Synthesis and structures of 1,1′-bis(diphenylphosphino)metallocenyl complexes M(η 5-C5H4PPh2) 2Ru(H2O)2(OTs)2 (M = Fe, Ru, or Os)

Article abstract of DOI:10.1007/s11172-006-0313-0

The reaction of equimolar amounts of M(η⁵-C ₅H₄PPh₂)₂ (M = Fe, Ru, or Os) and [Ru(H₂O)₆](OTs)₂ afforded the M(η⁵-C₅H₄PPh₂)

Full text of DOI:10.1007/s11172-006-0313-0

Russian Chemical Bulletin, International Edition, Vol. 55, No. 4, pp. 683—686, April, 2006
683
Synthesis and structures of 1,1´ꢀbis(diphenylphosphino)metallocenyl
complexes M(η5ꢀC5H4PPh2)2Ru(H2O)2(OTs)2 (M = Fe, Ru, or Os)
T. A. Peganova,ꢀ N. V. Vologdin, P. V. Petrovskii, I. D. Nesterov, K. A. Lyssenko, and O. V. Gusev
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (495) 135 5085. Eꢀmail: gusev@ineos.ac.ru
5
The reaction of equimolar amounts of M(η ꢀC5H4PPh2)2 (M = Fe, Ru, or Os) and
5
[Ru(H2O)6](OTs)2 afforded the M(η ꢀC5H4PPh2)2Ru(H2O)2(OTs)2 complexes, which were
characterized by elemental analysis and 1H, 13C, and 31P NMR spectroscopy. The structure of
the osmocene complex was established by Xꢀray diffraction.
Key words: 1,1´ꢀbis(diphenylphosphino)metallocene, complexes, ruthenium, iron, osmium.
Chelate diꢀ and triphosphine ruthenium comꢀ
plexes belong to an important class of coordinaꢀ
tion compounds. Earlier,1 we have demonstrated
that the cisꢀ[Ru(Ph2P{CH2}2PPh2)2(OTs)]OTs and
RuPhP(CH2CH2CH2PPh2)2(OTs)2 complexes catalyze
alternating copolymerization of ethylene with carbon
monoxide.
In the present study, we synthesized ruthenium comꢀ
plexes with the 1,1´ꢀbis(diphenylphosphino)metallocenyl
ligands. We used 1,1´ꢀbis(diphenylphosphino)metalloꢀ
cenyl complexes as ligands taking into account the folꢀ
lowing fact. Earlier, it has been demonstrated that pallaꢀ
dium complexes with these ligands exhibit high chemoꢀ
selectivity due to their ability to form the M—Pd bond2—5
and, in some cases, these complexes are superior to comꢀ
plexes with organic diphosphines in activity.6
(H2O)2(OTs)2 complexes (M = Fe (1), Ru (2), or Os (3)),
which were characterized by elemental analysis and H,
13C, and 31P NMR spectroscopy.
1
The 31P NMR spectra of compounds 1—3 show sinꢀ
glets at δ 58.1 (1), 54.7 (2), and 58.1 (3), which is indicaꢀ
tive of the presence of the symmetry plane in these molꢀ
ecules. The cyclopentadienyl ligands are characterized by
pairs of broadened singlets at δ 4.18 and 4.26 (1), 4.61
1
and 4.65 (2), and 4.81 and 4.87 (3) in the H NMR
spectra and pairs of singlets and triplets for the quaternary
carbon atoms at δ 70—80 in the 13C NMR spectra. The
1H and 13C NMR spectra provide evidence for the presꢀ
ence of two tosylate residues in each molecule, as follows
from the presence of pairs of doublets at δ 7.08 and
7.29 (1), 7.08 and 7.29 (2), and 7.08 and 7.28 (3) and four
singlets at δ 125—141. The phenyl rings at the phosphorus
atoms appear as three multiplets at δ 7.2—7.6 in the
1H NMR spectra and four signals at δ 125—140 in the
13C NMR spectra, the signals for the quaternary carbon
atom and the signals for the C atoms in the meta and
ortho positions being decoupled from the phosphorus
atoms. The signals for the protons of water molecules are
The reaction of equimolar amounts of 1,1´ꢀbis(diꢀ
phenylphosphino)metallocene and [Ru(H2O)6](OTs)2
(Scheme 1) afforded the M(η5ꢀC5H4PPh2)2Ruꢀ
Scheme 1
1
not observed in the H NMR spectra due, apparently, to
their rapid exchange.
The structure of complex 3 was studied by Xꢀray difꢀ
fraction (Fig. 1, Table 1). The cyclopentadienyl groups in
osmocene 3 adopt a staggered conformation with the
P(1)—C(1)—C(6)—P(2) pseudotorsion angle of –37.4°.
