Complex of bis(triphenylphosphine)platinum(0) with but-2-yne-1,4-diol: Synthesis and molecular structure

Article abstract of DOI:10.1134/S1070328410110035

Reduction of (PPh₃)₂PtCl₂ with hydrazine hydrate in ethanol followed by treatment with an equivalent of an alkyne gave (butynediol)bis(triphenylphosphine)platinum(0), (PPh₃) ₂Pt[C₂(CH₂

Full text of DOI:10.1134/S1070328410110035

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2010, Vol. 36, No. 11, pp. 801–803. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © S.S. Shapovalov, A.A. Pasynskii, Yu.V. Torubaev, 2010, published in Koordinatsionnaya Khimiya, 2010, Vol. 36, No. 11, pp. 811–813.
Complex of Bis(triphenylphosphine)platinum(0)
with Butꢀ2ꢀyneꢀ1,4ꢀdiol: Synthesis and Molecular Structure
S. S. Shapovalov, A. A. Pasynskii*, and Yu. V. Torubaev
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
*Eꢀmail: aapas@rambler.ru
Received April 14, 2010
Abstract—Reduction of (PPh3)2PtCl2 with hydrazine hydrate in ethanol followed by treatment with an
equivalent of an alkyne gave (butynediol)bis(triphenylphosphine)platinum(0), (PPh3)2Pt[C2(CH2OH)2] (
I
).
has a square environment (Pt–C, 2.036(3) and
2.050(3) Å; Pt–P, 2.2719(8) and 2.2817(7) Å). In the coordinated butynediol, the C=C bond is lengthened
(1.287(4) Å) and the angles C–C C are reduced to 140.3(3)° and 144.6(3)°, probably because of the donaꢀ
According to Xꢀray diffraction data, the Pt atom in complex
I
≡
tion of four electrons to the Pt atom. In the crystal, complex
between the hydroxy groups of adjacent molecules.
I forms dimers stabilized by hydrogen bonds
DOI: 10.1134/S1070328410110035
It is known that the geometry of the coordinated
alkynes depends on the number of electrons formally
(
PPh3)2Pt[C2(СН2ОН)2] (
I
), a promising chelating
agent analogous to [Co2(CO)6][
μ
ꢀC2(СН2ОН)2] (II
).
donated from the triple
deficient metal center. For instance,
coordination of butꢀ2ꢀyneꢀ1,4ꢀdiol
C5H5Mn(CO)2][ ꢀC2(СН2ОН))2] results in the
reduction of the angle С–С from 180 to 152 [1].
In the complex [Co2(CO)6][ ꢀC2(СН2ОН)2], this
angle is 144° because of donation [2]. Such a
С
≡
С
bond to the electronꢀ
ꢀdonating
into
2е
EXPERIMENTAL
The starting reagent (PPh3)2PtCl2 was prepared as
described in [9]. Butꢀ2ꢀyneꢀ1,4ꢀdiol (Fluka) and
triphenylphosphine (Merck) were used as purchased.
An IR spectrum was recorded on a Specord 75 IR
spectrophotometer (KBr pellet).
[
μ
≡
С
°
°
μ
4
е
change in the alkyne ligand geometry allows chelation
with heterometals via replacement of the hydroxyl H
atoms (e.g., when the fragment R2Si [3] or was added dropwise to a suspension of (PPh3)2PtCl2
Synthesis of complex I. Hydrazine hydrate (0.4 ml)
(0.5 g) in propanꢀ2ꢀol (20 ml). The colorless solution
turned yellow. It was stirred for 10 min and then
butyneꢀ1,4ꢀdiol (0.06 g) was added. The mixture was
refluxed for 15 min and evaporated to dryness in a
water aspirator vacuum. The residue was recrystallized
from benzene–light petroleum (1 : 1). The yield was
0.39 g (61%), white crystals.
(C5H5Fe(CO)2)2Sn [4] is introduced). With a further
increase in the electron deficiency on the metalꢀconꢀ
taining fragment to six (e.g., in Co4(CO)10[μ4
ꢀ
C2(СН2ОН)2]), the angle С–С≡С is reduced to 125°,
which results in “proton chelation” through intramoꢀ
lecular hydrogen bonding between adjacent hydroxy
groups ((O)H—O, 1.834 Å) [5].
For C40H36O2P2Pt (
anal. calcd., %:
Found, %:
M
= 805)
H, 4.50;
H, 4.00;
In Pt(II) complexes, an alkyne usually donates two
electrons (as in, e.g., a 16
(CH3NH2)PtCl2][C2(С(СН3)2ОН)2], in which the
angle С–С is 161 [6]). At the same time, an alkyne
in 18 complexes of Pt(0) acts as a donor; in the
е analog of Zeise’s salt,
C, 59.63;
C, 59.09;
[
≡С
°
е
4е
IR (KBr,
≡С), 1480 w, 1430 s, 1090 m, 1010 m, 740 w, 700 s,
ν
, cm–1): 3600–3200 m.br, 1770 m
structurally characterized Pt(0) complexes with
monohydroxyalkynes (diphenylpropꢀ2ꢀynꢀ1ꢀol [7]
(С
540 m, 520 m, 510 m, 500 w.
and 1ꢀethynylcyclohexanol [8]), the angles С–С
are 146 and 139 , respectively, as in the aforemenꢀ
tioned binuclear cobalt complex [2].
≡С
Xꢀray diffraction analysis of complex I was carried
°
°
out at the Xꢀray Diffraction Center of the Institute of
Organoelement Compounds, Russian Academy of
Sciences. Crystallographic parameters and the data
It was interesting to try to obtain a diphosphine
complex of Pt(0) with butꢀ2ꢀyneꢀ1,4ꢀdiol, collection statistics for structure
I are given in table.
801

