Cationic ruthenium(II) complexes containing a chelating η1:η6-phosphinoarene ligand; PPh3, PMe3, NCMe, NC5H5)

Article abstract of DOI:10.1016/S0022-328X(02)01591-7

Reactions of the ruthenium(II) complex [RuCl₂(PPh₂(CH₂)₃-η⁶ -C₆H₅)], containing a chelating η¹:η⁶-phosphinoarene ligand, with NH₄PF₆, in the presence of a variety of neutral two-electron donor ligands, have yielded a series of new cationic complexes of the general formula [RuCl(L)(PPh₂(CH₂)₃-η⁶-C ₆H₅)][PF₆] [L-P(OPh)₃ (1), P(OMe)₃ (2), PPh₃ (3), PMe₃ (4), NCMe (5), NC₅H₅ (6)]. The structures of complexes 3 and 5 have been determined by X-ray crystallography. In all cases ¹H- and ¹³C{¹H}-NMR spectra showed characteristic upfield chemical shifts indicative of the presence of a π-bound arene ligand. The η⁶-C₆H₅ group displayed five inequivalent resonances in the ¹H-NMR spectra, in most cases showing three triplets and two doublets (vicinal coupling, ³J_HH=6.4-5.4 Hz) of relative intensities 1:1:1:1:1 and six peaks were observed for the η6-C₆H₅ ligand in the respective ¹³C{¹H}-NMR spectra, consistent with C₁ molecular symmetry at the ruthenium centre in solution. Detailed assignment of the η⁶-arene resonances has been achieved using a collection of ¹H-¹H COSY and ¹H-¹³C correlation experiments, combined with a consideration of the relative magnetic anisotropic shielding and the trans influence effects attributed to the ligands L.

Full text of DOI:10.1016/S0022-328X(02)01591-7

Journal of Organometallic Chemistry 659 (2002) 1Á9
/
www.elsevier.com/locate/jorganchem
Cationic ruthenium(II) complexes containing a chelating h1:h6-
phosphinoarene ligand; [RuCl(L)(PPh2(CH2)3-h6-C6H5)][PF6] (Lꢀ
P(OPh)3, P(OMe)3, PPh3, PMe3, NCMe, NC5H5)
/
Paul D. Smith a,*, Thomas Gelbrich b, Michael B. Hursthouse b
a Department of Chemistry and Materials, Manchester Metropolitan University, Manchester M1 5GD, UK
b Department of Chemistry, EPSRC National Crystallography Service, University of Southampton, Highfield, Southampton SO17 1BJ, UK
Received 16 April 2002; received in revised form 16 May 2002; accepted 16 May 2002
Abstract
Reactions of the ruthenium(II) complex [RuCl2(PPh2(CH2)3-h6-C6H5)], containing a chelating h1:h6-phosphinoarene ligand, with
NH4PF6, in the presence of a variety of neutral two-electron donor ligands, have yielded a series of new cationic complexes of the
general formula [RuCl(L)(PPh2(CH2)3-h6-C6H5)][PF6] [Lꢀ
/
P(OPh)3 (1), P(OMe)3 (2), PPh3 (3), PMe3 (4), NCMe (5), NC5H5 (6)].
1
The structures of complexes 3 and 5 have been determined by X-ray crystallography. In all cases H- and 13C{1H}-NMR spectra
showed characteristic upfield chemical shifts indicative of the presence of a p-bound arene ligand. The h6-C6H5 group displayed five
1
3
inequivalent resonances in the H-NMR spectra, in most cases showing three triplets and two doublets (vicinal coupling, JHH
6.4Á
5.4 Hz) of relative intensities 1:1:1:1:1 and six peaks were observed for the h6-C6H5 ligand in the respective 13C{1H}-NMR
spectra, consistent with C1 molecular symmetry at the ruthenium centre in solution. Detailed assignment of the h6-arene resonances
ꢀ
/
/
1
1
has been achieved using a collection of HÁ1
/
H COSY and HÁ13
C correlation experiments, combined with a consideration of the
/
relative magnetic anisotropic shielding and the trans influence effects attributed to the ligands L. # 2002 Elsevier Science B.V. All
rights reserved.
Keywords: Arene; Chelating ligand; Phosphine; Ruthenium
1. Introduction
The varied array of areneÁ
known is largely due to the strong areneÃmetal bond,
in addition to the availability of reactive arene-contain-
ing compounds and the ready accessibility of both
Ru(II) and Ru(0) oxidation states [1]. AreneÁruthenium
complexes are important precursors for catalytic hydro-
genation reactions [2] and have established an increas-
ingly significant role in organic synthesis and
homogeneous catalysis [3]. One of the critical reactions
in catalytic cycles can involve the progressive removal of
the arene group from h6 to h4 and h2, however, the
complete disengagement of the arene may be an
unwanted side reaction. An obvious way of preventing
ring loss during reactions is to tether the arene moiety
on to another pendant donor atom and hence capitalise
on the chelate effect. Mirkin et al. have previously
reported tethered h6-areneÁ
eight-electron donor ligand Ph2PCH2CH2OPh [4] and in
/Rh(I) complexes using the
/
ruthenium complexes
/
recent years there have been a number of chelated h6-
areneÁ
/
Ru(II) complexes published in the literature [5Á
/
/
18]. These complexes have provided a challenge in both
the synthesis of new ligands and new methods for
preparing organometallics. Examples of tethered h6-
areneÁRu(II) complexes have now been prepared which
/
contain a h6-arene ring strapped to a variety of pendant
donor atoms such as, carbene [5], pyrazole [6], alcohol
[7], phosphine [8Á
pyrazoleÁphosphine groups [18]. Thermogravimetric
analysis and H-NMR spectroscopy have demonstrated
that Ru(II) complexes containing a chelating areneÁ
/15] thioether [16], arsine [17] and
/
1
/
phosphine ligand are significantly more stable towards
arene displacement than their non-chelating counter-
parts [10b]. This study has examined the effects of a
* Corresponding author. Fax: ꢁ
E-mail address: p.smith@mmu.ac.uk (P.D. Smith).
/
44-161-2476357
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 5 9 1 - 7

2
P.D. Smith et al. / Journal of Organometallic Chemistry 659 (2002) 1Á9
/
chelating phosphinoarene moiety since they provide a
rigid ligand framework by bonding to the metal in a
(h1:h6)
fashion
[8Á
/
15].