The Cp rings are inclined toward the ruthenium atom
(dihedral angle is 6.0°). The phosphorus atoms deviate
from the plane of the Cp groups toward the metal atom by
0.21 and 0.14 Å.
The ruthenium atom in molecule 3 has a distorted
octahedral coordination (Fig. 2). The ruthenium and osꢀ
mium atoms are at a nonbonded distance (4.330(1) Å).
M = Fe (1), Ru (2), Os (3)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 659—661, April, 2006.
1066ꢀ5285/06/5504ꢀ0683 © 2006 Springer Science+Business Media, Inc.

684
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 4, April, 2006
Peganova et al.
Table 1. Selected bond length (d) and bond angles (ω) in molecule 3
Bond
d/Å
Bond
d/Å
Bond
d/Å
Os(1)—C(1)
Os(1)—C(6)
Os(1)—C(5)
Os(1)—C(2)
Os(1)—C(10)
Os(1)—C(7)
Os(1)—C(8)
Os(1)—C(4)
2.143(5)
2.148(4)
2.165(5)
2.174(5)
2.182(5)
2.184(5)
2.194(5)
2.201(5)
Os(1)—C(3)
Os(1)—C(9)
Ru(1)—O(4)
Ru(1)—O(1)
Ru(1)—O(2W)
Ru(1)—O(1W)
Ru(1)—P(1)
Ru(1)—P(2)
2.208(5)
2.217(5)
2.114(3)
2.145(3)
2.190(3)
2.222(3)
2.2544(13)
2.2926(13)
S(1)—O(3)
S(1)—O(2)
S(1)—O(1)
S(1)—C(35)
S(2)—O(5)
S(2)—O(6)
S(2)—O(4)
S(2)—C(42)
1.436(4)
1.449(4)
1.490(3)
1.769(5)
1.443(5)
1.440(5)
1.464(4)
1.763(6)
Angle
ω/deg
Angle
ω/deg
97.84(5)
104.9(2)
102.1(2)
102.3(2)
118.02(16)
118.93(17)
108.17(15)
98.8(2)
103.0(2)
99.9(2)
126.15(15)
114.55(16)
110.85(16)
114.3(2)
Angle
ω/deg
O(4)—Ru(1)—O(1)
O(4)—Ru(1)—O(2W)
O(1)—Ru(1)—O(2W)
O(4)—Ru(1)—O(1W)
O(1)—Ru(1)—O(1W)
O(2W)—Ru(1)—O(1W)
O(4)—Ru(1)—P(1)
O(1)—Ru(1)—P(1)
O(2W)—Ru(1)—P(1)
O(1W)—Ru(1)—P(1)
O(4)—Ru(1)—P(2)
O(1)—Ru(1)—P(2)
O(2W)—Ru(1)—P(2)
O(1W)—Ru(1)—P(2)
171.30(12)
86.77(13)
85.17(13)
86.34(14)
88.92(13)
79.10(13)
94.83(10)
89.04(9)
94.31(10)
173.25(10)
88.47(10)
98.74(10)
167.28(10)
88.84(10)
P(1)—Ru(1)—P(2)
C(1)—P(1)—C(17)
C(1)—P(1)—C(11)
C(17)—P(1)—C(11)
C(1)—P(1)—Ru(1)
C(17)—P(1)—Ru(1)
C(11)—P(1)—Ru(1)
C(6)—P(2)—C(23)
C(6)—P(2)—C(29)
C(23)—P(2)—C(29)
C(6)—P(2)—Ru(1)
C(23)—P(2)—Ru(1)
C(29)—P(2)—Ru(1)
O(3)—S(1)—O(2)
O(3)—S(1)—O(1)
O(2)—S(1)—O(1)
O(3)—S(1)—C(35)
O(2)—S(1)—C(35)
O(1)—S(1)—C(35)
O(5)—S(2)—O(6)
O(5)—S(2)—O(4)
O(6)—S(2)—O(4)
O(5)—S(2)—C(42)
O(6)—S(2)—C(42)
O(4)—S(2)—C(42)
S(1)—O(1)—Ru(1)
S(2)—O(4)—Ru(1)
111.8(2)
110.8(2)
107.0(2)
108.1(2)
104.2(2)
115.8(4)
109.5(3)
112.0(3)
108.4(3)
106.7(3)
103.6(2)
124.65(19)
126.9(2)
Tol
Attempts to introduce the second diphosphine molꢀ
ecule by replacing the tosylate anions or water failed.
