Synthesis and characterization of [(Cp*)Ru(PPh3)(N-base)]X and [(η5-C9H7)Ru(PPh3)(N-base)]X complexes (see abstract)

Article abstract of DOI:10.1016/S0277-5387(02)01335-9

The reactions of [(η⁵-Cp*)Ru(PPh₃)₂ (CH₃CN)]X (1) and [(η⁵-indenyl)Ru(PPh₃)₂ (CH₃CN)]X (2) (η⁵-Cp* = η⁵-C₅Me_5; η⁵- indenyl = η⁵-C₉H₇; X = BF₄ or PF₆) with 2,2′-bipyridine (bipy.) and 1,10-phenanthroline (phen.) in benzene or toluene yielded complexes of the type [(η⁵-Cp*)Ru(PPh₃)(L₂)]X where L₂ = bipy, X=BF₄ (3) and L₂=phen, X=PF₆ (4); [(η⁵-indenyl)Ru(PPh₃)₂(L₂)]X where L₂ = bipy, X = PF₆ (5) and L₂ = phen, X = PF₆ (6). Complex 6 has been established by single crystal X-ray diffraction analysis. Complex 6 crystallizes in the monoclinic space group P 21/c, with a = 14.6020 (12), b = 12.7100 (17) and c = 18.981 (2) A?, β = 98.982 (9)°, V = 3479.5 (7) A?³ and Z = 4. These complexes can also be prepared from reactions of [(η⁵- Cp*)Ru(PPh₃)₂Cl] (7) and [(η⁵-indenyl)Ru(PPh₃)₂Cl] (8) with the corresponding ligands in the presence of NH₄PF₆ or NH₄BF₄ in toluene. All the complexes were characterized by spectral and analytical data.

Full text of DOI:10.1016/S0277-5387(02)01335-9

Polyhedron 22 (2003) 307Á312
/
www.elsevier.com/locate/poly
Synthesis and characterization of [(Cpꢀ)Ru(PPh3)(N-base)]X and
[(h5-C9H7)Ru(PPh3)(N-base)]X complexes: crystal and molecular
structure of the complex [(h5-C9H7)Ru(PPh3)(phen)]PF6
(Cpꢀꢁ
/
C5Me5, indenylꢁ
/
C9H7; N-basesꢁ
/
bipy. and phen.; Xꢁ
/
BF4
or PF6)
Kollipara Mohan Rao ꢀ, Evergreen K. Rymmai
Department of Chemistry, North Eastern Hill University, Shillong 793 022, India
Received 8 July 2002; accepted 9 October 2002
Abstract
The reactions of [(h5-Cpꢀ)Ru(PPh3)2(CH3CN)]X (1) and [(h5-indenyl)Ru(PPh3)2(CH3CN)]X (2) (h5-Cpꢀꢁ
indenylꢁ BF4 or PF6) with 2,2?-bipyridine (bipy.) and 1,10-phenanthroline (phen.) in benzene or toluene yielded
h5-C9H7; Xꢁ
complexes of the type [(h5-Cpꢀ)Ru(PPh3)(L2)]X where L2ꢁ PF6 (4); [(h5-inde-
bipy, XꢁBF4 (3) and L2ꢁphen, Xꢁ
nyl)Ru(PPh3)2(L2)]X where L2ꢁbipy, XꢁPF6 (5) and L2ꢁphen, XꢁPF6 (6). Complex 6 has been established by single crystal
X-ray diffraction analysis. Complex 6 crystallizes in the monoclinic space group P 21/c, with aꢁ14.6020 (12), bꢁ12.7100 (17) and
/
h5-C5Me5; h5-
/
/
/
/
/
/
/
/
/
/
/
/
3
3479.5 (7) A and Zꢁ
4. These complexes can also be prepared from reactions of [(h5-
/
˚
˚
cꢁ
/
18.981 (2) A, bꢁ
/
98.982 (9)8, Vꢁ
/
Cpꢀ)Ru(PPh3)2Cl] (7) and [(h5-indenyl)Ru(PPh3)2Cl] (8) with the corresponding ligands in the presence of NH4PF6 or NH4BF4 in
toluene. All the complexes were characterized by spectral and analytical data.