The
synthesis
of
[RuCl2(PPh2(CH2)3-h6-C6H5)], via a thermal arene-
substitution reaction, provided a convenient route to a
new chelated areneÁ
/
phosphineÁRu(II) complex [8].
/
Further work has now explored the reactions of this
complex with NH4PF6, in the presence of a variety of
neutral two-electron donor ligands using similar proce-
dures to those previously described in the literature [19].
These reactions have afforded a range of new chiral 18
electron Ru(II) ‘half-sandwich’ style cationic derivatives,
[RuCl(L)(PPh2(CH2)3-h6-C6H5)][PF6] [Lꢀ
/P(OPh)3 (1),
P(OMe)3 (2), PPh3 (3), PMe3 (4), NCMe (5), NC5H5
(6)], which contain a chelated h1:h6-phosphinoarene
ligand scaffold. A common characteristic of h6-areneÁ
ruthenium complexes of this type is various distortions
to the co-ordinated arene ring, arising from electronic
/
Fig. 1. ORTEP drawing of 3. Hydrogen atoms have been omitted for
chlarity.
effects [20Á22], which influence structural and spectro-
/
scopic properties. In all instances substantial upfield
1
chemical shifts are observed in the H- and 13C{1H}-
NMR spectra, which confirm the presence of a p-bound
arene ligand [23,24]. This paper describes the synthesis,
structures and NMR studies of complexes 1Á
NMR data has established the significance of these new
ruthenium complexes
/6. The
chelating h1:h6-phosphinoareneÁ
/
as excellent spectroscopic probes.
2. Results and discussion
2.1. Synthesis and characterisation
The mononuclear, cationic complexes 1Á/6 were iso-
lated as yellowÁorange, air-stable, high melting, non-
/
Fig. 2. ORTEP drawing of 5. Hydrogen atoms have been omitted for
chlarity.
hygroscopic, crystalline solids in good yield. All the
compounds demonstrated good solubility in acetone
and acetonitrile, but sparingly soluble in dichloro-
methane and chloroform, and insoluble in ether, hydro-
Table 1
˚
Selected bond lengths (A) and angles (8) for 3
1
carbons and alcohols. All H-, 13C{1H}- and 31P{1H}-
Bond lengths
NMR spectra were recorded in d6-acetone with the
[PF6]ꢂ counterion, in order to eliminate any potential
solvent or anion effects. The proposed formulas were
confirmed by microanalytical data. Complex 5 could be
Ru(1)ÃC(4)
Ru(1)ÃC(5)
Ru(1)ÃC(6)
Ru(1)ÃC(7)
Ru(1)ÃC(8)
2.243(3) Ru(1)ÃC(9)
2.225(3) Ru(1)ÃCl(1)
2.292(4) Ru(1)ÃP(1)
2.282(4) Ru(1)ÃP(2)
2.249(4) CÃC(arene)
2.258(3)
2.4000(8)
2.3307(9)
2.3718(9)
1.380(6)Á1.431(5)
/
readily identified by the appearance of a n(CÅ
/
N)
stretching vibration at 2298 cmꢂ1
.
Bond angles
P(1)ÃRu(1)ÃP(2) 97.04(3) P(2)ÃRu(1)ÃCl(1) 87.48(3)
P(1)ÃRu(1)ÃCl(1) 90.74(3)
2.2. Crystal structures
The molecular structures of complexes 3 and 5 have
been determined by single crystal X-ray analysis and are
shown with atom labelling in Figs. 1 and 2, respectively.
Selected bond distances and angles are listed in Tables 1
and 2. The ruthenium centres in both complexes can be
considered to possess pseudo-octahedral geometry, since
P(1) angles are all ca. 908, with the h6-C6H5 ligand
occupying three facial coordination sites. The Ru(1)Ã
Cl(1) distances in 3 and 5 are comparable to similar
complexes [25]. The Ru(1)ÃP(1) distances for 3 and 5
/
/
resemble those previously reported for related tethered
h1:h6-phosphinoarene complexes [8,9,11,13,14,18a]. The
the P(1)Ã
/
Ru(1)Ã
/
Cl(1), LÃ
/
Ru(1)Ã
/
Cl(1) and LÃ
/
Ru(1)Ã
/

P.D. Smith et al. / Journal of Organometallic Chemistry 659 (2002) 1Á
/9
3
Table 2
2.3. 1H-NMR studies
˚
Selected bond lengths (A) and angles (8) for 5
The spectrum for [RuCl2(PPh2(CH2)3-h6-C6H5)]
showed three well-separated peaks, one doublet at d
5.16 ppm and two triplets at d 5.77 and 6.39 ppm, of
relative intensities 2:2:1 due respectively to the ortho,
meta and para h6-C6H5 ring protons [8]. This assign-
ment may be interpreted on a first-order basis since
Hortho is strongly coupled only to Hmeta and consistent
with ideal Cs molecular symmetry at the metal centre in
solution. This produces a characteristic ‘2:2:1’ resonance
pattern for the h6-arene ligand, where a mirror plane,
the lone symmetry element, reflects the two ortho and
meta arene protons and is co-planar with the para
proton. The large chemical shift dispersion for the h6-
arene ring protons, 1.3 ppm, is unusual in that the
Bond lengths
Ru(1)ÃC(4)
Ru(1)ÃC(5)
Ru(1)ÃC(6)
Ru(1)ÃC(7)
Ru(1)ÃC(8)
2.206(3) Ru(1)ÃC(9)
2.183(3) Ru(1)ÃCl(1)
2.249(3) Ru(1)ÃP(1)
2.251(3) Ru(1)ÃN(1)
2.195(3) CÃC(arene)
2.196(3)
2.4319(7)
2.3218(9)
2.046(3)
1.387(5)Á1.428(5)
/
Bond angles
P(1)ÃRu(1)ÃN(1) 86.34(8) N(1)ÃRu(1)ÃCl(1) 87.81(7)
P(1)ÃRu(1)ÃCl(1) 86.35(3)
average RuÃ
/
C(arene) distances for 3 and 5 are 2.258(4)
shielding range commonly exhibited by areneÁ
/ruthe-
˚
and 2.213(3) A, respectively, which for 5 lie within the
range expected for h6-areneÁ
Ru(II) complexes [20].
