D6. This is strong evidence of a crucial sol-
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Mono- or Diplatinum Complexes with a π-Conjugated Pentadiynyl Ligand
Scheme 4. Reaction of ClCH2CϵCCϵCPh (1a) with Pt(PPh3).
vent effect on the products. There are no reports of the Mechanistic Aspects of the Transformation of
corresponding platinacyclobutene analogues generated Monoplatinum Complexes
from a similar reaction of propargyl halides with Pt-
Chen reported that treatment of PPh3 with a cationic η3-
(PPh3)4.
allenyl/propargyl platinum complex [(PPh3)2Pt(η3-CH2-
Treatment of 1a with an equimolar amount of Pt0 and
CCH)]+ afforded a phosphane adduct platinacyclobutene
2 equiv. of PPh3 from Pt(C2H4)(PPh3)2 in C6D6 generated
complex [(PPh3)2PtBr{η2-CH2C(PPh3)=CH}]+.[13] Cationic
cis-2a as a kinetic product. Thus, we examined the reaction
η3-allenyl/propargyl platinum complexes easily react with
of cis-2a with an equimolar amount of PPh3 in various sol-
nucleophiles at the central carbon of the η3-allenyl/proparg-
vents (Scheme 5). Both H and 31P NMR analyses showed
platinacyclobutene 5 in CDCl3 and [D7]dmf and not in
1
yl ligand, which is in contrast to the reactivity of the neu-
tral η1-propargyl- or η1-allenyl platinum complexes.[6,7,14]
C6D6 and [D8]thf. In particular, 5 was feasibly produced in
Therefore, complex 5 is probably formed via the corre-
CDCl3 similarly to the reaction of 1a with Pt(PPh3)4, as
shown in Scheme 4, possible due to the stability of metalla-
cyclobutene complexes in the solvents. Complex trans-2a
sponding cationic η3-type complex [(PPh3)2Pt{η3-
CH2CC(CϵCPh)}]+ (6), which could be produced as an
equilibrium isomer of 2a by the spontaneous dissociation
was observed only in C6D6 within 10 min, and thus the cis–
of a chloride ion (Scheme 6). Although cationic η3-type
trans isomerization may proceed more rapidly in C6D6 than
complex 6 was not observed directly by NMR spectroscopic
in other solvents, which is also supported by the results
shown in Scheme 4. NMR spectroscopic monitoring of the
reaction of cis-2a with PPh3 in C6D6 at room temperature
showed that trans-2a increased to 82% and cis-2a decreased
to 10% after 1.5 h. In [D8]thf, the cis–trans isomerization
proceeded smoothly to give cis-2a and trans-2a in 38 and
analysis of cis-2a in any solvent tested, complex 5 resulted
from the addition of PPh3 in both CDCl3 and [D7]dmf
(Scheme 5). The equilibrium may lie in favor of cationic
complex 6 in a polar solvent, similarly to the case of allenyl/
propargyl palladium analogues.[15] Thus it is reasonable that
5 was not observed in the less-polar solvent C6D6. However,
59% yield, respectively, after 4 h. On the other hand, trans-
the fact that 5 was produced in the polar solvent [D8]thf
2a was not observed in CDCl3 or [D7]dmf even after 2 h.
shows that such solvent effects may be related to the relative
stability of the products in solution.
Scheme 6. Plausible mechanism for the generation of 5.
Scheme 5. Reaction of cis-2a with PPh3.
Wojcicki reported that the reactions of η1-propargylplati-
When a similar reaction was carried out in the presence num complex (PPh3)2PtBr(η1-CH2CϵCPh) or cationic η3-
of NaOTf (OTf=OSO3CF3), the platinacyclobutene com- allenyl/propargylplatinum complex [(PPh3)2Pt(η3-CH2-
plex [(PPh3)2Pt{η2-CH2C(PPh3)=C(CϵCPh)}]+OTf– (5- CCH)]+ with large excess amounts of PMe3 in thf led to
OTf) was obtained as the sole product in 98% yield. The tautomerization
product
[(PMe3)3Pt{η1-C(Ph)=C=
NMR spectral features are similar to that of 5, and the CH2}]+.[16] However, corresponding tris(triphenylphos-
composition of 5-OTf was also elucidated by elemental phane)platinum products such as [(PPh3)3Pt(η1-CH2Cϵ
analysis.