# 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Pentamethylcyclopentadienyl; Indenyl; Ruthenium; Molecular structures; Bipyridine; Phenanthroline
1. Introduction
to electronic and steric factors in the case of the Cpꢀ
analogue and ring slippage nature from h5 to h3 and
back to h5 of the indenyl ligand [5]. In the literature
there are reports [6] of the reactions of [(h5-
Cp)Ru(PPh3)2X] with N-donor heterocyclic bases yield-
ing cationic and bridged complexes depending on the
halides coordinated to the ruthenium. Here we would
like to report the syntheses of [(Cpꢀ)Ru(PPh3)(N-
base)]X and [(h5-indenyl)Ru(PPh3)(N-base)]X com-
plexes from the reaction of acetonitrile complexes 1
and 2 with bipyridine and phenanthroline heterocyclic
bases and present their results.
The cyclopentadienyl bisphosphine ruthenium [(h5-
Cp)Ru(PPh3)2Cl] chemistry has been studied extensively
[1,2] with a variety of ligands. However, the correspond-
ing analogues of Cpꢀ and indenyl bisphosphine ruthe-
nium chemistry have not been studied extensively due to
lack of good synthetic procedures for preparation of the
starting complexes. Recently, Bruce et al. [3] published a
high yield synthesis of the Cpꢀ analogue [(h5-
Cpꢀ)Ru(PPh3)2Cl] by modifying the old procedures [4].
One can expect these complexes [(h5-Cpꢀ)Ru(PPh3)2Cl]
and [(h5-indenyl)Ru(PPh3)2Cl] to exhibit high reactivity
with comparison to the cyclopentadienyl analogue due
2. Experimental
The solvents were dried by standard methods. Infra-
ꢀ Corresponding author. Tel.: ꢂ
364-550076
E-mail address: kmrao@nehu.ac.in (K.M. Rao).
/
91-364-550041/551505; fax: ꢂ91-
/
red spectra were recorded as KBr pellets using a PerkinÁ
/
Elmer model 983, spectrophotometer. The 1H NMR
0277-5387/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 1 3 3 5 - 9

308
K.M. Rao, E.K. Rymmai / Polyhedron 22 (2003) 307Á312
/
spectra were recorded on a Bruker ACF 300 spectro-
meter and referenced to external tetramethylsilane
(TMS) and the coupling constants, J, are given in
Hertz. 31P {1H} NMR chemical shifts are reported
relative to H3PO4 (85%). Elemental analyses were
performed by the service center RSIC, NEHU, Shillong.
The complexes [(h5-Cpꢀ)Ru(PPh3)2Cl] [3] (7) and
[(h5-indenyl)Ru(PPh3)2Cl] [7] (8) were prepared by the
literature methods. Ruthenium trichloride trihydrate
was obtained from Arrora Matthey (P) Limited and
used as such.
1H NMR (CDCl3, d ppm): 6.8Á
9.5 (m, 23H, protons
of phenyl groups of triphenylphosphine and bipyridine),
/
1.3 (s, 15H, Cpꢀ). 31P NMR (CDCl3, d ppm): 49.6 (s,
PPh3), ꢃ
147 (septet, PF6ꢃ).
/
2.3.2. By the reaction of [(h5-Cpꢀ)Ru(PPh3)2Cl]
The complex [(h5-Cpꢀ)Ru(PPh3)2Cl] (0.1 g, 0.125
mmol) and 2,2?-bipyridine (0.03 g, 0.192 mmol) were
refluxed for 14 h in 20 ml toluene in the presence of
NH4BF4 (0.03 g, 0.28 mmol). The redÁbrown solution
/
was concentrated to about 5 ml and was then precipi-
tated out in hexane. The product was washed with Et2O
few times, alcohol (twice) and finally with ether. The
compound was recrystallized in acetone and hexane
mixture to yield orange crystals of the complex [(h5-
Cpꢀ)Ru(PPh3)(bipy)]BF4. Yield: 0.54 g, 57%.