However, the average Ru(1)ÃC(arene) distances observed
for 3 are notably longer than those anticipated for this
class of organometallics. Although, the complexed
aromatic rings in 3 and 5 are essentially planar there is
significant buckling of the h6-arene ligand where the
nium complexes is more often in the order of 0.3Á
/
0.6
/
ppm. For example the h6-arene protons of the closely
related (h6-C6H5CH3)RuCl2(PBun3); show a multiplet
between d 5.6 and 4.96 ppm [26]. However, other
complexes, which contain the h6-toluene ligand, have
/
displayed
a
similar
1H-NMR
signature
to
[RuCl2(PPh2(CH2)3-h6-C6H5)] where the h6-C6H5CH3
ring is subject to restricted rotation [22,25].
Ru(1)Ã
/
C(arene) distances trans to a P-donor are substan-
tially greater than those trans to the Ru(1)Ã
/
Cl(1) group.
The substantial upfield shifts of the metal bound
arene resonances relative to the free arene fragment arise
from a combination of the following effects: the with-
drawal of p-electron density from the aromatic ring by
the metal resulting in a quenching of the ring currents by
interaction with the metal, metal to arene p-interactions
causing an increase in the total electron density at the
aromatic ring and by the magnetic anisotropy of the rest
of the complex. Although, it is considered that these
explanations offer a rationale for the upfield shifts in
such complexes, a more precise description is not yet
available [27]. However, it is reasonable to expect that
the magnitude of the shielding for the h6-arene ligand
will correlate closely with the electron density on the
metal and the metal to arene p-interactions.
The asymmetric metal-ring bonding exhibited by these
complexes has been attributed to the trans bond
weakening properties of the tertiary phosphine [20].
The structural data obtained for 3, Table 1, has shown
that the h1:h6-phosphinoarene ligand exerts a greater
trans influence than PPh3, since the Ru(1)Ã
Ru(1)ÃC(7) distances are longer than the Ru(1)Ã
and Ru(1)ÃC(9) distances, which lie trans to the PPh3
ligand. This is consistent with the observed rutheniumÃ
phosphorous bond lengths, where the Ru(1)ÃP(1) dis-
tance, labelled for the h1:h6-phosphinoarene moiety, is
slightly shorter than the Ru(1)ÃP(2) bond assigned to
/
C(6) and
/
/
C(8)
/
/
/
/
the PPh3 ligand. The steric constraints of the bulky PPh3
group will hinder the approach of this ligand towards
1
The H-NMR spectrum for the h6-arene group in 1
the metal, and account for the longer Ru(1)Ã
distance relative to Ru(1)ÃP(1). A striking feature of
the crystal structure for 3 was the longer Ru(1)ÃC(arene)
distances compared to 5, see Tables 1 and 2, in
particular the Ru(1)ÃC(6) and Ru(1)ÃC(7) bonds,
where the free end of the arene was significantly lifted
from the ruthenium in 3. This can be attributed to
electronic factors and the steric influence of the PPh3
ligand. In both 3 and 5, the trigonal RuClPL fragment
adopts a staggered arrangement relative to the carbon
atoms of the aromatic ring. An examination of tri-
methylene straps in both complexes, showed co-planar-
ity of the benzylic carbon atom, C(3), with the carbon
atoms of the attached arene, without significant distor-
tion of bond lengths or angles in the tether.
/
P(2)
displayed a coupling pattern of three triplets and two
doublets of relative intensities 1:1:1:1:1 (vicinal cou-
/
/
3
pling, JHH
ꢀ
/
6.4Á5.4 Hz), see Table 3. Complex 1
/
possess C1 symmetry and as a result all five arene
proton environments on the h6-C6H5 group are unique.
/
/
1
From the HÁ1
/
H COSY spectrum it was possible to
confirm that the triplet at d 6.42 ppm was due to the
para ring proton H7, since it can be seen to be coupling
strongly to the other two triplet signals at d 6.11 and
6.02 ppm. The 2D-NMR experiment also showed the
doublet at d 5.84 ppm coupled to the triplet at d 6.02
ppm and the doublet at d 6.49 ppm coupled to the
triplet at d 6.11 ppm, giving the respective sets of ortho
and meta protons on adjacent sides of the h6-arene ring.
In an effort to further assign these peaks it was necessary

4
P.D. Smith et al. / Journal of Organometallic Chemistry 659 (2002) 1Á9
/
Table 3
Selected 1H-NMR data for complexes 1Á
6 (d ppm)
/
Complex
H5
H6
H7
H8
H9
1
2
3
4
5
6
5.84 (d)
5.57 (d)
3.96 (d)
6.27 (d)
5.59 (d)
5.97 (d)
6.20 (t)
6.42 (m)
5.98 (t)
6.50 (m)
6.70 (t)
6.17 (t)
6.42 (t)
6.82 (t)
6.92 (t)
6.66 (t)
6.64 (t)
6.64 (t)
6.11 (t)
6.62 (t)
6.66 (t)
5.96 (t)
6.06 (t)
6.41 (t)
6.49 (d)
6.42 (m)
6.18 (d)
6.50 (m)
5.86 (d)
5.51 (d)
to consider the influence of the P(OPh)3 ligand on the
h6-C6H5 ring. The ortho arene ring proton H9 is trans to
the P(OPh)3 ligand on the ruthenium and since the
phosphite will exert a trans influence due to its p-acid
character [20], the electron density at this ortho position
will be reduced. This will cause a decrease in the
shielding effect of the ruthenium atom at this site.
Consequently, one of the ortho protons is shielded
relative to its counterpart on the opposite side of the
arene ring and it is therefore proposed that the H9
proton appears as the furthest downfield doublet at d
6.49 ppm. The allocation of the remaining h6-arene
protons is then consistent with the assignments shown in
Table 3.
[RuCl(PPh3)(PPh2(CH2)2-h5-C5H4)] [28], showed an
unusual high-field resonance assignable to the h5-C5H4
group at d 2.29 ppm. The origin of this shift was
ascribed to the anisotropic shielding effect of the
aromatic ring current of a phenyl group in PPh3. These
effects are associated with the interaction of the cyclic
delocalisation of the aromatic p-electrons of the phenyl
groups in PPh3 and nuclei, which lie directly above or
below a phenyl ring and as a consequence are signifi-
cantly shielded. A similar high-field shift was observed
1
in the H-NMR spectrum of 3, showing a well-defined
doublet at d 3.96 ppm. The other spectra in this study
do not contain such high-field arene signals, which can
be assigned to the h6-C6H5 ligand and it would appear
that PPh3 is responsible for this unusual chemical shift.