Testing of compounds 1—3 as catalysts for copolymerizaꢀ
tion of ethylene and carbon monoxide did not show activꢀ
ity of these compounds. Apparently, this behavior can be
attributed to the occurrence of the fast equilibrium beꢀ
tween the κ1 and κ3 bonds of the tosylate anions in soluꢀ
tion (Scheme 2) (this fact has been demonstrated7 for
the Ru(PPh3)2(H2O)(CO)(OTs)2 complex), resulting in
strengthening of the Ru—OTs bond.
O(2)
S(1)
Ph
C(4) C(10)
O(1)
H(1WB)
C(9)
C(5)
O(3)
O(1W)
H(1WA)
P(2)
C(6)
C(3)
Os(1)
H(2WA)
Ru(1)
C(1)
Ph
C(8)
C(7)
O(2W)
H(2WB)
C(2)
P(1)
Scheme 2
Ph
O(5)
O(4)
Ph
S(2)
O(6)
Tol
Fig. 1. Overall view of complex 3. The phenyl and tolyl rings are
omitted.
The phosphorus atoms of diphosphine are in cis positions;
the P(1)—Ru(1)—P(2) angle is 97.84(5)°. There are two
H2O molecules in trans positions with respect to the phosꢀ
phorus atoms. Two tosylate anions are κ1ꢀcoordinated
to the ruthenium atom and occupy the apical posiꢀ
tions. Two oxygen atoms of the tosylate residues are
linked to the water molecules by hydrogen bonds (O...O,
2.698(5)—2.949(5) Å).
Experimental
All reactions were carried out under argon using the stanꢀ
dard Schlenk technique. The solvents were purified according to

Ruthenium bis(diphenylphosphino)metallocenes
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 4, April, 2006
685
H(2WA)
O(2W)
O(6)
O(5)
O(3)
S(1)
C(47)
H(2WB)
H(1WA)
O(2)
C(46)
C(42)
H(1WB)
P(1)
C(36)
C(37)
S(2)
O(1W)
C(45)
C(38)
C(35)
C(40)
O(4)
O(1)
Ru(1)
C(39)
C(44)
C(43)
C(41)
C(48)
P(2)
Fig. 2. Coordination polyhedron of the ruthenium atom in complex 3.
1
standard procedures. The H, 13C, and 31P NMR spectra were
0.27 g (60%). Found (%): C, 49.40; H, 4.14; Os, 16.09.
recorded on a Bruker AMXꢀ400 spectrometer; the chemical
shifts are given on the δ scale relative to Me4Si and 85% H3PO4
using CDCl3 as the solvent. The [Ru(H2O)6](OTs)2 compound
was prepared according to the aboveꢀdescribed procedure.8
1,1´ꢀBis(diphenylphosphino)ferrocenylrutheniumdiaquaꢀ
ditosylate (1). The [Ru(H2O)6](OTos)2 complex (0.35 g,
0.63 mmol) was added to a solution of 1,1´ꢀbis(diphenylꢀ
phosphino)ferrocene (0.34 g, 0.62 mmol) in THF (30 mL). The
resulting suspension was stirred at 20 °C for 20 h. The resulting
orangeꢀbrown solution was concentrated in vacuo to dryness.
The residue was extracted with benzene and filtered. The benꢀ
zene filtrate was concentrated to 3 mL and allowed to stand for
2 h for crystallization. The yellow precipitate that formed was
filtered off, washed with a minimum amount of benzene, and
dried in vacuo. The yield was 0.35 g (57%). Found (%): C, 55.49;
H, 4.85. C48H46FeO8P2RuS2. Calculated (%): C, 55.76; H, 4.48.
1H NMR, δ: 2.36 (s, 6 H, 2 Me, OTs); 4.18 and 4.26 (both s,
4 H each, Cp); 7.08 (d, 4 H, OTs, J = 2.0 Hz); 7.27 (m, 8 H, Hm,
Ph); 7.29 (d, 4 H, OTs, J = 2.0 Hz); 7.34 (m, 4 H, Hp, Ph); 7.57
(m, 8 H, Ho, Ph). 31P NMR, δ: 58.12 (s). 13C NMR, δ: 21.33 (s,
Me, OTs); 72.46 and 75.58 (both s, CH, Cp); 78.82 (t, C, Cp,
JC,P = 28.3 Hz); 125.83 (s, CH, OTs); 127.75 (t, mꢀCH, Ph,
JC,P = 4.8 Hz); 128.88 (s, CH, OTs); 129.84 (s, pꢀCH, Ph);
C
48H46O8OsP2RuS2. Calculated (%): C, 49.35; H, 3.97;
Os, 16.28. 1H NMR, δ: 2.36 (s, 6 H, 2 Me, OTs); 4.81 and 4.87
(both s, 4 H each, Cp); 7.08 (d, 4 H, OTs, J = 2.0 Hz); 7.22 (m,
8 H, Hm, Ph); 7.28 (d, 4 H, OTs, J = 2.0 Hz); 7.34 (m, 4 H, Hp,
Ph); 7.59 (m, 8 H, Ho, Ph). 31P NMR, δ: 58.13 (s). 13C NMR, δ:
21.33 (s, Me, OTs); 69.46 and 71.43 (both s, CH, Cp); 75.43 (t,
C, Cp, JC,P = 27.5 Hz); 125.85 (s, CH, OTs); 127.80 (t, mꢀCH,
Ph, JC,P = 4.4 Hz); 128.88 (s, CH, OTs); 129.96 (s, pꢀCH, Ph);