2.1. Preparation of [(Cpꢀ)Ru(PPh3)2(CH3CN)]PF6
(1)
The complex [(CpꢀRu(PPh3)2Cl] (0.5 g, 0.277 mmol)
and NH4PF6 (0.15 g, 0.920 mmol) were refluxed in 20 ml
of MeCN for 5 h. The orange red suspension turned
yellow and a white precipitate appeared. The white
precipitate was filtered off and the yellow solution was
evaporated to dryness in a rotavapor. The yellow solid
was dissolved in CH2Cl2 (5 ml) and filtered to remove
excess of NH4PF6. It was then precipitated out in
hexane to give an orange yellow complex. The product
IR data (n cmꢃ1): 527m, 694s, 746m, 924m, 1023br,
1092br, 1299m, 1403m, 1435s, 1475m, 1500m, 1526m,
1551m, 1573m, 1581w, 1661m, 2915m.
1H NMR (CDCl3, d ppm): 6.8Á
9.5 (m, 23H, protons
/
of phenyl groups of triphenylphosphine and bipyridine),
1.3 (s, 15H, Cpꢀ). 31P NMR (CDCl3, d ppm): 49.6 (s,
PPh3).
was collected and washed. Yieldꢁ
1H NMR (CDCl3, d ppm): 1.3 (s, Cpꢀ, 15H), 2.1 (s,
3H), 6.8Á7.5 (m, 30H).
/83.89%.
2.4. Synthesis of [(h5-Cpꢀ)Ru(PPh3)(phen)]PF6 (4)
/
The complex [(h5-Cpꢀ)Ru(PPh3)2(CH3CN)]PF6 (0.1
g, 0.105 mmol) and 1,10-phenanthroline (0.025 g, 0.126
mmol) were refluxed in benzene (40 ml) (the complex
was initially dissolved in minimum amount of
2.2. Preparation of [(h5-
indenyl)Ru(PPh3)2(CH3CN)]PF6 (2)
CH2Cl2*/3 ml) for 1 h. The initially yellow solution
The same procedure was used in the preparation of
[(h5-indenyl)Ru(PPh3)2(CH3CN)]PF6 except the [(h5-
indenyl)Ru(PPh3)2Cl] complex was used instead of the
[(Cpꢀ)Ru(PPh3)2Cl] complex.
turned into a deep redÁ
/
purple color within 10 min. The
solution was evaporated to dryness and CH2Cl2 (5 ml)
was added to dissolve the product. The dissolved
compound was filtered into 50 ml of hexane to
precipitate out the product. The compound was ob-
tained by centrifuge and then washed with hexane and
Et2O. The compound was recrystallised in acetone and
hexane mixture to yield orange crystals of the complex
[(h5-Cpꢀ)Ru(PPh3)(phen)]PF6. Yield: 0.7 g, 78%.
IR data (n cmꢃ1): 510m, 526m, 698m, 720s, 753w,
779m, 804w, 848vs, 939w, 1028s, 1084m, 1123m, 1202m,
1285m, 1376m, 1405m, 1426m, 1441w, 1479m, 1633m,
2914w, 3435w.
1H NMR (CDCl3, d ppm): 2.1 (s, 3H), 4.2 (t, H
indenyl), 3.8 (d, 2H indenyl), 6.8Á
/
7.5 (m, 34H).
2.3. Synthesis of [(h5-Cpꢀ)Ru(PPh3)(bipy)]X, Xꢁ
PF6 or BF4 (3)
/
2.3.1. By the reaction of [h5-
Cpꢀ)Ru(PPh3)2(CH3CN)]PF6
The complex can be synthesized from the reaction of
[(h5-Cpꢀ)Ru(PPh3)2(CH3CN)]PF6 (0.1 g, 0.105 mmol)
with 2,2?-bipyridine (0.018 g, 0.115 mmol) in benzene
(45 ml) (the complex was initially dissolved in a
1H NMR (CDCl3, d ppm): 7.0Á
9.7 (m, 23H, protons
/
of phenyl groups of triphenylphosphine and phen.), 1.45
(s, 15H, Cpꢀ). 31P NMR (CDCl3, d ppm): 49.88 (s,
minimum amount of CH2Cl2*
/
3 ml) on refluxing for
PPh3), ꢃ
143 (septet, PF6ꢃ).
