Reactions of Ru(Cp*) complexes with P(o-tolyl)3

Article abstract of DOI:10.1016/j.jorganchem.2007.06.003

Reaction of [Ru(Cp^*)(CH₃CN)₃](PF₆) with P(o-tolyl)₃ affords [Ru(Cp^*){(η⁶-o-tolyl)P(o-tolyl)₂}](PF₆) (4) in which the P-atom is not coordinated to the metal. The solid-state structure of 4 has been determined. A related reaction with P(p-tolyl)₃ reveals a small quantity [Ru(Cp^*){(η⁶-p-tolyl)P(o-tolyl)₂}](PF₆), in solution, but mostly the expected bis-phosphine complex. Reaction of the Ru(IV) dication, [Ru(Cp^*)(η³-PhCHCHCH₂)(DMF)₂](PF₆)₂, with P(o-tolyl)₃ gives a mixture of the phosphonium salt, C₆H₅CH{double bond, long}CHCH₂P(o-tolyl)₃ (9) and the dication [Ru(Cp^*) (η⁶-C₆H₅CH{double bond, long}CHCH₂P(o-tolyl)₃)](PF₆)₂ (10). Salt 9 forms via attack of the P-atom on the allyl ligand. The latter product results from complexation of 9 via the phenyl group of the former allyl ligand. It would seem that the sterically demanding P(o-tolyl)₃ ligand is not readily compatible with the Ru(Cp^*) fragment, in either the +2 or +4 oxidation state. Detailed NMR studies are reported.

Full text of DOI:10.1016/j.jorganchem.2007.06.003

Journal of Organometallic Chemistry 692 (2007) 4043–4051
www.elsevier.com/locate/jorganchem
Reactions of Ru(Cp*) complexes with P(o-tolyl)3
a
a
a,
b,
b
Helen Caldwell , Sheila Isseponi , Paul S. Pregosin *, Alberto Albinati *, Silvia Rizzato
a
Laboratory of Inorganic Chemistry, ETHZ, 8093 Zu¨rich, Switzerland
Department of Structural Chemistry (DCSSI), University of Milan, 20133 Milan, Italy
b
Received 25 April 2007; received in revised form 25 May 2007; accepted 4 June 2007
Available online 15 June 2007
Abstract
Reaction of [Ru(Cp*)(CH3CN)3](PF6) with P(o-tolyl)3 affords [Ru(Cp*){(g6-o-tolyl)P(o-tolyl)2}](PF6) (4) in which the P-atom is not
coordinated to the metal. The solid-state structure of 4 has been determined. A related reaction with P(p-tolyl)3 reveals a small quantity
[Ru(Cp*){(g6-p-tolyl)P(o-tolyl)2}](PF6), in solution, but mostly the expected bis-phosphine complex. Reaction of the Ru(IV) dication,
[Ru(Cp*)(g3-PhCHCHCH2)(DMF)2](PF6)2, with P(o-tolyl)3 gives a mixture of the phosphonium salt, C6H5CH@CHCH2P(o-tolyl)3
(9) and the dication [Ru(Cp*)(g6-C6H5CH@CHCH2P(o-tolyl)3)](PF6)2 (10). Salt 9 forms via attack of the P-atom on the allyl ligand.
The latter product results from complexation of 9 via the phenyl group of the former allyl ligand. It would seem that the sterically
demanding P(o-tolyl)3 ligand is not readily compatible with the Ru(Cp*) fragment, in either the +2 or +4 oxidation state. Detailed
NMR studies are reported.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Ru(g6-o-tolyl)P(o-tolyl)2; NMR; X-ray; P-allylation
1. Introduction
Cp*)(g6-arene)](anion) complex salts, where the arene
might be a solvent molecule or an organic reagent
[18a,18b,18e]. For reactions involving EAr3 ligands, with
E = As, Sb or Bi, an aryl moiety on the E-atom can com-
pete with the electron pair on the E-atom for the ruthenium
center [19]. In a rare example (not involving a Cp ring), one
aromatic ring of Binap has been shown to be capable of an
g6 bonding mode [18c]. Normally, such arene complexes of
Ru(II) do not readily dissociate the arene, although there
are indications in the literature that this reaction is likely
in acetonitrile solution [18b]. There are not many reports
on Ru(II) arene complexes where the g6-arene contains
strongly electron withdrawing groups [18d], supporting
the idea that the relative stability of such complexes may
depend markedly on the arene and/or the remaining
ligands.