By comparison with the cyclopentadienyl counterpart
[28], it is plausible that this signal is due to an analogous
shielding effect between one of the phenyl rings in PPh3
and the ortho H5 arene proton. Presumably, the tethered
arene must orientate about the [RuCl(PPh3)(PPh2-
(CH2)3)] tripodal set in solution to facilitate this type
of intramolecular interaction. Related non-chelated
complexes such as [(h6-C6H6)RuCl(PPh3)(PMePh2)]-
[PF6] [19c] fail to show analogous signals because of
The 1H-NMR spectrum recorded for complex 2
showed four resonances which could be attributed to
the h6-arene group in a coupling pattern of two triplets,
one multiplet and one doublet of relative intensities
1:1:2:1, respectively. The assignments given in Table 3
were verified using a HÁ1
1
/
H COSY experiment and the
multiplet centred at d 6.42 ppm was identified as
comprising of meta and ortho protons from opposite
sides of the h6-C6H5 ring and the triplet at d 6.82 ppm
was assigned to the para proton, H7. The H9 ortho
proton, which lies trans to the P(OMe)3 ligand, will
experience deshielding and as a consequence appear as a
downfield doublet. Hence, the multiplet at d 6.42 ppm
has been attributed to the overlap of the H6 and H9
protons.
the rapid rotation about the RuÃ/arene bond; such
rotation is of course not possible in these complexes.
The spectrum for 3 also displayed an unexpected low-
field resonance, showing a triplet at d 6.92 ppm. The
1HÁ1
H COSY spectrum was consistent with this signal
/
1
The most noteworthy characteristic of the H-NMR
arising from the H7 proton in the para position of the
co-ordinated arene ring. The 2D-NMR experiment also
showed the doublet at d 3.96 ppm coupled to the triplet
at d 5.98 ppm and the doublet at d 6.18 ppm coupled to
the triplet at d 6.66 ppm, giving the respective sets of
ortho and meta protons on adjacent sides of the h6-
arene ring. The appearance of the low-field triplets at d
6.92 and 6.66 ppm, assigned to H7 and H6 respectively,
spectrum exhibited by 3 was the remarkably large
chemical shift dispersion, 3 ppm, displayed by the h6-
arene ligand. Assignment of these resonances was again
1
achieved from the HÁ1
/
H COSY experiment, combined
with a consideration of the influence of the PPh3 ligand
1
on the arene protons (see Table 3). H-NMR studies of
the analogous tethered cyclopentadienyl derivative

P.D. Smith et al. / Journal of Organometallic Chemistry 659 (2002) 1Á
/9
5
presumably results from the lifting free end of the h6-
C6H5 ring away from the ruthenium, as shown in the
crystal structure of 3.
The 1H-NMR spectrum obtained for complex 4
displayed four resonances which could be attributed to
the h6-arene group in a coupling pattern of two triplets,
one multiplet and one doublet of relative intensities
steric constraints around the ruthenium centre. Thus the
magnitude of the trans deshielding influence displayed
by these phosphorus ligands on the H9 ortho proton
exhibits interplay between both electronic and steric
factors.
A distinctive feature of the 1H-NMR spectrum
recorded for 5 was the two adjacent triplets at d 6.70
and 6.64 ppm (Table 3). The HÁ1
1
1:1:2:1, respectively. The assignments shown in Table 3
were consistent with HÁ1
/
H COSY spectrum
1
/
H correlation data, where the
was consistent with the signal at d 6.64 ppm arising
from the para H7 proton. Further assignment of this
spectrum required consideration of the magnetic aniso-
tropic effects of the neighbouring groups in 5 and the
multiplet centred at d 6.50 ppm was identified as
comprising of an meta and ortho proton from opposite
sides of the h6-C6H5 ring and the triplet at d 6.67 ppm
was assigned to the para proton, H7. The H9 proton,
which is trans to the PMe3 ligand would be expected to
experience deshielding due to the trans influence of the
phosphine group, and appear as a downfield doublet.
Therefore, the multiplet at d 6.50 ppm can be ascribed
to the overlap of the meta H6 triplet and ortho H9
doublet.
shielding contributions attributed to the carbonÃ
/
nitro-
gen triple bond in the MeCN ligand has two distinct
susceptibilities, perpendicular and parallel to the bond
axis [31]. If a hydrogen atom lies in a region parallel to
the molecular axis it experiences deshielding and in a
perpendicular orientation it is shielded. In 5 the meta H6
proton of the h6-arene ring occupies a position where it
The trans influence exerted by the phosphine and
experiences deshielding from the carbonÃ/nitrogen triple
phosphite ligands in complexes 1Á/4 can be attributed to
bond and it is proposed that this shifts the triplet due to
this proton to low-field, producing the triplet at d 6.70
ppm. The assignment of remaining peaks in this
spectrum follows the labelling outlined in Table 3,
their p-acceptor interactions via backdonation from a
filled metal d-orbital on the Ru(II) centre to an empty
orbital on the phosphorus ligand. This empty phospho-
rus orbital has been described as being an antibonding
verified by a 1HÁ1
trans to the MeCN ligand appears at a high-field
chemical shift, d 5.86 ppm, compared to complexes 1Á
/
H COSY experiment. The H9 proton,
PÁ
on the phosphorus atom, the energy of the PÁ
orbital is lowered in energy, providing an increase in
backbonding ability. The phosphorus ligands in 1Á4 can
be placed in the following order of p-acidity, PMe3B
PPh3BP(OMe)3BP(OPh)3, where triphenylphosphite
/
R s orbital [29]. As electronegative groups are placed
/
R s*
/
4. This indicates that the trans influence exerted by
MeCN was weak compared to the P-donor ligands,
which matches the crystal structure data, where the
/
/
/
/
Ru(1)Ã
/
C(9) distance in 5 was shorter relative to 3 (see
has the greatest p-acceptor capability. Hence, it might
be expected that complex 1 would show the most
pronounced trans influence and exhibit the furthest
Tables 1 and 2).
The spectrum for the metal-bound arene group in 6
displayed five well-separated signals between d 6.64 and
5.51 ppm and the allocation of these resonances is
downfield doublet in the 1H-NMR spectra of 1Á
4.