/
2 h. The yellow solution turned into a deep red color.
The solution was concentrated to about 5 ml and hexane
(40 ml) was added to precipitate out the product. The
red brown product was washed with hot hexane and
dried. Yield: 0.07 g, 82%.
IR data (n cmꢃ1): 527m, 694s, 746m, 924m, 1023br,
843s, 1299m, 1403m, 1435s, 1475m, 1500m, 1526m,
1551m, 1573m, 1581w, 1661m, 2915m.
2.5. Synthesis of [(h5-indenyl)Ru(PPh3)(bipy)]PF6
(5)
The complex [(h5-indenyl)Ru(PPh3)2(CH3CN)]PF6
(0.1 g, 0.108 mmol) and 2,2?-bipyridine (0.02 g, 0.128
mmol) in benzene (45 ml) (the complex was initially
dissolved in minimum amount of CH2Cl2*3 ml) were
/

K.M. Rao, E.K. Rymmai / Polyhedron 22 (2003) 307Á
/312
309
refluxed for 3 h. The yellow solution turned into a deep-
redÁbrown color within 10 min. Upon concentration of
the solution to about 5 ml, a brownÁred compound was
Table 1
Crystal data and experimental details for [(h5-C9H7)Ru(PPh3)-
(phen)]PF6
/
/
precipitated out. The product obtained was centrifuged
and washed with hot hexane and Et2O. The compound
was recrystallised in acetone and hexane mixture to yield
orange crystals of the complex [(h5-indenyl)Ru(PPh3)-
(bipy)]PF6. Yield: 0.74 g, 84%.
Empirical formula
Formula weight
Temperature (K)
C39H30F6N2P2Ru
803.66
293(2)
˚
Wavelength (A)
0.70930
monoclinic
P21/c
Crystal system
Space group
IR data (n cmꢃ1): 510m, 529m, 696m, 720m, 747m,
845s, 993w, 1029m, 1083m, 1119w, 1200m, 1285m,
1432m, 1441m, 1479m, 1633m, 2915m, 3050m.
˚
a (A)
14.6020(12)
12.7100(17)
18.981(2)
98.982(9)
3479.5(7)
4
˚
b (A)
˚
c (A)
1H NMR (CDCl3, d ppm): 7.0Á
9.6 (m, 27H, protons of
/
b (8)
Volume (A )
3
˚
phenyl groups of triphenylphosphine and bipy and
indenyl groups), 4.11 (d, 2H, indenyl), 5.3 (t, 1H indenyl).
Z
rcalc (Mg mꢃ3
)
1.534
0.606
31P NMR (CDCl3, d ppm): 66 (s, PPh3), ꢃ
138
/
Absorption coefficient (mmꢃ1
F(000)
Crystal size (mm)
)
(septet, PF6ꢃ).
1624
0.4ꢄ0.3ꢄ0.25
Data collection range (2u) (8) 1.41Á
/
24.91
2.6. Synthesis of [(h5-indenyl)Ru(PPh3)(phen)]PF6
(6)
Index ranges
05h 517, 05k 515,
ꢃ225l 522
Reflections collected/unique
Completeness to 2uꢁ24.91
Absorption correction
Max/min transmission
Refinement method
5374/5374 [Rintꢁ0.0000]
84.0%
Psi-scan
The complex was prepared by using the same
procedure except phenanthroline (0.025 g, 0.126 mmol)
was added instead of bipyridine. Yield: 0.78 g, 81%
IR data (n cmꢃ1): 513m, 529m, 592w, 696s, 720m,
745m, 843s, 996w, 1090s, 1184w, 1285w, 1412m, 1480m,
1501m, 1530w, 1625m, 1937m, 2849w, 2916w, 2945w,
3050w.
1.000 and 0.972
Full-matrix least-squares on F2
5374/0/571
Data/restraints/parameters
Final R indices [I ꢀ2s(I)]
R indices (all data)
Goodness-of-fit on F2
R1ꢁ0.0367, wR2ꢁ0.0944
R1ꢁ0.0484, wR2ꢁ0.1026
1.033
Largest difference peak and
ꢃ3
0.734 and ꢃ0.488.