802
SHAPOVALOV et al.
P(2A)
O(3A)
C(78A)
C(40
O(2
A)
P(1A)
C(39A)
A
)
P(3A)
Pt(1A)
C(77A)
C(79
A)
C(37A)
O(4A)
Pt(2
A)
C(38A)
C(80A)
O(1A)
P(4A)
Molecular structure I and the association of molecules in the crystal.
Structure
I
was solved by the direct methods and
RESULTS AND DISCUSSION
refined anisotropically (isotropically for H atoms) by
the leastꢀsquares method on F2 with the SHELXTL
program [10]. The H atoms were located geometriꢀ
cally. Atomic coordinates and other parameters of
structure I have been deposited with the Cambridge Crysꢀ
tallographic Data Collection (no. 772 612; deposit@c
cdc.cam.ac.uk or http://www.ccdc.cam. ac.uk).
By analogy with the synthesis of (PPh3)2Pt(С2Ph2
)
[11], we reduced (PPh3)2PtСl2 with hydrazine hydrate
in ethanol and then treated the reaction mixture, withꢀ
out isolating an intermediate product, with an equivaꢀ
lent of an alkyne:
CH2OH
1) N2H4
2) C4H6O2
⋅ H2O/EtOH
C
(PPh3)2PtCl2
(PPh3)2Pt
C
CH2OH
(I)
Note that the use of an excess of the alkyne does butynediol molecule in complex
not increase the yield of the complex but makes its isoꢀ complex II, the crystal structure
lation substantially more difficult.
I
is a
contains dimeric
pairs with fourꢀmembered rings of the Hꢀbonded oxyꢀ
gen atoms. Intermolecular contacts O H in structure
are 1.92–2.00 Å. Intramolecular contacts H(О) in
4е donor. As in
I
⎯
According to Xꢀray diffraction data, the crystal of
complex I consists of two independent molecules (figꢀ
I
O⎯
structure I (2.21 Å) are much weaker than those in the
ure). The complex has a square structure (Pt–C,
2.036(3)–2.050(3) Å; Pt–P, 2.2719(8)–2.2817(7) Å).
aforementioned complex Co4(CO)10[μ4ꢀC2(СН2ОН) ]
2
with the “chelated proton” (1.83 Å) [5].
The
С
≡
≡С
bond lengths (1.287(4) Å) and the angles
С (140.3(3)°–144.6(3) in structure are nearly
equal to those in complex II [2]. Apparently, the (PPh3)2Ni[C2(СН2ОН)2] [12], the angle С–С
С
⎯
С
°)
I
Note
that
in
the
related
complex
is
≡
С
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 36
No. 11
2010

COMPLEX OF BIS(TRIPHENYLPHOSPHINE)PLATINUM(0)
803
Selected crystallographic parameters and the data collection
statistics for complex I
tetrameric structure with oxygenꢀcontaining eightꢀ
membered rings.
Parameter
Diffractometer
Radiation; , Å
Value
ACKNOWLEDGMENTS
Bruker APEX III CCD
λ
MoKα; 0.71073
This work was supported by the Russian Foundaꢀ
tion for Basic Research (project no. 09ꢀ03ꢀ00961) and
the Division of Chemistry and Materials Sciences of
the Russian Academy of Sciences (grant OKh 1.3).
Temperature, K
Space group
100(2)
P1
a
, Å
, Å
12.8490(6)
13.3722(6)
20.2943(10)
97.956(10)
99.354(10)
96.171(10)
3377.2(3)
4
b
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c
, Å
, deg
, deg
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RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 36
No. 11
2010