A variety of complexes of ruthenium continue to attract
interest both for their organometallic and catalytic chemis-
try [1–14]. The now readily available Ru(II) salts, [Ru(Cp
or Cp*)(CH3CN)3](PF6) [4e], have been widely employed
as starting materials in the synthesis, study and catalytic
reactions of an increasing number of half sandwich com-
plexes. Equally popular are the Ru–g6-arene complexes
[15–17] and/or complexes that contain tertiary phosphine
ligands [1,2,5,6,8,14–17].
The ease with which [Ru(Cp or Cp*)(CH3CN)3](PF6)
forms coordinatively unsaturated complexes, and subse-
quently reacts with organic arenes, has led to the observa-
tion of a relatively large number of cationic [Ru(Cp or
We report here some unexpected coordination behav-
ior involving the Ru(Cp*) fragment and, primarily, the
*
Corresponding authors. Tel.: +41 44 632 29 15; fax: +41 44 633 10 71
tris o,
m and p-tolyl phosphine compounds, 1–3,
(P.S. Pregosin).
respectively.
E-mail address: paul.pregosin@inorg.chem.ethz.ch (P.S. Pregosin).
0022-328X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.06.003

4044
H. Caldwell et al. / Journal of Organometallic Chemistry 692 (2007) 4043–4051
d 31P = 42.7. A related reaction with the p-tolyl phosphine,
3, gave mostly 6, d 31P = 41.2 as expected.
P
P
P
3
3
3
PF6
PF6
1
2
3
Ru
P
Ru
NCCH3
(m-tolyl)3 (m-tolyl)3
NCCH3
P
P
P
(p-tolyl)3 (p-tolyl)3
2. Results and discussion
5
6
Monitoring the reaction of [Ru(Cp*)(CH3CN)3](PF6)
with 2 equiv. of o-tolyl phosphine, 1, via NMR suggested
that [Ru(Cp*){(g6-o-tolyl)P(o-tolyl)2}](PF6) (4) was formed,
in addition to ca. 1 equiv. of unreacted phosphine. Complex
4 could be isolated in good yield (see Eq. (1)) from the reac-
tion mixture as a yellow powder.
PF6
Ru
P
7
PF6
PF6
However, a small amount (ca. 4%) of the (g6-p-tolyl),
salt, 7, d 31P = 25.9 could be observed in solution. Support
+
Ru
Ru
P
3
NCCH3
NCCH3
H3CCN
P
1
for this structure comes from both the H (see Fig. 4) and
13C NMR spectra from which the characteristic low fre-
quency chemical shifts of the complexed arene, 7 are read-
4
1
ily measured. The similarity in parts of the H spectrum of
4 and 7 is coincidental.1 Obviously, the difference in stabil-
ity between 6 and 7 is not so large as to prevent the forma-
tion of a readily detectable amount of the somewhat
surprising arene complex, 7.
ð1Þ
The 31P NMR spectrum reveals a singlet at d = ꢀ36.7.
This chemical shift appears at an unusually low frequency,
and provides an indication of the formation of the unex-
pected product. Fig. 1 shows this signal (as an inset) as well
as the four well-resolved proton resonances of the com-
plexed o-tolyl group (d = 5.40, 5.69, 5.74 and 5.84). Fig. 2
shows sections of the one-bond (left) and 13C, 1H long-range
(right) correlations, from which one can assign the four
13CH and the two fully substituted carbon signals of the
complexed arene moiety at d > 100 ppm. These 1H and
13C absorptions are all shifted to relatively low frequency,
in keeping with the literature [20]. There are three non-
equivalent methyl resonances in both the 1H and 13C spectra
and these can be assigned using Overhauser methods.