1H NMR (CDCl3, d ppm): 7.0Á
8.6 (m, 27H, protons
/
˚
hole (e A
)
of phenyl groups of triphenylphosphine and phen. and
indenyl groups), 5.28 (d, 2H, indenyl), 5.7 (t, 1H
indenyl). 31P NMR (CDCl3, d ppm): 61 (s, PPh3),
The non-hydrogen atoms were refined anisotropically.
All the hydrogen atoms were geometrically fixed and
allowed to refine using a riding model. The final cycle of
full-matrix least-squares refinement, based on 5374
ꢃ
/
149 (septet, PF6ꢃ).
The complexes 3, 4, 5, and 6 can also be prepared
from the reactions of the corresponding chloro analo-
gues 7 and 8 with N-donor bases in presence of salts
observed reflections (I ꢀ
/
2s(I) and 571 variable para-
NH4BF4 or NH4PF6 in refluxing toluene for 12Á
/15 h.
meters, converged with Rꢁ
/
0.0367 and Rwꢁ0.0944. An
/
ORTEP drawing of 6 is shown in Fig. 1. Selected bond
distances and angles are given in Table 2.
3. Crystal structure determination of [(h5-
indenyl)Ru(PPh3)(phen)]PF6 (6)
4. Results and discussion
An orangeÁred crystal of suitable size of 6 was
/
mounted on the end of a glass fibre and mounted on a
The reaction of the chloro complexes [(h5-
Cpꢀ)Ru(PPh3)2Cl] and [(h5-indenyl)Ru(PPh3)2Cl] with
bipyridine and phenanthroline takes place by refluxing
in toluene for more than 12 h to yield cationic complexes
Nonius MACH3 diffractometer with graphite mono-
˚
0.70930 A) radiation for the
chromatized Mo Ka (lꢁ
/
cell determination and intensity data collection. The unit
cell parameters were derived and refined by using
of the type 3Á6, respectively. However, these reactions
/
randomly selected reflections in the u range 88Á118.
/
takes place in a more facile manner when acetonitrile
complexes of the type [(h5-indenyl)Ru(PPh3)2-
(CH3CN)]PF6 and [(h5-Cpꢀ)Ru(PPh3)2(CH3CN)]PF6
were used.
Crystal data collection parameters are summarized in
Table 1. All crystallographic calculations were per-
formed with the use of the MAXUS [8] software. The
structure was solved by direct methods [9] (SHELXS
1997). Lorentz and polarization corrections were ap-
plied. An empirical absorption correction was employed
by using psi-scan where the maximum and minimum
transmission factors were 1.000 and 0.972 respectively.
[(Ar)Ru(PPh3)2(CH3CN)]PF6 ꢂL2
ArꢁCpꢀ (1) and indenyl (2)
0
[(Ar)Ru(PPh3)(L2)]PF6
L2ꢁbipy or phen
toluene

310
K.M. Rao, E.K. Rymmai / Polyhedron 22 (2003) 307Á312
/
The interesting thing of these reactions are when the
reactions, viz [(h5-indenyl)Ru(PPh3)2Cl] and [(h5-
Cpꢀ)Ru(PPh3)2Cl] with bipyridine and phenanthroline,
were carried out in methanol or ethanol the organic
fragment, i.e. pentamethylcyclopentadienyl and indenyl,
comes out from the complex and forms simple N-base
substituted coordination complexes. A similar result was
observed in the case of [(h5-indenyl)Ru(PPh3)2Cl] re-
fluxed in methanol [7] at 85 8C, the complex decom-
posed and a mixture of ruthenium carbonyl complexes
were formed, which were not characterized. Whereas a
similar reaction carried out with the complex [(h5-
Cp)Ru(PPh3)2Cl] in ethanol yielded a complex of the
type [(h5-Cp)Ru(PPh3)L]X (Xꢁ
/
Clꢃ, PF6ꢃ) [10]. In
polar solvents like methanol, acetonitrile, etc. the [(h5-
Cp)Ru(PPh3)2Cl] complex readily dissociates and forms
a
solvated complex [11] of the type [h5-
Cp)Ru(PPh3)2(S)]ꢂ. A similar process is expected for
these complexes [(h5-Cpꢀ)Ru(PPh3)2Cl] (7) and [(h5-
indenyl)Ru(PPh3)2Cl] (8). However, the process of
Fig. 1. ORTEP view of the complex [(h5-C9H7)Ru(PPh3)(phen)]PF6
showing 30% probability thermal ellipsoids along with the atom
numbering scheme.