CCϵCPh)]+Cl– and [(PPh3)3Pt{η1-C(CϵCPh)=C=CH2}]+-
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Cl– were not observed. The steric repulsion between PPh3 Mechanistic Aspect of the Coordination of Diplatinum to
on the Pt atom, which is more bulky than PMe3, may desta- 1a
bilize the tris(phosphane)-coordinated platinum complexes,
Complex cis-2a reacted with Pt(C2H4)(PPh3)2 to produce
so that the products are also related to the bulkiness of the
diplatinum complexes 7 and/or 8 in good-to-moderate yield
phosphane ligand.
in each solvent (Scheme 8). Hence, in the reaction of excess
amounts of Pt0(PPh3)2, cis-2a is first kinetically generated,
after which the second Pt0(PPh3)2 may coordinate to cis-2a.
Reaction of Pentadiynyl Halides 1a with Two Equivalents of
Pt(C2H4)(PPh3)2
Complex 8 was not observed in the less-polar solvent C6D6,
which is in contrast to intermediate 7, similarly to the for-
mation of complex 5. Dissociation of a Cl– ion together
with η1–η3 rearrangement of the pentadiynyl ligand easily
occurs to generate 6, followed by the addition of the second
platinum moiety to produce η2:η1-coordinating dimetal
complex 8. Therefore, a dimetal complex such as 8 includ-
ing 7 should be explored as a new intermediate in metal-
catalyzed reactions of polyynyl compounds containing pro-
pargyl/allenyl compounds.
Reaction of 1a with 2 equiv. of Pt(C2H4)(PPh3)2 afforded
cis-2a and a new η1,η2-coordinated diplatinum complex cis-
(PPh3)2PtCl[η1-CH2CϵC{(PPh3)2Pt(η2-CϵCPh)}] (7) in
1
C6D6 (Scheme 7). Complex 7 shows a H NMR signal at δ
= 2.84 ppm as a broad singlet with a 195Pt satellite (JHPt
=
66.5 Hz), which indicates that the methylene protons of the
η1-pentadiynyl ligand are bonded to the Pt atom. The
chemical shift and the 195Pt satellites are almost identical to
those of cis-2a. The 31P NMR spectrum of 7 consists of
four nonequivalent signals, that is, δ = 18.6 (d, JPP
=
16.7 Hz), 21.3 (dd, JPP = 16.7, 5.6 Hz), 26.9 (dd, JPP = 31.6,
5.6 Hz), and 27.8 (d, JPP = 31.6 Hz) ppm, which support
the cis arrangements of four phosphane ligands, as shown
in Scheme 7. Pt0–η2-alkyne complexes are well known,[17]
and dimetal coordination to alkynes has been reported.[18]
In contrast, a similar reaction was carried out in CDCl3
to generate a noble platinum adduct platinacyclobutene
complex (PPh3)2Pt[η2-CH2C{(PPh3)2PtCl}C(CϵCPh)] (8)
together with cis-2a and 7. The 1H NMR spectra of 8 show
a broad singlet signal at δ –0.42 ppm with JHPt = 82.5 Hz,
which is assigned to the methylene protons of the metallacy-
clic form, similar to complex 5. Diplatinum complexes 7
and 8 were observed in both [D7]dmf and [D8]thf. The ge-
ometry of the σ-bonded Pt(PPh3)2Cl unit, attached to the
platinacyclobutene ring, could not be clearly established,
because complex 8 is less stable in solution and detectable
only in the early stage of the reaction, but the perceived
coordination and the composition of 8 are also supported
by comparison with protonation product 10 as shown be-
Scheme 8. Reaction of cis-2a with Pt(C2H4)(PPh3)2.
Protonolysis of Platinacyclobutene 5 or 8
Complex 5 did not react with nucleophiles such as
low (Scheme 9). It is interesting to note that complex 8 MeOH and HNEt2. The methylene carbon atom of 5 may
1
shows a different structure from the dipalladium complex have high electron density because the H NMR signal of
prepared by treatment of 1a with 2 equiv. of Pd0(PPh3) the methylene protons appears upfield; hence, the reactivity
(Scheme 1, C).[3] To the best of our knowledge, this is the of electrophiles was examined. Treatment of 1a with
first example of metallacyclobutene coordination with an- Pt(PPh3)4 in CDCl3 resulted in complex 5 (Scheme 4), after
other metal.
which 5 reacted with the excess amounts of HCl, an electro-
Scheme 7. Reaction of ClCH2CϵCCϵCPh (1a) with 2 equiv. of Pt(C2H4)(PPh3)2.