Crystals suitable for X-ray diffraction have been
obtained and Fig. 3 shows two views of the cation. A selec-
tion of bond lengths and bond angles is given in the caption
to the figure. The immediate coordination sphere of the
metal contains the Cp* and one g6-o-tolyl group. One of
the remaining two o-tolyl groups is situated away from
the metal, below the plane of the complexed arene moiety
thereby minimizing possible steric effects between the
P(o-tolyl)2 group and the Cp*. As expected the Ru–C(g6-
o-tolyl) separations for C11, C12 and C16 are somewhat
longer than for C13–C15, presumably due to the steric
effects associated with the P(o-tolyl)2 group. These Ru–C
bond lengths are in the region expected for Ru–arene com-
plexes [21–31]. The five Ru–C(Cp*) separations are all nor-
mal and not significantly different.
IV
Ru
(PF6)2
DMF
DMF
8
We have recently prepared the Ru(IV) dicationic allyl
complex 8 [32]. This salt is an interesting catalytic precur-
sor in a Friedel-Crafts type coupling reaction [32]. Given
the ease with which the DMF molecules can be replaced,
the salt 8 was allowed to react with 2 equiv. of P(o-tolyl)3
in acetone solution at room temperature. The crude iso-
lated solid product, which was washed with ether to
remove excess unreacted phosphine, proved to be a mix-
ture of two components, 9 and 10, in a ratio of ca. two
to one (see Scheme 1). The two phosphorus chemical
1
The spin system for the four protons of the coordinated p-tolyl ring is
AA0M, M0X (X = 31P), so that it will never be first order, and the
appearance of a triplet and a doublet for 7 is somewhat deceptive. The
four protons of the coordinated o-tolyl ring can afford a first order
spectrum.
The analogous reaction with 2 equiv. of the meta tolyl
phosphine, 2, gave the expected bis-phosphine product, 5,

H. Caldwell et al. / Journal of Organometallic Chemistry 692 (2007) 4043–4051
4045
Fig. 1. The complete 1H NMR spectrum for 4 (bottom trace) showing the non-equivalent o-tolyl methyl groups and (top left) the expansion of the region
containing the arene protons 3–6, plus (top right) the 31P signal. Once the arene ring is complexed, the 31P spin–spin coupling to the ring protons is reduced
in magnitude and often not resolved (CD2Cl2, 500 MHz).
Fig. 2. One-bond correlation (left) showing the four 13C chemical shifts for the CH resonances in the complexed arene and long-range correlation (right)
indicating the positions of the two arene ipso-carbons for salt 4, close to 102 ppm (CD2Cl2, 125 MHz).
shifts are found at d = 26.1 and d = 24.2 (see Fig. 5) for
the major and minor components, respectively. In the
1H NMR spectrum of the major species, the four protons
of the allyl fragment appear as three resonances at (a)
3JPH = 4.3 Hz, (b) d = 6.02 ppm (@CHCH2, as a complex
multiplet strongly overlapped with the complexed arene
resonances of 10) and (c) d = 4.77 (PCH2) with
3
2JPH = 14.0 Hz and JHH = 7.5 Hz. The first two chemical
3
d = 7.05
(PhACH@)
with
3JHH = 15.4 Hz
and
shifts plus the 15.4 Hz JHH coupling are in agreement

4046
H. Caldwell et al. / Journal of Organometallic Chemistry 692 (2007) 4043–4051
with a trans olefin fragment. The presence of the 14 Hz
31P coupling to the a-carbon was proven by a 31P, 1H
correlation.
H
C
P
Ph
C
H
C
H2
χ
β
α
The analogous proton allyl signals for the minor product,
3
10, were found at (a) d = 6.92 (PhACH@ JHH = 14.9 Hz
4
3
and JPH = 4.0 Hz), (b) d = 6.30 (@CHCH2 JHH = 14.9,
3JHH = 7.3 and JPH = 4.0 Hz) and (c) d = 4.92 (PCH2
3
3JPH = 14.1 Hz and JHH = 7.3 Hz). Once again the pres-
3
ence of 31P coupling was shown by a 31P, H correlation,
1
and the two relatively high frequency proton chemical shifts
plus the 14.9 Hz 3JHH coupling are in agreement with a trans
olefin fragment.