/
1
Indeed the H-NMR spectrum of 1 shows a downfield
shown in Table 3. These assignments are consistent with
the HÁ1
doublet at d 6.49 ppm for the h6-arene group, which has
been assigned to the H9 ortho proton. The H-NMR
/
H COSY spectrum and the anisotropic shield-
ing effect attributed to the aromatic ring current in the
1
1
spectra of complexes 2 and 4 both display downfield
mutiplets at d 6.42 and 6.50 ppm respectively, which
have been attributed to the overlap of the H9 and H6
resonances. Whilst for 3 the H9 proton appears as a
doublet at d 6.18 ppm. From this data it does not
appear that there is any obvious correlation between the
p-acidity of the phosphorus ligand and the deshielding
of the H9 ortho proton in the h6-C6H5 ring. However,
besides the electronic attributes of the phosphorus
ligands, steric effects will also influence the degree of
pyridine ligand. The 1HÁ1
/
H correlation data showed
that the triplet at d 6.17 ppm and the doublet at d 5.97
ppm corresponded to a pair of adjacent meta and ortho
protons on the same side of the h6-arene ring. These two
proton signals are displaying contrasting shielding
effects compared to their counterparts on the opposite
side of the h6-C6H5 ligand. It is proposed that the
aromatic ring current of the pyridine ligand would exert
an intramolecular shielding affect upon the meta H6
proton, where this nuclei lies in a region above the plane
of the NC5H5 ring.
metal d to PÁR s* p overlap. Whereby the additional
/
steric constraints of the larger ligands will hinder their
approach towards the metal and limit the extent of p-
backbonding. PPh3 has the largest cone angle of the four
phosphorus ligands used [30], which coincides with an
One additional aspect of the 1H-NMR spectra for 1Á
6
/
that merits comment is the resonances assigned to the
methylene protons in the chelating link. In most cases
three independent multiplets were observed in the range
1
upfield H9 doublet in the H-NMR spectrum of 3 (see
Table 3). PPh3 is not the weakest p-acid in this series, yet
it appears to exert the poorest trans influence, due to the
d 3.13Á1.97 ppm, where the furthest downfield signals is
/
allocated to the methylene group directly linked to the
h6-C6H5 ring, while the adjacent slightly further upfield

6
P.D. Smith et al. / Journal of Organometallic Chemistry 659 (2002) 1Á9
/
multiplet has been assigned the methylene groups
attached to the phosphine. This assignment is consistent
with related complexes, which contain a chelating h1:h6-
phosphinoarene ligand [8,13,14]. The presence of dia-
stereotopic methylene protons in these complexes is in
agreement with C1 symmetry at the ruthenium centre
yielding a racemic chiral complex.
3. Conclusions
In summary, the exchange of
a chloride in
[RuCl2(PPh2(CH2)3-h6-C6H5)], for the ligands L lowers
1
the point symmetry at the ruthenium to C1 and the H-
and 13C-NMR spectra, in most cases, displayed a set of
five and six signals assigned to the h6-arene ring,
respectively. The comparative chemical shifts of the
1H- and 13C-NMR resonances for complexes 1Á
6, have
/
demonstrated a high degree of sensitivity towards the
chemical nature of the incoming ligands, L. Where
ligands which are strong p-acids exhibit a significant
trans influence on the h6-C6H5 ring across the complex
due to their ability to withdraw metal dp-electrons. The
magnetic anisotropic shielding attributed to the indivi-
dual ligands also has an important effect on the
chemical shifts of the co-ordinated arene nuclei.
2.4. 13C{1H}-NMR studies
For complexes 1Á
the h6-C6H5 ligand in the 13C{1H}-NMR spectra within
the shielding range d 106Á79 ppm, confirming the C1
/6 six resonances were observed for
/
molecular symmetry of these cations in solution. Table 4
highlights the assignments given to these 13C resonances,
which have been verified using 1HÁ13
C correlation
/
experiments. In the cases of 2 and 4, a complete
allocation of all the 13C peaks was not possible, due to
the overlap of some h6-arene peaks in the 1H-NMR
spectra (Table 3). The ipso carbons, C4, of the h6-C6H5
4. Experimental
4.1. General
ring for these complexes lied within the range d 103Á88
/
ppm. It is worth noting the 13C spectra obtained for the
h6-C6H5 ring in 3, see Table 4, where the three down-
field resonances at d 100.98, 99.39 and 99.29 ppm, have
been assigned to the para C7 carbon and the meta C6
and C8 carbons respectively. This data is consistent the
All syntheses were carried out under a dry nitrogen
atmosphere using conventional Schlenk techniques.
Reagents and solvents were obtained from normal
commercial sources and were used without further
purification unless otherwise stated. Diethyl ether was
distilled from sodium, MeCN from CaH2, and MeOH
from magnesium turnings with iodine, all were stored
under nitrogen. [RuCl2(PPh2(CH2)3-h6-C6H5)] was pre-
pared by methods previously described in the literature
[8]. Elemental analysis where performed by the Micro
Analytical Laboratory, Department of Chemistry, The
University of Manchester. All NMR spectra were
recorded on a JEOL GSX Delta 270 MHz machine at
ambient temperature and the 31P{1H}-NMR spectra
were referenced to H3PO4.
long RuÃ
particular for RuÃ
/
C(arene) distances shown in the structure of 3, in
/
C6 and RuÃC7, where the free end of
/
the arene is significantly lifted from the ruthenium.
Three methylene resonances arising from the alkyl
chelating link in the h1:h6-phosphinoarene ligand are
observed in the range d 30.7Á
/
19.02 ppm. The carbon
bound directly to the phosphine can be easily identified
as a well-defined doublet in the region d 24.84Á22.81
/
ppm (1JPC
ꢀ
/
34.7Á29.7 Hz).