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Mono- or Diplatinum Complexes with a π-Conjugated Pentadiynyl Ligand
phile generated from the reaction of H2O with Me3SiCl in variable-temperature (VT) NMR experiments indicate that
situ, thus yielding the cationic platinum complex [(PPh3)2- no equilibration of syn and anti configurations of the allyl
PtCl{η1-C(CϵCPh)=C(PPh3)CH3}]+Cl– (9; Scheme 9). moiety or cis and trans environments of phosphorus occur
1
Complex 9 shows a H NMR signal at δ = 2.14 ppm as a on the NMR timescale up to 50 °C in CDCl3. Several η1,η3-
broad singlet with a 195Pt satellite (JHPt = 67.2 Hz), which coordinated dimetal complexes have been reported.[19]
is indicated by the methylene protons of the η1-
C(CϵCPh)=C(PPh3)CH3 ligand. 31P NMR spectroscopic
data, δ = 19.0 (d, JPP = 31.6 Hz), 20.3 (d, JPP = 16.7 Hz),
and 23.0 (dd, JPP = 31.6, 16.7 Hz) ppm, indicate that three
phosphane ligands exist in one cis and one anti arrange-
ment. The phosphorus attached to carbon shows smaller
values of the 195Pt satellite (JPPt = 145.1 Hz) compared to
the phosphorus ligands coordinated to platinum (JPPt
=
4252.3 Hz, 1731.3 Hz). Other isomers, such as, [(PPh3)2-
Pt{η3-CH2C(PPh3)CH(CϵCPh)}]+Cl–, were not observed
in situ.
Similarly, subsequent addition of HCl to diplatinum
complex 8, which was generated in situ by the reaction of
1a with 2 equiv. of Pt(C2H4)(PPh3)2 in CHCl3, gave new
diplatinum complex [(PPh3)2Pt{η3-CH2C{cis-(PPh3)2-
1
PtCl}CH(CϵCPh)}]+Cl– (10). The H NMR spectrum in-
dicates that three different π-allyl protones exist in complex
10 (δ = 2.23, 3.20, and 3.58 ppm) and that the 31P NMR
spectrum consists of four nonequivalent signals, that is, δ =
17.7 (d, JPP = 18.6 Hz, JPPt = 4182.8, 48.3 Hz), 16.4 (d, JPP
= 11.2 Hz, JPPt = 4004.6 Hz), 15.2 (d, JPP = 11.2 Hz, JPPt
= 3995.2 Hz), 14.6 (d, JPP = 18.6 Hz, JPPt = 1787.8,
39.0 Hz) ppm, in accordance with a η3,η1-allyl diplatinum
structure, as shown in Scheme 9. Although 5 and 8 have
similar platinacyclobutene frameworks, the regioselectivity
of their protonation was different. The reason for the differ-
ence in regioselectivity is not clear.
Figure 2. The molecular structure of the (PPh3)2Pt[η3-CH2C{cis-
(PPh3)2PtCl}CH(syn-CϵCPh)]+ cation (10) is drawn with thermal
ellipsoids at the 50% probability level. All hydrogen atoms and a
counteranion are omitted for clarity. Selected bond lengths [Å] and
angles [°]: C1–C2 1.396(13), C2–C3 1.439(16), C3–C4 1.449(14),
C4–C5 1.179(15), C1–Pt1 2.172(11), C2–Pt1 2.227(12), C3–Pt1
2.186(9), C2–Pt2 2.083(13), Pt1–P1 2.265(2), Pt1–P2 2.302(3), Pt2–
P3 2.355(3), Pt2–Pt4 2.248(2), Pt2–Cl1 2.356(2); C1–C2–C3
115.4(11), Pt1–C2–Pt2 122.5(4).
Conclusions
The reactions of pentadiynyl halides XCH2CϵCCϵCPh
(1) with mPt0 and nPPh3 afforded various mono- or diplati-
num complexes (PPh3)nPtmX(CH2CCCCPh) (2, 3, 5, 7, 8).
The coordination mode of pentadiynyl species on platinum
crucially depended on the following factors: (i) the ratio of
pentadiynyl halide, phosphane ligand, and Pt0; (ii) the sol-
Scheme 9. Reaction of 5 or 8 with HCl.