In 10 one finds a rather strongly second order group of
multiplets between 5.6 ppm and 5.9 ppm, which are
assigned as the complexed arene proton signals, whereas
the Ph protons of the allyl fragment in 9 are found at rou-
tine positions.
The PCH2 proton resonances in both 9 and 10 can be
correlated to aliphatic 13CH2 signals at d = 29.3 and
d = 29.2, for the major and minor products, respectively.
1
Both 13C resonances show relatively large JP,C values of
ca. 52 Hz which are typical for sp3 hybridized carbons
1
attached to a quaternary P-atom [33]. We note that JP,C
in the known phosphonium salt, Ph3PCH2CH@CH2, at
2
49.7 Hz and JPH at 14.9 Hz [33b] are in excellent agree-
ment with our measured values.
Strong evidence in support of the (g6-C6H5) ligand in 10
comes from the 13C NMR results. One finds three 13C
NMR CH signals for the complexed arene of 10 at the
expected low frequencies: d = 85.1 (ortho) d = 87.3 (meta)
and at d = 87.12 (para) in the ratio 2:2:1 respectively. The
olefinic carbons of the trans double bonds in both 9 and
10 are found in a typical region for such sp2 carbons.
For both 9 and 10 one observes 3 equiv. methyl reso-
1
nances in both the H and 13C spectra, thereby completing
the solution structure proof. We note that there is a report
+
of a complexed ammonium ion, CH2@CHCH2ANEt3
,
derived from the attack of triethylamine, as a nucleophile,
on a Ru(IV) allyl complex [34].
To investigate whether other bulky PR3 donors might
also chose to avoid P-complexation, we studied related
reactions using the phosphite ligands, 11 and 12. Reaction
of [Ru(Cp*)(CH3CN)3](PF6) with 2.1 equiv. of tris ortho
xenyl phosphite, 11, leads to predominantly the mono-
phosphite product. However, a series of weak signals in
the 1H spectrum in the region between 5.4 ppm and
6.2 ppm suggest the presence of a small proportion, less
than 5%, of arene complexed species. Reaction of
[Ru(Cp*)(CH3CN)3](PF6) with 1.1 equiv. of the phosphite
12 resulted in the mono-phosphite complex, Ru(Cp*)-
(12)(CH3CN)2](PF6) (14) with no trace of arene complexed
Fig. 3. ORTEP views of the cation of salt 4 showing 50% probability
ellipsoids. Ru–C(1), 2.172(6), Ru–C(2), 2.188(5), Ru–C(3), 2.180(6), Ru–
C(4), 2.174(6), Ru–C(5), 2.184(7), Ru–C(11), 2.254(5), Ru–C(12), 2.222(6),
Ru–C(13), 2.207(5), Ru–C(14), 2.204(6), Ru–C(15), 2.199(6), Ru–C(16),
2.216(6), Ru-center of the cp*,1.819(6), Ru-center of the complexed arene,
1.705(6), P(1)–C(11), 1.846(5) P(1)–C(21), 1.825(6), P(1)–C(31), 1.844(7),
C(21)–P(1)–C(31), 99.2(3) C(21)–P(1)–C(11), 101.5(3), C(31)–P(1)–C(11),
101.9(3).