dissociation of the metalꢀ
/
chloride bond in complexes
7 and 8 seems to be slower as evidenced from the
reactions of these complexes with ligands in polar
solvents in which the metalꢀ
intact, instead the Cpꢀ or indenyl ligands break away.
Surprisingly, complexes 3Á6 are formed when the
/
chloride bond remains
/
Table 2
reactions are carried out in very less polar solvents.
All these complexes were isolated as orange red
crystals after recrystallization from acetone and hexane
mixture. The complexes are soluble in dichloromethane,
chloroform, etc. and insoluble in non-polar solvents like
hexane. The IR spectra of all these complexes exhibited
very strong bands due to phenyl groups of triphenylpho-
sphine and N bases, and PF6 exhibited a strong band for
nPF at 840 cmꢃ1. Proton NMR spectra of the Cpꢀ
complexes 3 and 4 exhibited a sharp resonance at
around d 1.4 ppm for methyl protons of Cpꢀ ligand.
In the case of indenyl complexes 5 and 6 a doublet and
triplet at around d 4.7 and 5.5 ppm approximately were
observed for the cyclopentadienyl ring protons of the
indenyl group indicating a downfield shift from the
starting complex, which is due to the cationic nature of
the complex. In the parent complex [(h5-inde-
nyl)Ru(PPh3)2Cl], these protons were observed at d
3.9 doublet and d 4.6 triplet, respectively. This indicates
that there is a downfield shift of these protons after
substituting one PPh3 with the N-donor heterocyclic
ligand. The proton NMR spectra of all the complexes
5
˚
Bond lengths (A) and angles (8) for [(h -C9H7)Ru(PPh3)(phen)]PF6
Bond lengths
Ru(1)ꢀN(1)
Ru(1)ꢀN(2)
Ru(1)ꢀC(8)
Ru(1)ꢀC(9)
Ru(1)ꢀC(7)
Ru(1)ꢀP(1)
Ru(1)ꢀC(1)
Ru(1)ꢀC(6)
P(1)ꢀC(22)
P(1)ꢀC(28)
P(1)ꢀC(34)
P(2)ꢀF(5)
2.104(3)
2.110(3)
2.160(4)
2.173(4)
2.186(4)
P(2)ꢀF(2)
1.579(5)
1.340(5)
1.366(5)
1.339(5)
1.355(5)
1.415(7)
1.439(6)
1.440(6)
1.358(8)
1.424(7)
1.346(6)
1.417(6)
1.450(6)
1.415(7)
1.415(8)
N(1)ꢀC(10)
N(1)ꢀC(14)
N(2)ꢀC(21)
N(2)ꢀC(15)
2.2875(11) C(1)ꢀC(2)
2.293(4)
2.301(4)
1.830(4)
1.833(4)
1.845(4)
1.470(5)
1.501(6)
1.526(5)
1.549(4)
1.572(4)
C(1)ꢀC(6)
C(1)ꢀC(9)
C(2)ꢀC(3)
C(3)ꢀC(4)
C(4)ꢀC(5)
C(5)ꢀC(6)
C(6)ꢀC(7)
C(7)ꢀC(8)
C(8)ꢀC(9)
P(2)ꢀF(4)
P(2)ꢀF(1)
P(2)ꢀF(3)
P(2)ꢀF(6)
Bond angles
N(1)ꢀRu(1)ꢀN(2)
N(1)ꢀRu(1)ꢀC(8)
N(2)ꢀRu(1)ꢀC(8)
N(1)ꢀRu(1)ꢀC(9)
N(2)ꢀRu(1)ꢀC(9)
C(8)ꢀRu(1)ꢀC(9)
N(1)ꢀRu(1)ꢀC(7)
N(2)ꢀRu(1)ꢀC(7)
C(8)ꢀRu(1)ꢀC(7)
C(9)ꢀRu(1)ꢀC(7)
N(1)ꢀRu(1)ꢀP(1)
N(2)ꢀRu(1)ꢀP(1)
C(8)ꢀRu(1)ꢀP(1)
C(9)ꢀRu(1)ꢀP(1)
77.46(12) C(7)ꢀRu(1)ꢀP(1)
140.84(18) N(1)ꢀRu(1)ꢀC(1)
141.18(18) N(2)ꢀRu(1)ꢀC(1)
105.17(17) C(8)ꢀRu(1)ꢀC(1)
156.17(15) C(9)ꢀRu(1)ꢀC(1)
110.02(12)
97.50(14)
118.96(14)
62.10(18)
37.50(16)
62.66(17)
146.38(11)
121.70(13)
95.50(13)
62.08(16)
62.59(16)
37.60(15)
147.62(10)
36.50(14)
38.1(2)
C(7)ꢀRu(1)ꢀC(1)