Single crystals of complex 10 were grown by slow dif- vent; and (iii) the temperature. η1-Pentadiynylplatinum
fusion of hexane into dichloromethane solution, and the complex 2 was selectively generated in the reactions of 1
structure was confirmed by X-ray crystallography (Fig- with an equimolar amount of Pt(C2H4)(PPh3)2 or Pt-
ure 2). Platinum atoms coordinate as η1 and η3 modes. The (PPh3)4 in C6D6. Complex 2 isomerized into η1-(penta-1,2-
bond lengths of C1–C2 and C2–C3 are between those of dien-4-yn-3-yl)platinum 3 in the presence of catalytic
single and double bonds, and hence, the three-carbon moi- amounts of Pt(PPh3)4 under heating. Platinacyclobutene 5
ety reveals a π–allyl structure derived from diplatinum coor- was easily generated by treatment of Pt(PPh3)4 with 1a in
dination. (PPh3)2PtCl and PhCϵC moieties attached to the CDCl3 or [D7]dmf. We also found that excess amounts of
1
allyl group show syn geometry. H NMR analysis of the Pt(PPh3)2 resulted in the η2,η1-coordinating diplatinum
obtained crystals shows spectra similar to those of 10 gener- complex 8. Furthermore, complex 8 has a novel dinuclear
ated from the reaction of 8 with HCl in situ. In addition, structure, which was easily generated by the reaction of 1a
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2 H, Ph), 7.55–7.60 (m, 6 H, Ph), 7.65–7.69 (m, 6 H, Ph) ppm.
31P{1H} NMR (202.46 MHz, C6D6): δ = 18.2 (d, JPP = 16.7 Hz,
JPPt = 4336.5 Hz, PPh3), 21.2 (d, JPP = 16.7 Hz, JPPt = 1936.1 Hz,
PPh3) ppm. 13C{1H} NMR (125.77 MHz, C6D6): δ = 13.3 (dd, JCP
with excess amounts of Pt(PPh3)2 in CDCl3, [D7]dmf, or
[D8]thf. Therefore, these complexes may be intermediates
in the catalytic reactions of polyynyl, especially propargyl/
allenyl, compounds. Metallacyclobutene complexes 5 and 8
reacted with HCl to give novel mono- or diplatinum com-
plexes 9 and 10, respectively.
= 91.2, 3.8 Hz, CH2), 67.6 (d, JCP = 6.7 Hz, 1 C), 75.2 (d, JCP
=
2.9 Hz, 1 C), 79.0 (d, JCP = 4.8 Hz, 1 C), 93.6 (d, JCP = 11.5 Hz,
1 C), 124.6 (Ph), 127.8–128.5 (m, Ph), 129.8 (Ph), 130.7 (Ph), 130.8
(d, JCP = 60.5 Hz, Ph), 132.3 (d, JCP = 46.1 Hz, Ph), 132.5 (Ph),
134.8 (d, JCP = 10.6 Hz, Ph), 135.5 (d, JCP = 10.6 Hz, Ph) ppm.
M.p. 131.0–134.1 °C (decomp.). C47H37ClP2Pt (894.28): calcd. C
63.12, H 4.17; found C 63.16, H 4.13.
Experimental Section
Materials and Measurements: Mostly commercially available rea-
gents were used without further purification. All reactions and ma-
nipulations of air- and moisture-sensitive compounds were carried
out under an atmosphere of dry nitrogen by using standard vacuum
line techniques. 1H, 31P, and 13C NMR were recorded with a JEOL
JNM-ECP500 or a JNM-ECP600NK spectrometer. Data are re-
ported as follows: chemical shift in ppm (δ), multiplicity (s = sing-
let, d = doublet, t = triplet, dd = doublet of doublets, br. s = broad
singlet, m = multiplet), coupling constant [Hz], and integration.