1
species observable in the H NMR spectrum. Product 13,
Ru(Cp*) (11)(CH3CN)2](PF6), could be isolated by layer-

H. Caldwell et al. / Journal of Organometallic Chemistry 692 (2007) 4043–4051
4047
1
Fig. 4. Expansion of the region of the H spectrum between 5.7 ppm and 6 ppm showing the arene resonances for the small quantity of the g6-complex
arising from the p-tolyl phosphine (CD2Cl2, 500 MHz).
ing an acetone solution of the crude product with diethyl
ether and cooling to ꢀ40 °C. Presumably the oxygen atoms
of these phosphite ligands provide enough flexibility such
that the three P-substituents can be comfortably placed in
a position remote from the Cp* ring.
tively, i.e., the loss of the two acetonitrile molecules. For
14, these are more or less the only signals between m/e
600–900. Moreover, the strongest signals in the mass spec-
tra of the isomeric bis-phosphine salts 5 and 6, correspond
to the cation of 7, i.e., ‘‘Ru(Cp*)(phosphine)’’. Although
these mass spectra do not prove structure, it seems
likely that these are the 18e g6-arene cations. All of the
NMR and mass spectral observations support the idea that
P-coordination will not always result in the most stable
species.
P
O
t-Bu
P
O
3
3
Ph
t-Bu
11
12
3. Conclusions
The solution NMR data for 9 and 10 support the view
that the reaction of the bulky phosphine 1 with the Ru(IV)
allyl, 8 does not lead to a stable routine P-coordinated
It is interesting that the most intense set of peaks in the
MALDI mass spectra of 13 and 14 correspond to Ru(Cp*)
(11), m/z = 775, and Ru(Cp*) (12), m/z = 883.5, respec-
(PF6)2
IV
II
Ru
(PF6)2
P
P(o.tolyl)3
Ru
DMF
3
DMF
DMF
DMF
dissociation
(PF6)2
(PF6)
II
II
Ru
Ru
DMF
complexation
- DMF and solvent
Solvent
DMF
P(o.tolyl)3
10, minor
(PF6)
P(o.tolyl)3
9 major
Scheme 1.

4048
H. Caldwell et al. / Journal of Organometallic Chemistry 692 (2007) 4043–4051
The 31P resonance for the PF6 anion, although not
noted in the preparative sections, was found for each salt,
at d = ꢀ144.4 as a sharp septet.
Crystallography. Air stable, yellow crystals of 4, suitable
for X-ray diffraction were obtained by crystallization from
dichloromethane/diethyl ether solution. A crystal of 4 was
mounted on a Bruker APEX diffractometer, equipped with
a CCD detector, and cooled, using a cold nitrogen stream,
to 150(2) K for the data collection. The space group was
determined from the systematic absences, while the cell
constants were refined, at the end of the data collection,
with the data reduction software SAINT [36]. The experimen-
tal conditions for the data collections, crystallographic and
other relevant data are listed in Table 1 and in Supplemen-
tary Material (as a cif file).
The collected intensities were corrected for Lorentz and
polarization factors [36], and empirically for absorption
using the SADABS program [37]. The structure was solved
by direct and Fourier methods and refined by full matrix
P
2
least squares [38], minimizing the function [ w(Fo ꢀ (1/
2 2
k)Fc ) ] and using anisotropic displacement parameters
for all atoms, except the hydrogens. The contribution of
the hydrogen atoms, in their calculated position was
included in the refinement using
a riding model
2
˚
(B(H) = aB(Cbonded) (A ), where a = 1.4 for the hydrogen
atoms of the methyl groups and a = 1.2 for the others).
No extinction correction was deemed necessary. Upon con-
vergence the final Fourier difference map showed no signif-
icant peaks. The scattering factors used, corrected for the
real and imaginary parts of the anomalous dispersion, were
Fig. 5. A section of the 1H NMR spectrum showing the two aliphatic
PCH2 resonances for 9 and 10 (left) (acetone-d6, 400 MHz) plus the two
31P resonances (right) (CD2Cl2, 202 MHz). The observed doublet of
doublets stems from 3J(31P,1H) and 3J(1H,1H).