/
Table 4
Selected 1C-NMR data for complexes 1Á
6 (d ppm)
/
Complex
C4
C5
C6
94.08
C7
C8
C9
1
2
3
4
5
6
103.44
99.11
96.27
95.5
88.8
101.1
101.28
101.64
99.29
106.08
104.41/97.76
97.97
86.93
92.18
99.85
85.07
79.77
104.41/97.76
99.39
102.62
100.98
99.36
101.25/98.67
99.93
92.75
85.21
91.34
103.02
101.25/98.67
83.71
85.85
97.96
99.13
101.07
98.06

P.D. Smith et al. / Journal of Organometallic Chemistry 659 (2002) 1Á
/9
7
4.2. Synthesis of [RuCl(P(OPh)3)(PPh2(CH2)3-h6-
C6H5)][PF6] (1)
130.39, 130.31, 127.74, 127.57 (Ph), 104.41 (ortho or
meta h6-C6H5), 102.62 (para h6-C6H5), 101.64 (meta
h6-C6H5), 99.11 (ipso h6-C6H5), 97.76 (ortho or meta
A mixture of [RuCl2(PPh2(CH2)3-h6-C6H5)] (100 mg,
0.21 mmol) and P(OPh)3 (130 mg, 0.42 mmol) in the
presence of NH4PF6 (68.4 mg, 0.42 mmol) in MeOH (20
ml) was refluxed for 1 h. The yellow solution was
allowed to cool to room temperature (r.t.), filtered,
concentrated under reduced pressure (5 ml) and Et2O
(50 ml) added giving a yellow microcrystalline solid,
which was collected. This product was further purified
h6-C6H5), 86.93 (ortho h6-C6H5), 54.31 (d, JPC
ꢀ8.8
/
2
Hz, P(OMe)3), 30.45 (Ph2PCH2CH2CH2-h6-C6H5),
ꢀ
34.7 Hz, Ph2PCH2CH2CH2-h6-C6H5),
/
1
22.87, (d, JPC
18.60 (Ph2PCH2CH2CH2-h6-C6H5). 31P{1H}-NMR
2
(109 MHz, CD3COCD3, 298 K): d 121.58 (d, JPP
ꢀ
/
2
86.3 Hz, P(OMe)3), 27.36 (d, JPP
ꢀ86.4 Hz,
/
Ph2P(CH2)3-h6-C6H5), ꢂ
/143.81 (sept, PF6).
by recrystallisation from a CH2Cl2Á/EtOH solvent
4.4. Synthesis of [RuCl(PPh3)(PPh2(CH2)3-h6-
C6H5)][PF6] (3)
mixture via slow evaporation and the yellow crystals
were filtered from the mother liquor, washed with EtOH
(2ꢃ
/
5 ml) then dried under vacuum. Yield: 123 mg,
This compound was prepared as for 1 from
65%. Anal. Calc. for C39H36ClF6O3P3Ru: C, 52.27; H,
1
4.05. Found: C, 52.92; H, 4.06%. H-NMR (270 MHz,
[RuCl2(PPh2(CH2)3-h6-C6H5)] (100 mg, 0.21 mmol),
P(Ph)3 (110 mg, 0.42 mmol) and NH4PF6 (68.4 mg,
0.42 mmol) in MeOH (20 ml). Yield: 107 mg, 55%. Anal.
Calc. for C39H36ClF6P3Ru: C, 55.23; H, 4.28. Found: C,
CD3COCD3, 298 K): d 7.89Á
/
7.81 (m, 4H, Ph), 7.58Á
/
7.51 (m, 5H, Ph), 7.28Á7.01 (m, 16H, Ph), 6.49 (d,
/
3JHH
ꢀ
/
6.4 Hz, 1H, ortho h6-C6H5), 6.42 (t, JHH
ꢀ
/
6.0
6.2 Hz, 1H,
55.28; H, 4.32%. 1H-NMR (270 MHz, CD3COCD3, 298
3
Hz, 1H, para h6-C6H5), 6.11 (t, JHH
ꢀ
/
K): d 7.93Á
/
ꢀ6.2 Hz,
/
3
3
6.97 (m, 25H, Ph), 6.92 (t, JHH
meta h6-C6H5), 6.02 (t, JHH
ꢀ
/
6.0 Hz, 1H, meta h6-
1H, para h6-C6H5), 6.66 (t, 3JHH
ꢀ
6.4 Hz, 1H, meta h6-
/
3
C6H5), 5.84 (d, 3JHH
(m, 2H, Ph2PCH2CH2CH2-h6-C6H5), 2.77 (m, 2H,
2.23 (m, 2H,
ꢀ
/
5.4 Hz, 1H, ortho h6-C6H5), 2.95
C6H5), 6.18 (d, 3JHH
ꢀ
/
6.4 Hz, 1H, ortho h6-C6H5), 5.98
3
3
(t, JHH
ꢀ
/
6.0 Hz, 1H, meta h6-C6H5), 3.96 (d, JHH
ꢀ
/
Ph2PCH2CH2CH2-h6-C6H5),
5.7 Hz, 1H, ortho h6-C6H5), 3.07 (m, 2H, Ph2PCH2-
CH2CH2-h6-C6H5), 2.34 (m, 4H, Ph2PCH2CH2CH2-h6-
C6H5, Ph2PCH2CH2CH2-h6-C6H5). 13C{1H}-NMR (68
MHz, CD3COCD3, 298 K): d 135.13, 135.03, 134.90,
134.71, 134.57, 134.44, 134.09, 133.97, 131.83, 131.52,
131.38, 129.52, 129.37, 129.18, 129.03 (Ph), 100.98 (para
h6-C6H5), 99.39 (meta h6-C6H5), 99.29 (meta h6-C6H5),
97.97 (ortho h6-C6H5), 96.27 (ipso h6-C6H5), 92.18
Ph2PCH2CH2CH2-h6-C6H5). 13C{1H}-NMR (68 MHz,
CD3COCD3, 298 K): d 152.03, 151.83, 135.37, 134.95,
134.81, 132.33, 130.47, 129.67, 129.59, 129.52, 128.66,
128.51, 126.48, 122.08, 122.02 (Ph), 106.08 (ortho h6-
C6H5), 103.04 (ipso h6-C6H5), 101.28 (meta h6-C6H5),
101.10 (para h6-C6H5), 94.08 (meta h6-C6H5), 88.80
(ortho h6-C6H5), 29.51 (Ph2PCH2CH2CH2-h6-C6H5),
1
24.62 (d, JPC
ꢀ
/
33.7 Hz, Ph2PCH2CH2CH2-h6-C6H5),
(ortho h6-C6H5), 30.17 (Ph2PCH2CH2CH2-h6-C6H5),
19.67 (Ph2PCH2CH2CH2-h6-C6H5). 31P{1H}-NMR
ꢀ
32.2 Hz, Ph2PCH2CH2CH2-h6-C6H5),
/
1
24.84 (d, JPC
2
(109 MHz, CD3COCD3, 298 K): d 114.46 (d, JPP
ꢀ
/
19.50 (Ph2PCH2CH2CH2-h6-C6H5). 31P{1H}-NMR
58.9 Hz, P(OPh)3), 28.35 (d, 2JPP
Ph2P(CH2)3-h6-C6H5), ꢂ
143.67 (sept, PF6).