The H and C contents were determined by elemental analysis by
using a Perkin–Elmer 2900II CHNS/O analyzer. Melting points
were determined with a Yanaco MP-500D micro melting point ap-
paratus.
cis-2b: Prepared by a method similar to that for cis-2a (off-white
solid, 65%). 1H NMR (500.16 MHz, C6D6): δ = 2.79 (dd, JHP
=
9.2, 6.7 Hz, JHPt = 77.6 Hz, 2 H, CH2), 6.79–6.97 (m, 21 H, Ph),
7.44 (dd, J = 8.0, 1.9 Hz, 2 H, Ph), 7.53–5.58 (m, 6 H, Ph), 7.64–
7.69 (m, 6 H, Ph) ppm. 31P{1H} NMR (202.46 MHz, C6D6): δ =
18.4 (d, JPP = 16.8 Hz, JPPt = 4330.0 Hz, PPh3), 19.1 (d, JPP
16.8 Hz, JPPt
1955.7 Hz, PPh3) ppm. 13C{1H} NMR
(125.77 MHz, C6D6): δ = 10.9 (dd, JCP = 91.2, 2.9 Hz, CH2), 68.0
(d, JCP = 6.7 Hz, 1 C), 75.3 (d, JCP = 2.9 Hz, 1 C), 79.0 (d, JCP
=
=
=
4.8 Hz, 1 C), 93.2 (d, JCP = 11.5 Hz, 1 C), 124.6 (Ph), 127.7–128.5
(m, Ph), 129.8 (d, JCP = 2.7 Hz, Ph), 130.7 (d, JCP = 2.9 Hz, Ph),
130.8 (d, JCP = 59.5 Hz, Ph), 132.5 (Ph), 132.8 (d, JCP = 47.0 Hz,
Ph), 134.8 (d, JCP = 10.6 Hz, Ph), 135.7 (d, JCP = 10.6 Hz, Ph)
ppm. M.p. 123.5–126.0 °C (decomp.). C47H37BrP2Pt (938.73):
calcd. C 60.13, H 3.97; found C 59.92, H 3.92.
Reaction of ClCH2CϵCCϵCPh (1a) with Pt(C2H4)(PPh3)2: To a
solution of ClCH2CϵCCϵCPh (1a; 1.6 mg, 0.0092 mmol) and an
appropriate amount of trioxane as an internal standard dissolved
in dry C6D6 (0.6 mL) in an NMR tube under an atmosphere of
dry nitrogen was added Pt(C2H4)(PPh3)2 (6.9 mg, 0.0092 mmol).
The NMR tube was sealed under a nitrogen atmosphere, and the
reaction was followed by 1H and 31P NMR spectroscopy. cis-(PPh3)2-
PtCl(η1-CH2CϵCCϵCPh) (cis-2a) was obtained after 10 min
(90%). Then the NMR tube was heated at 50 °C in an oil bath.
trans-(PPh3)2PtCl(η1-CH2CϵCCϵCPh) (trans-2a) was produced in
47% yield after 24 h. Data for trans-2a: 1H NMR (500.16 MHz,
C6D6): δ = 1.64 (t, JHP = 7.6 Hz, JHPt = 103.3 Hz, 2 H, CH2), 6.89–
7.11 (m, 21 H, Ph), 7.36–7.38 (m, 2 H, Ph), 8.01–8.06 (m, 12 H,
Isomerization Reaction of cis-2b in the Presence of Pt(PPh3)4: To a
solution of cis-2b (9.4 mg, 0.010 mmol) and an appropriate amount
of trioxane as an internal standard dissolved in degassed dry C6D6
(0.6 mL) in an NMR tube was added Pt(PPh3)4 (1.2 mg,
0.00096 mmol). The NMR tube was sealed under a nitrogen atmo-
sphere and heated at 50 °C in an oil bath. The reaction was fol-
1
lowed by H and 31P NMR spectroscopy. After 24 h, a mixture of
trans-2b and trans-(PPh3)2PtBr[η1-C(CϵCPh)=C=CH2] (trans-3b)
was observed in 37% yield (trans-2b/trans-3b = 19:81). Data for
trans-3b: 1H NMR (500.16 MHz, C6D6): δ = 3.28 (t, JHP = 4.0 Hz,
JHPt = 56.2 Hz, 2 H, CH2) ppm. 31P{1H} NMR (202.46 MHz,
C6D6): δ = 21.5 (s, JPPt = 3018.2 Hz, PPh3) ppm.
Ph) ppm. 31P{1H} NMR (202.46 MHz, C6D6): δ = 25.4 (s, JPPt
=
3100.0 Hz, PPh3) ppm. 13C{1H} NMR (125.77 MHz, C6D6): δ =
14.3 (CH2), 66.3 (C), 75.1 (C), 77.9 (C), 91.7 (C), 124.1 (Ph), 128.3–
128.6 (m, Ph), 130.5 (Ph), 130.6 (d, JCP = 54.7 Hz, Ph), 132.5 (Ph),
135.5–135.6 (m, Ph) ppm.