Table 1
phosphine complex. Whether inter- or intra-molecular, the
P-atom prefers to attack the Ru(IV) allyl complex at a ter-
minal allyl carbon center, with subsequent reductive elimi-
nation to afford a Ru(II) species. The phosphonium salt, 9,
which forms, is relatively stable, but then so is the Ru(II)
g6-C6H5CH@CHCH2P(o-tolyl)3 arene complex, 10. It
would seem that, just as found for the reaction leading to
4, the sterically demanding ligand 1, is not readily compat-
ible with the Ru(Cp*) fragment, in either the +2 or +4 oxi-
dation state. The bulky phosphite ligands 11 and 12,
behave in a conventional manner to form 13 and 14,
although there is a hint that some very modest quantities
of arene complexes may be present using 11.
X-ray crystallographic data for compound 4
Molecular formula
Molecular weight
T (K)
C31H36F6P2Ru
685.61
150 (2)
Diffractometer
Crystal system
Space group (no.)
Bruker APEX CCD
Orthorhombic
P212121(19)
11.390 (2)
˚
a (A)
˚
b (A)
12.149 (2)
˚
c (A)
21.631 (3)
2993.4 (7)
3
˚
V (A )
Z
4
d(calc) (g cmꢀ3
)
1.521
6.88
l (cmꢀ1
)
Transmission
0.79915–1.00000
Radiation
Mo Ka (graphite monochromated)
˚
k (A)
0.71073
1.92 < h < 24.49
19728
4. Experimental
h Range (°)
Data collected
All reactions and manipulations were performed under
an N2 atmosphere using standard Schlenk techniques.
The solvents and reagents were dried and distilled using
standard procedures and stored under nitrogen. NMR
spectra were recorded with Bruker DPX-300, 400, and
500 MHz spectrometers. For salts 4–7, 9 and 10, the spec-
tra were measured at 273 K to avoid decomposition.
Chemical shifts are given in ppm; coupling constants (J)
in Hertz. Elemental analyses and mass spectroscopic stud-
ies [35] were performed at ETHZ.
Unique data
4954
4593
Data observed (no)
2
2
[jFoj > 2.0r(jFj )]
Parameters refined (nv)
Rint
361
0.0321
0.0437
0.0931
1.142
R (observed reflections)
R2w (observed reflections)
GoF
Flack’s parameter
0.06(5)
P
P
P
P
R = (jFo ꢀ (1/k)Fcj)/ jFoj R2w = [ w(Fo ꢀ (1/k)Fc2)2/ wjFo j ].
2
2 2
P
GOF = [ w(Fo ꢀ (1/k)Fc2)2/(no ꢀ nv)]1/2
.
2

H. Caldwell et al. / Journal of Organometallic Chemistry 692 (2007) 4043–4051
4049
taken from the literature [39]. The handedness of the struc-
ture was confirmed by refining the Flack’s parameter [40].
All calculations were carried out by using the PC version
of the programs: WINGX [41], SHELX-97 [38] and ORTEP [42].
was stirred for 2 h at room temperature after which time
the solvent was removed under vacuum. The resulting crude
product was washed with diethyl ether to afford a yellow
1
solid. Yield: 76.5 mg (47%). H NMR (500 MHz, CD2Cl2,
0 °C) d (ppm): 1.16 (s, 15H, C5Me5), 2.20 (s, 18H, 6Me),
2.72 (s, 3H, MeCN), 6.99 (m, 6H, H2), 7.03 (m, 6H, H6),
7.11 (m, 6H, H5), 7.14 (m, 6H, H4). 13C{1H}NMR (125
MHz, CD2Cl2, 0 °C) d (ppm): 5.7 (MeCN), 9.8 (C5Me5),
21.9 (6Me), 93.4 (C5Me5), 128.0 (C5), 129.8 (MeCN), 130.8
(C4), 131.3 (C6), 134.5 (C2), 135.2 (C1), 137.8 (C3).
31P{1H}NMR (202 MHz, CD2Cl2, 0 °C) d (ppm): 42.7.