ꢀ/58.9 Hz,
ꢀ
/
2
(109 MHz, CD3COCD3, 298 K): d 22.92 (d, JPP
2
/
51.1Hz, Ph2P(CH2)3-h6-C6H5), 17.49 (d, JPP
ꢀ51.3
/
Hz, PPh3), ꢂ143.59 (sept, PF6).
/
4.3. Synthesis of [RuCl(P(OMe)3)(PPh2(CH2)3-h6-
C6H5)][PF6] (2)
4.5. Synthesis of [RuCl(PMe3)(PPh2(CH2)3-h6-
C6H5)][PF6] (4)
This compound was prepared as for
1 from
[RuCl2(PPh2(CH2)3-h6-C6H5)] (100 mg, 0.21 mmol),
P(OMe)3 (52.1 mg, 0.42 mmol) and NH4PF6 (68.4 mg,
0.42 mmol) in MeOH (20 ml). Yield: 116 mg, 78%. Anal.
Calc. for C24H30ClF6O3P3Ru: C, 40.6; H, 4.26. Found:
This compound was prepared as for 1 from
[RuCl2(PPh2(CH2)3-h6-C6H5)] (100 mg, 0.21 mmol),
PMe3 (32 mg, 0.42 mmol) and NH4PF6 (68.4 mg, 0.42
mmol) in MeOH (20 ml). Yield: 86 mg, 62%. Anal. Calc.
for C24H30ClF6P3Ru: C, 43.54; H, 4.57. Found: C,
43.25; H, 4.65%. 1H-NMR (270 MHz, CD3COCD3, 298
1
C, 40.49; H, 4.2%. H-NMR (270 MHz, CD3COCD3,
298 K): d 7.79Á
/
7.71 (m, 2H, Ph), 7.63Á7.43 (m, 8H, Ph),
/
3
6.82 (t, JHH
ꢀ
/
6.1 Hz, 1H, para h6-C6H5), 6.62 (t,
K): d 7.97Á
/
7.90 (m, 2H, Ph), 7.72Á7.39 (m, 8H, Ph),
/
3JHH
ꢀ
/
6.0 Hz, 1H, meta h6-C6H5), 6.42 (m, 2H, ortho
6.67 (t, 3JHH
ꢀ
6.0 Hz, 1H, para h6-C6H5), 6.50 (m, 2H,
3
/
/
and meta h6-C6H5), 5.57 (d, JHH
ꢀ
/
5.9 Hz, 1H, ortho
10.5 Hz, 9H, P(OMe)3), 2.87
ortho and meta h6-C6H5), 6.27 (d, JHH
ꢀ
5.7 Hz, 1H,
3
h6-C6H5), 3.61 (d, JPH
ꢀ
/
ortho h6-C6H5), 5.69 (t, JHH
ꢀ
6.0 Hz, 1H, meta h6-
/
3
3
(m, 2H, Ph2PCH2CH2CH2-h6-C6H5), 2.46 (m, 2H,
Ph2PCH2CH2CH2-h6-C6H5), 2.05 (m, 2H, Ph2PCH2-
C6H5), 3.13 (m, 2H, Ph2PCH2CH2CH2-h6-C6H5), 2.31
(m, 2H, Ph2PCH2CH2CH2-h6-C6H5), 1.97 (m, 2H,
CH2CH2-h6-C6H5).
CD3COCD3, 298 K): d 134.06, 133.92, 133.06, 132.93,
13C{1H}-NMR
(68
MHz,
Ph2PCH2CH2CH2-h6-C6H5), 1.34 (d, JPH
ꢀ10.9 Hz,
/
2
9H, PMe3). 13C{1H}-NMR (68 MHz, CD3COCD3, 298

8
P.D. Smith et al. / Journal of Organometallic Chemistry 659 (2002) 1Á9
/
K): d 135.11, 134.96, 134.04, 133.88, 131.95, 129.77,
129.62, 129.49, 129.34 (Ph), 101.25 (ortho or meta h6-
C6H5), 99.85 (ortho h6-C6H5), 99.36 (para h6-C6H5),
98.67 (ortho or meta h6-C6H5), 95.5 (ipso h6-C6H5),
Table 5
Crystal and structure refinement data for complexes 3 and 5
Complex
3
5
85.21 (meta h6-C6H5), 29.16 (Ph2PCH2CH2CH2-h6-
Empirical formula
Formula weight
Temperature (K)
C39H36ClF6P3Ru C23H24ClF6NP2Ru
848.11
150(2)
1
C6H5), 23.82 (d, JPC
626.89
150(2)
ꢀ33.7 Hz, Ph2PCH2CH2CH2-
/
h6-C6H5), 19.79 (Ph2PCH2CH2CH2-h6-C6H5), 18.73 (d,
˚
Wavelength (A)
0.71073
Monoclinic
P21/c
0.71073
Monoclinic
P21/c
1JPC
CD3COCD3, 298 K): d 21.48 (d, JPP
ꢀ
/
34.7 Hz, PMe3). 31P{1H}-NMR (109 MHz,
Crystal system
Space group
Unit cell dimensions
2
ꢀ63.7 Hz
/
Ph2P(CH2)3-h6-C6H5, 3.46 (d, JPP
ꢀ62.1 Hz, PMe3),
/
2
˚
a (A)
9.45570(10)
20.0501(3)
18.4173(3)
90
7.78080(10)
21.7979(4)
14.2215(3)
90
ꢂ
/
143.92 (sept, PF6).
˚
b (A)
˚
c (A)
4.6. Synthesis of [RuCl(NCMe)(PPh2(CH2)3-h6-
C6H5)][PF6] (5)
a (8)
b (8)
g (8)
91.9066(8)
90
90.4530(6)
90
3
˚
V (A )
Z
3489.76(9)
4
1.614
2411.96(7)
4
1.726
This compound was prepared as for
1 from
[RuCl2(PPh2(CH2)3-h6-C6H5)] (100 mg, 0.21 mmol)
and NH4PF6 (68.4 mg, 0.42 mmol) in MeCN (20 ml).
Orange block-like crystals were obtained from a
Dcalc (mg mꢂ3
)
Absorption coefficient
0.725
0.953
(mmꢂ1
F(000)
Crystal
)
1720
Block, orange
1256
Block, orange
MeCNÁEt2O solvent mixture via slow vapour diffusion.