Reaction of 1a with Pt(PPh3)4: The reactions were carried out in
each solvent similarly to the reaction of 1a with Pt(C2H4)(PPh3)2.
The results are summarized in Scheme 4. Data for [(PPh3)2Pt{η2-
CH2C(PPh3)=C(CϵCPh)}]+Cl– (5): 1H NMR (500.16 MHz,
CDCl3): δ = –0.05 (dd, JHP = 6.7, 3.7 Hz, JHPt = 83.7 Hz, 2 H,
CH2), 5.68 (d, J = 6.7 Hz, 2 H, Ph), 6.83 (dd, J = 7.3, 6.7 Hz, 2 H,
Ph), 6.98 (t, J = 7.3 Hz, 1 H, Ph), 7.07–7.11 (m, 6 H, Ph), 7.16–
7.39 (m, 24 H, Ph), 7.42–7.47 (m, 6 H, Ph), 7.52–7.57 (m, 6 H, Ph),
7.68–7.72 (m, 3 H, Ph) ppm. 31P{1H} NMR (202.46 MHz, CDCl3):
δ = 4.1 (dd, JPP = 26.9, 26.1 Hz, JPPt = 606.6 Hz, CPPh3), 21.0 (dd,
JPP = 26.1, 9.3 Hz, JPPt = 2521.3 Hz, PtPPh3), 22.3 (dd, JPP = 26.9,
9.3 Hz, JPPt = 2169.6 Hz, PtPPh3) ppm.
Reaction of BrCH2CϵCCϵCPh (1b) with Pt(C2H4)(PPh3)2: The
reaction of BrCH2CϵCCϵCPh (1b) was carried out similarly to
that of 1a. cis-(PPh3)2PtBr(η1-CH2CϵCCϵCPh) (cis-2b) was ob-
tained after 10 min (76%). trans-(PPh3)2PtBr(η1-CH2Cϵ
CCϵCPh) (trans-2b) was produced in 69% yield after heating for
1
1 h. Data for trans-2b: H NMR (500.16 MHz, C6D6): δ = 1.72 (t,
JHP = 7.6 Hz, JHPt = 101.4 Hz, 2 H), 6.91–7.12 (m, 21 H), 7.38–
7.41 (m, 2 H), 8.00–8.05 (m, 12 H) ppm. 31P{1H} NMR
(202.46 MHz, C6D6): δ = 25.1 (s, JPPt = 3067.1 Hz, PPh3) ppm.
13C{1H} NMR (125.77 MHz, C6D6): δ = 14.3 (CH2), 66.9 (C), 75.5
(C), 77.9 (C), 91.0 (C), 124.0 (Ph), 128.1–128.6 (m, Ph), 130.5 (Ph),
130.9 (d, JCP = 55.7 Hz, Ph), 132.5 (Ph), 135.5–135.7 (m, Ph) ppm.
[(PPh3)2Pt{η2-CH2C(PPh3)=C(CϵCPh)}]+OTf– (5-OTf): To
a
solution of cis-2a (100 mg, 0.112 mmol) dissolved in degassed dry
CHCl3 (10 mL) was added PPh3 (28.9 mg, 0.110 mmol) and NaOTf
(37.4 mg, 0.217 mmol) under an atmosphere of nitrogen. The reac-
tion mixture was stirred for 1 h at room temperature. The reaction
mixture was concentrated under vacuum, and the obtained residue
was dissolved in dry CH2Cl2. After filtration, the filtrate was con-
centrated under vacuum again, and the residue was washed with
benzene. Recrystallization from CHCl3 and hexane gave a yellow
cis-2a: Pt(C2H4)(PPh3)2 (244 mg, 0.326 mmol) was added to a dry
benzene solution (7 mL) of 1a (67.9 mg, 0.389 mmol) under an at-
mosphere of dry nitrogen. After 30 min at room temperature, the
volume of the solvent was reduced to half by rotary evaporation.