4''
3''
5''
2''
7''
1
Ru
6''
6
1''
P
5
3
7'
2'
3'
4'
4
1'
2
6'
7
5'
5''
4''
3''
2''
Ru
P
Ru
[RuCp*(g6-o-tol)P(o-tol)2]PF6 (4). A solution of P(o-
NCCH3
2
1''
P
(p-tol)3P
4
tol)3 (157.3 mg, 0.517 mmol) in 3 mL acetone was added
5
1
1
1'
to
a
solution of [RuCp*(CH3CN)3]PF6 (108.6 mg,
2
2'
3'
3
0.215 mmol) in 3 mL acetone. The yellow reaction mixture
was stirred for 2 h at room temperature after which time
the solvent was removed under vacuum. The resulting
crude product was washed with diethyl ether to afford a
pale yellow solid. Yield 125.6 mg (85%). Crystals suitable
for diffraction were obtained by layering a dichlorometh-
ane solution of the crude product with diethyl ether.
1H NMR (500 MHz, CD2Cl2, 0 °C) d (ppm): 1.95 (s,
15H, C5Me5), 2.10 (s, 3H, Me7), 2.39 (s, 3H, Me70), 2.74
(s, 3H, Me700) 5.40 (d, J = 5.8 Hz, 1H, H6), 5.69 (t,
J = 5.8 Hz, 1H, H5), 5.74 (d, J = 5.4 Hz, 1H, H3), 5.84
(t, J = 5.4. Hz, 1H, H4), 6.90 (dd, J = 7.203, 3.65 Hz, 1H,
H60), 7.16 (m, 1H, H50), 7.21 (m, 1H, H3 ), 7.26 (m, 1H,
H600), 7.29 (m, 1H, H40), 7.38 (m, 1H, H400), 7.41 (m, 1H,
H300), 7.42 (m, 1H, H500). 13C{1H}NMR (125 MHz,
CD2Cl2, 0 °C) d (ppm): 10.6 (C5Me5), 18.8 (Me7), 21.4
(Me70), 22.2 (Me700), 86.8 (C5), 88.2 (C3), 88.3 (C6), 89.3
(C4), 96.7 (C5Me5), 102.0 (C2), 102.6 (C1), 126.9 (C30),
127.4 (C600), 129.9 (C40), 130.0 (C200), 131.2 (C50), 131.5
(C300), 137.8 (C400), 142.3 (C10), 148.0 (C100). 31P{1H}NMR
(202 MHz, CD2Cl2, 0 °C) d (ppm): ꢀ36.7. Elemental Anal.
Calc. for C31H36F6P2Ru: C, 54.31; H, 5.29. Found: C,
53.55; H, 5.34%. Mass spectrometry: m/z: 541.1 [M+].
3
3
4'
4
5'
[RuCp*(P(p-tol)3)2CH3CN]PF6 (6) and [RuCp*(g6-p-
tol)P(p-tol)2]PF6 (7). A solution of P(p-tol)3 (114.8 mg,
0.377 mmol) in 3 mL acetone was added to a solution of
[RuCp*(CH3CN)3]PF6 (90.6 mg, 0.179 mmol) in 3 mL ace-
tone. The yellow reaction mixture was stirred for 2 h at room
temperature after which time the solvent was removed under
vacuum. Theresultingcrude productwaswashedwith diethyl
ether to afford a yellow solid that was found to be a mixture of
6 and 7. Yield: 151.2 mg. 1H NMR (500 MHz, CD2Cl2, 0 °C)
d (ppm): 1.15 (s, 15H, C5Me5, 6), 1.92 (s, 15H, C5Me5, 7), 2.30
(s, 3H, H7, 7), 2.37 (s, 18H, 6Me, 6), 2.64 (s, 3H, MeCN, 6),
5.76 (d, J = 6.4 Hz, 2H, H3, 7), 5.97 (dd, JPH = 6.7 Hz,
J = 6.4 Hz, 2H, H2, 7), 7.02 (m, 12H, H3, 6), 7.06 (m, 12H,
H2, 6). 13C{1H}NMR (125 MHz, CD2Cl2, 0 °C) d (ppm):
5.6 (MeCN, 6), 9.6 (C5Me5, 6), 10.9 (C5Me5, 7), 18.4 (Me,
C5, 7), 21.3 (6Me, 6), 87.9 (C2, 7), 88.3 (C3, 7), 92.8
(C5Me5), 102.0 (C4, 7), 128.8 (C3, 6), 129.5 (MeCN, 6),
132.3 (C1, 6), 134.1 (C2, 6), 140.6 (C4, 6). 31P{1H}NMR(202
MHz, CD2Cl2, 0 °C) d (ppm): 41.2 (6), 25.9 (7). Elemental
Anal. Calc. for 96% C54H60NF6P3Ru and 4%
C31H36F6P2Ru: C, 62.58; H, 5.83. Found: C, 61.94; H,
6.06%. Mass spectrometry: m/z: 305 P(p-tol)3, 541
[M+ꢀCH3CN–P(p-tol)3] 6 and [M+] 7, 845 [M+ꢀCH3CN] 6.