/
Yield: 112 mg, 74%. Anal. Calc. for C23H24ClF6NP2Ru:
C, 44.06; H, 3.86; N, 2.23. Found: C, 43.87; H, 3.87; N,
Crystal size (mm3)
u Range for data
collection (8)
0.15ꢃ0.12ꢃ0.07 0.10ꢃ0.07ꢃ0.07
2.96Á26.00 3.01Á26.00
/
/
1
2.2%. IR (KBr): 2298 cmꢂ1 [n(NCMe)]. H-NMR (270
MHz, CD3COCD3, 298 K): d 7.78Á
/
7.49 (m, 10H, Ph),
6 Hz, 1H, meta h6-C6H5), 6.64 (t,
Reflections collected
14 142
15 886
4730 [Rintꢀ0.0410]
3
6.70 (t, JHH
Independent reflections 6800
[Rintꢀ0.0317]
99.0%
ꢀ
/
3JHH
ꢀ
/
6.2 Hz, 1H, para h6-C6H5), 6.06 (t, JHH
ꢀ6.0
/
3
Completeness to
99.3%
Hz, 1H, meta h6-C6H5), 5.86 (d, JHH
ꢀ5.8 Hz, 1H,
/
3
uꢀ26.008
Max/min transmission 0.9510 and 0.8990 0.9363 and 0.9107
ortho h6-C6H5), 5.59 (d, JHH
ꢀ
5.8 Hz, 1H, ortho h6-
/
3
C6H5), 3.06 (m, 2H, Ph2PCH2CH2CH2-h6-C6H5), 2.66
(m, 2H, Ph2PCH2CH2CH2-h6-C6H5), 2.47 (m, 2H,
Ph2PCH2CH2CH2-h6-C6H5); 2.25 (s, 3H, NCMe).
13C{1H}-NMR (68 MHz, CD3COCD3, 298 K): d
135.76, 133.66, 132.27, 131.58, 129.49, 128.93 (Ph),
126.95 (NCMe), 101.07 (para h6-C6H5), 99.93 (meta
h6-C6H5), 97.96 (ipso h6-C6H5), 91.34 (meta h6-C6H5),
Refinement method
Full-matrix least- Full-matrix least-
squares on F2
6800/7/515
squares on F2
4703/0/332
Data/restraints/
parameters
Final R indices
[F2ꢀ2s(F2)]
R indices (all data)
R1ꢀ0.0418,
wR2ꢀ0.0896
R1ꢀ0.0491,
wR2ꢀ0.0927
1.019
R1ꢀ0.0340,
wR2ꢀ0.0748
R1ꢀ0.0428,
wR2ꢀ0.0775
1.024
Goodness-of-fit on F2
85.07 (ortho h6-C6H5), 83.71 (ortho h6-C6H5), 30.42
Largest difference peak 1.637 and ꢂ1.589 1.230 and ꢂ0.674
(Ph2PCH2CH2CH2-h6-C6H5), 23.59 (d, JPC
ꢀ34.4 Hz,
/
1
ꢂ3
˚
and hole (e A
)
Ph2PCH2CH2CH2-h6-C6H5), 21.05 (Ph2PCH2CH2-
CH2-h6-C6H5); 3.32 (NCMe). 31P{1H}-NMR (109
MHz, CD3COCD3, 298 K): d 28.85 (s, Ph2P(CH2)3-
3
6.41 (t, JHH
ꢀ
/
6.2 Hz, 1H, meta h6-C6H5), 6.17 (t,
h6-C6H5), ꢂ
/
141.56 (sept, PF6).
3JHH
ꢀ
/
6.0 Hz, 1H, meta h6-C6H5), 5.97 (d, JHH
ꢀ5.9
/
3
Hz, 1H, ortho h6-C6H5), 5.51 (d, JHH
ꢀ5.8 Hz, 1H,
/
3
4.7. Synthesis of [RuCl(NC5H5)(PPh2(CH2)3-h6-
C6H5)][PF6] (6)
ortho h6-C6H5), 2.95 (m, 2H, Ph2PCH2CH2CH2-h6-
C6H5), 2.64 (m, 2H, Ph2PCH2CH2CH2-h6-C6H5), 2.03
(m, 2H, Ph2PCH2CH2CH2-h6-C6H5). 13C{1H}-NMR
(68 MHz, CD3COCD3, 298 K): d 156.78 (NC5H5),
139.23 (NC5H5), 135.78, 132.91, 131.98, 131.01, 129.36,
128.67 (Ph), 126.14 (NC5H5), 103.02 (meta h6-C6H5),
99.13 (ipso h6-C6H5), 98.06 (para h6-C6H5), 92.75 (meta
h6-C6H5), 85.85 (ortho h6-C6H5), 79.77 (ortho h6-
C6H5), 30.51 (Ph2PCH2CH2CH2-h6-C6H5), 22.61 (d,
This compound was prepared as for
1 from
[RuCl2(PPh2(CH2)3-h6-C6H5)] (100 mg, 0.21 mmol),
Py (32.2 mg, 0.42 mmol) and NH4PF6 (68.4 mg, 0.42
mmol) in MeOH (20 ml). Yellow block-like crystals
were obtained from a MeCNÁEt2O solvent mixture via
/
slow vapour diffusion. Yield: 125 mg, 79%. Anal. Calc.
for C26H26ClF6NP2Ru: C, 46.96; H, 3.94; N, 2.11.
Found: C, 46.42; H, 3.69; N, 2.0%. 1H-NMR (270
MHz, CD3COCD3, 298 K): d 8.79 (dd, 2H, NC5H5),
1JPC
ꢀ
29.7 Hz, Ph2PCH2CH2CH2-h6-C6H5), 20.15
/
(Ph2PCH2CH2CH2-h6-C6H5). 31P{1H}-NMR (109
MHz, CD3COCD3, 298 K): d 26.95 (s, Ph2P(CH2)3-
7.77 (m, 1H, NC5H5), 7.69Á
/
7.11 (m, 10H, Ph), 7.08 (m,
6.1 Hz, 1H, para h6-C6H5),
2H, NC5H5), 6.64 (t, 3JHH
ꢀ
/
h6-C6H5), ꢂ
/
143.81 (sept, PF6).

P.D. Smith et al. / Journal of Organometallic Chemistry 659 (2002) 1Á
/9
9
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Full details have been deposited with the Cambridge
Crystallographic Data Centre, CCDC nos. 181837 and
181838 for the complexes 3 and 5, respectively. Copies
of this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge CB2
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