After the addition of hexane (200 mL), the yellow precipitate was
collected on a glass filter and washed with diethyl ether and pen-
1
1
tane to give an off-white solid of cis-2a (250 mg, 86%). H NMR
solid of 5-OTf (137.4 mg, 98%). H NMR (600.18 MHz, CDCl3):
(500.16 MHz, C6D6): δ = 2.64 (dd, JHP = 9.2, 6.1 Hz, JHPt
=
δ = –0.03 (dd, JHP = 6.6, 4.2 Hz, JHPt = 85.0 Hz, 2 H, CH2), 5.78
73.3 Hz, 2 H, CH2), 6.80–6.96 (m, 21 H, Ph), 7.45 (d, J = 6.7 Hz, (d, J = 8.4 Hz, 2 H, Ph), 6.84 (dd, J = 7.8, 7.2 Hz, 2 H, Ph), 6.97
2366 Eur. J. Inorg. Chem. 2010, 2361–2368
www.eurjic.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Mono- or Diplatinum Complexes with a π-Conjugated Pentadiynyl Ligand
(dd, J = 8.4, 7.2 Hz, 1 H, Ph), 7.08–7.12 (m, 6 H, Ph), 7.17–7.41
(m, 24 H, Ph), 7.44–7.49 (m, 6 H, Ph), 7.53–7.57 (m, 6 H, Ph), 7.70
C), 127.8–132.0 (m, Ph), 133.7–135.0 (m, Ph) ppm. M.p. 147.9–
149.3 °C (decomp.). C83H68Cl2P4Pt2 (1650.40): calcd. C 60.40, H
(t, J = 7.2 Hz, 3 H, Ph) ppm. 31P{1H} NMR (242.95 MHz, CDCl3): 4.15; found C 60.40, H 4.40. Single crystals of 10 for X-ray diffrac-
δ = 4.2 (t, JPP = 26.6 Hz, JPPt = 604.6 Hz, CPPh3), 21.0 (dd, JPP
26.6, 8.7 Hz, JPPt = 2517.8 Hz, PtPPh3), 22.3 (dd, JPP = 26.6,
8.7 Hz, JPPt
2156.7 Hz, PtPPh3) ppm. 13C{1H} NMR
(125.77 MHz, CDCl3): δ = –5.5 (dd, JCP = 76.3, 4.8 Hz, JPPt
365.4 Hz, CH2), 89.1 (q, JCP = 5.6 Hz, 1 C), 115.9 (d, JCP = 5.8 Hz,
JCPt = 37.6 Hz, 1 C), 120.9 (q, JCF = 319.5 Hz, CF3), 122.3 (s, Ph),
127.1–130.0 (m, Ph), 130.1 (dd, JCP = 22.0, 1.9 Hz, 1 C), 149.3 (d,
JCP = 115.4 Hz, JCPt = 598.0 Hz, 1 C) ppm. M.p. 161.4–165.5 °C
(decomp.). C66H52F3O3P3PtS (1270.18): calcd. C 62.41, H 3.78;
found C 62.29, H 4.04.
=
tion analysis were obtained by slow diffusion of hexane into a con-
centrated CH2Cl2 solution of 10.
=
Crystal Data for 10: C83H68Cl2P4Pt2, M = 1650.43, colorless, tri-
clinic, a = 13.6897(7) Å, b = 16.8795(9) Å, c = 20.2072(12) Å, α =
70.8631(16)°, β = 78.6225(15)°, γ = 81.8964(15)°, V = 4309.9(4) Å3,
=
¯
T = 153Ϯ1 K, space group P1 (#2), Z = 2, µ(Mo-Kα) =
34.019 cm–1, 33945 reflections measured, 15498 independent reflec-
tions (Rint = 0.058). The final R1 values were 0.0719 [IϾ2σ(I)]. The
final wR(F2) values were 0.0896 [IϾ2σ(I)]. The goodness of fit on
F2 was 0.979. CCDC-690680 contains 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/cif.
Reaction of 1a with Pt(C2H4)(PPh3)2: The reactions were carried
out in each solvent similarly to the reaction of 1a with
Pt(C2H4)(PPh3)2. The results are summarized in Scheme 7. cis-
(PPh3)2PtCl[η1-CH2CϵC{(PPh3)2Pt(η2-CϵCPh)}] (7) and (PPh3)2-
Pt[η2-CH2C{(PPh3)2PtCl}C(CϵCPh)] (8) gradually decomposed in
solution. Thus they cannot be isolated. Data for 7: 1H NMR
(500.16 MHz, C6D6): δ = 2.84 (br. s, JHPt = 66.5 Hz, 2 H, CH2)
Acknowledgments
ppm. 31P{1H} NMR (202.46 MHz, C6D6): δ = 18.6 (d, JPP
=
This work was supported in part by a Grant-in-Aid for Scientific
Research on Priority Areas (Reaction Control of Dynamic Com-
plexes) from the Ministry of Education, Culture, Sports, Science,
and Technology, Japan (No. 15036247 and 16033243). We are
grateful to Professor Hideo Kurosawa and Professor Sensuke Ogo-
shi of Osaka University for their valuable suggestions. We also
thank Mr. Fumio Asanoma and Mr. Shouhei Katao for assistance
in obtaining elementary analysis data.