show a multiplet at d 7.0Á9.5 ppm due to the phenyl
/
158.85(15) P(1)ꢀRu(1)ꢀC(1)
104.85(15) N(1)ꢀRu(1)ꢀC(6)
38.00(18) N(2)ꢀRu(1)ꢀC(6)
64.24(19) C(8)ꢀRu(1)ꢀC(6)
C(9)ꢀRu(1)ꢀC(6)
C(7)ꢀRu(1)ꢀC(6)
91.56(14) P(1)ꢀRu(1)ꢀC(6)
108.91(13) C(1)ꢀRu(1)ꢀC(6)
protons of triphenylphosphine and heterocyclic N-
donor ligands. The 31P NMR spectra of complexes 3
and 4 exhibited a single sharp resonance for triphenyl-
phosphine at d 49 ppm in contrast to the starting
complex [(h5-Cpꢀ)Ru(PPh3)2Cl] at d 38.9 ppm. In the
case of the indenyl complexes, the 31P NMR spectra of
triphenylphosphine exhibited a single sharp resonance
90.52(9)
94.64(9)

K.M. Rao, E.K. Rymmai / Polyhedron 22 (2003) 307Á
/312
311
around d 66 and 61 ppm, complexes for 5 and 6,
respectively.
was displaced. Similar reactions carried out with the
complex [(h5-Cp)Ru(PPh3)2Cl] in alcohol yielded the
desired products [10].
4.1. The structure of [(h5-C9H7)Ru(PPh3)(phen)]PF6
The structure of complex 6 is shown in Fig. 1. The
bond lengths and bond angles are listed in Table 2. The
ruthenium atom is bonded to a phenanthroline ligand,
one triphenylphosphine ligand and to an indenyl group
through the five-member ring. The geometry about the
metal atom can be regarded as distorted octahedral if
the h5-indenyl group is assumed to occupy three facial
coordinated positions.
6. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 188452 for complex 6. Copies
of the information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge, CB2
1EZ, UK (fax: ꢂ44-1223-336033; e mail: deposit@
/
The indenyl group is clearly bonded in a pentahapto
fashion to the metal, and displays the asymmetric
coordination generally observed with this ligand [12].
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
Thus the three Ruꢀ
/
C bond lengths, those involving the
Acknowledgements
˚
C(7), C(8) and C(9) atoms (2.186, 2.160 and 2.173 A,
respectively) are shorter than the two to the bridging
K.M.R. thanks the DST (DST SERC: SP/S1/F-22/
98), New Delhi for financial support. We also thank the
Mobin and Professor P. Mathur for their help to solve
the molecular structure using the National Single
Crystal X-ray facility at IIT Bombay.
˚
C(1) and C(6) carbon atoms (2.293 and 2.301 A). The
former three RuꢀC bond lengths fall within the range of
individual RuꢀC distances (2.16Á
/
˚
2.20 A) found for
/
/
structures of cyclopentadienyl ruthenium complexes [13]
while the other two are outside this range. This
asymmetry has been explained as slipping of h5-bonded
coordination to h3-coordination. The five-member ring
is not a regular pentagon, as observed in other
complexes [14]. The benzene ring is planar, shows no
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