134.45 (t, oꢀCH, Ph, JC,P = 4.6 Hz); 135.10 (t, CP, JC,P
22.0 Hz); 139.42 and 141.85 (both s, C, OTs).
Xꢀray diffraction data for compound 3 (C48H46O8OsP2RuS2•
•H2O) were collected at 120 K on an automated threeꢀcircle
Smart CCD 1000K diffractometer (MoꢀKα radiation, graphite
=
monochromator, ωꢀscanning technique, 2θ
≤ 58°). Crystals
max
at 120 K are monoclinic, a = 12.130(2) Å, b = 22.073(4) Å,
c = 17.372(3) Å, β = 102.003(3)°, V = 4549.8(13) Å3, dcalc
1.732 g cm–3, M = 1186.19, F(000) = 2360, µ = 33.41 cm–1
=
,
Z = 4 (Z´ = 1), space group P21/n. Of a total of 49674 measured
reflections, 11906 independent reflections were used in calculaꢀ
tions and refinement. A semiempirical absorption correction
was applied based on equivalent reflections using the SADABS
program.9 The structure was solved by direct methods and reꢀ
fined anisotropically by the fullꢀmatrix leastꢀsquares method
against F 2hkl. Analysis of difference Fourier maps demonstrated
that the water solvate molecule is disordered over two posiꢀ
tions. The coordinates of the hydrogen atoms were calculated
geometrically, whereas the H atoms of the disordered water
molecule were not located. The final R factors were as folꢀ
lows: R = 0.0457 based on 8637 reflections with I > 2σ(I ),
wR2 = 0.0916, and GOF = 1.148 based on all reflections. All
calculations were carried out using the SHELXTL 5.10 program
package.10 The atomic coordinates were deposited with the Camꢀ
bridge Structural Database.
134.45 (t, oꢀCH, Ph, JC,P = 4.8 Hz); 135.32 (t, CP, JC,P
=
27.5 Hz); 139.50 and 141.82 (both s, C, OTs).
1,1´ꢀBis(diphenylphosphino)ruthenocenylrutheniumdiaquaꢀ
ditosylate (2) was prepared analogously to compound 1 from
1,1´ꢀbis(diphenylphosphino)ruthenocene (0.36 g, 0.60 mmol)
and [Ru(H2O)6](OTs)2 (0.33 g, 0.60 mmol). The yield was 0.23 g
(37%). Found (%): C, 52.95; H, 4.02. C48H46O8P2Ru2S2. Calꢀ
culated (%): C, 53.43; H, 4.30. 1H NMR, δ: 2.36 (s, 6 H, 2 Me,
OTs); 4.61 and 4.65 (both s, 4 H each, Cp); 7.08 (d, 4 H, OTs,
J = 2.0 Hz); 7.22 (m, 8 H, Hm, Ph); 7.29 (d, 4 H, OTs, J =
2.0 Hz); 7.34 (m, 4 H, Hp, Ph); 7.58 (m, 8 H, Ho, Ph). 31P NMR,
δ: 54.74 (s). 13C NMR, δ: 21.33 (s, Me, OTs); 75.73 and 77.87
(both s, CH, Cp); 82.56 (t, C, Cp, JC,P = 21.6 Hz); 125.84 (s,
CH, OTs); 127.75 (t, mꢀCH, Ph, JC,P = 4.6 Hz); 128.87 (s, CH,
References
OTs); 129.94 (s, pꢀCH, Ph); 134.39 (t, oꢀCH, Ph, JC,P
4.6 Hz); 134.97 (t, CP, JC,P = 20.6 Hz); 139.41 and 141.84
(both s, C, OTs).
1,1´ꢀBis(diphenylphosphino)osmocenylrutheniumdiaquadiꢀ
tosylate (3) was prepared analogously to compound 1 from
1,1´ꢀbis(diphenylphosphino)osmocene (0.28 g, 0.4 mmol)
and [Ru(H2O)6](OTs)2 (0.22 g, 0.40 mmol). The yield was
=
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Received February 15, 2006;
in revised form April 6, 2006