16.7 Hz, JPPt = 4529.1 Hz, PPh3), 21.3 (dd, JPP = 16.7, 5.6 Hz, JPPt
= 1790.1 Hz, PPh3), 26.9 (dd, JPP = 31.6, 5.6 Hz, JPPt = 3490.7 Hz,
PPh3), 27.8 (d, JPP = 31.6 Hz, JPPt = 3449.8 Hz, PPh3) ppm. Data
for 8: 1H NMR (500.16 MHz, CDCl3): δ = –0.42 (br. s, JHPt
=
82.5 Hz, 2 H, CH2), 6.35 (d, JHH = 7.4 Hz, 2 H, Ph), 6.73 (dd, JHH
= 7.4, 7.3 Hz, 2 H, Ph), 6.83 (t, JHH = 7.3 Hz, 1 H, Ph) ppm.
31P{1H} NMR (202.46 MHz, CDCl3): δ = 22.4 (d, JPP = 3.7 Hz,
JPPt = 1953.8 Hz, PPh3), 24.4 (d, JPP = 3.7 Hz, JPPt = 2318.5 Hz,
PPh3), 25.6 (br. s, JPPt = 3648.9, 63.3 Hz, PPh3) ppm.
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Reaction of 5 with HCl: Pt(PPh3)4 (74.7 mg, 0.060 mmol) was
added to a dry solution of 1a (10.5 mg, 0.060 mmol) in CDCl3
(0.6 mL) at room temperature. After 10 min, 5 was observed in
90% NMR yield. Then, Me3SiCl (7.8 mg, 0.072 mmol) and H2O
(ca. 1 µL) were added to the NMR tube. After 3.0 min, [(PPh3)2-
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1
low stability in solution. H NMR (500.16 MHz, CDCl3): δ = 2.14
(br. s, JHPt = 67.2 Hz, 3 H, CH3), 6.57 (d, J = 7.3 Hz, 2 H, Ph),
7.05–7.75 (m, 48 H, Ph) ppm. 31P{1H} NMR (202.46 MHz,
CDCl3): δ = 19.0 (d, JPP = 31.6 Hz, JPPt = 145.1 Hz, CPPh3), 20.3
(d, JPP = 16.7 Hz, JPPt = 4252.3 Hz, PtPPh3), 23.0 (dd, JPP = 31.6,
16.7 Hz, JPPt = 1731.3 Hz, PtPPh3) ppm.
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in degassed dry CDCl3 (0.6 mL) at room temperature. After
10 min, 8 was observed in 54% NMR yield. Then, Me3SiCl
(5.2 mg, 0.048 mmol) and H2O (ca. 1 µL) were added to the NMR
tube. After 30 min, [(PPh3)2Pt{η3-CH2C{cis-(PPh3)2PtCl}CH-
(CϵCPh)}]+Cl– (10) was generated in 70% NMR yield based on
8. The volatiles were removed under vacuum, yielding a yellow oil.
This material was washed with hexane and Et2O and then recrys-
tallized from CH2Cl2 and hexane to give an off-white solid of 10
(21.7 mg, 33%). 1H NMR (500.16 MHz, CDCl3): δ = 2.23 (m, JHPt
= 41.5 Hz, 1 H, CH), 3.20 (m, JHPt = 53.0 Hz, 1 H, CH), 3.58 (br.
s, 1 H, CH), 6.95–7.12 (m, 20 H, Ph), 7.19–7.48 (m, 15 H, Ph) ppm.
31P{1H} NMR (202.46 MHz, CDCl3): δ = 14.6 (d, JPP = 18.6 Hz,
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3995.2 Hz, PPh3), 16.4 (d, JPP = 11.2 Hz, JPPt = 4004.6 Hz, PPh3),
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
2367

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Received: December 9, 2009
Published Online: April 30, 2010
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