Ru
NCCH3
(m-tol)3P
P
3
Ru
γ'
1'
2'
γ
1
4'
4
α'
P+
[RuCp*(P(m-tol)3)2CH3CN]PF6 (5). A solution of
P(m-tol)3 (97.0 mg, 0.319 mmol) in 2 mL acetone was added
α
2
3'
β'
3
β
P
to
a
solution of [RuCp*(CH3CN)3]PF6 (80.0 mg,
3
3
0.159 mmol) in 3 mL acetone. The yellow reaction mixture

4050
H. Caldwell et al. / Journal of Organometallic Chemistry 692 (2007) 4043–4051
[PhACH@CHACH2-P(o-tol)3]PF6 (9) and [RuCp*g6-
(dd, J = 8.7, 2.4 Hz, 3H), 7.47 (d, J = 2.1 Hz, 3H), 7.64
(dd, J = 8.7, 1.7 Hz, 3H). 31P{1H}NMR (121 MHz, ace-
tone-d6, room temperature) d (ppm): 133.6. Elemental Anal.
Calc. for C56H84N2O3F6P2Ru: C, 60.58; H, 7.63; N, 2.52.
Found: C, 60.47; H, 7.57; N, 2.52%. Mass spectrometry:
m/z: 883.5 [M+ꢀ2CH3CN].
C5H5ACH@CHACH2P (o-tol)3](PF6)2 (10). A solution
of P(o-tol)3 (34.9 mg, 0.115 mmol) in 1 mL acetone was
added to
a
solution of [RuCp*(DMF)2(g3-phenylal-
lyl)](PF6)2 (52.5 mg, 0.057 mmol) in 1 mL acetone. The reac-
tion mixture was stirred for 2 h at room temperature after
which time the solution was concentrated under vacuum to
precipitate a dark yellow powder. The solid was collected
and washed with diethyl ether. It was found to be a mixture
of 9 and 10. Yield: 53.5 mg. 1H NMR (400 MHz, acetone-d6,
0 °C) d (ppm): 1.94 (s, C5Me5), 2.39 (s, tolyl Me), 4.77 (dd,
JPH = 14.1, J = 7.5 Hz, Ha0), 4.92 (dd, JPH = 14.1,
J = 7.3 Hz, Ha), 6.02 (m, Hb0), 6.30 (ddd, J = 14.9, 7.3,
JPH = 4.0 Hz, Hb) 6.92 (dd, J = 14.9, JPH = 4.0 Hz, Hv),
7.05 (dd, J = 15.4, 4.3 Hz, Hv0). 1H NMR (500 MHz,
CD2Cl2, 0 °C) d (ppm): 5.64 (m, H3), 5.74 (m, H4), 5.83
(m, H2), 7.18 (m, H20), 7.30 (m, H40). 13C{1H}NMR
(125 MHz, CD2Cl2, 0 °C) d (ppm): 10.7 (C5Me5), 23.1 (d,
5. Supplementary materials
CCDC 645293 contains the supplementary crystallo-
graphic data for 4. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.
html, or from the Cambridge Crystallographic Data Cen-
tre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Acknowledgements
JPC = 17.2 Hz, tolyl methyl groups, 10), 23.2 (d, JPC
=
P.S.P. thanks the Swiss National Science Foundation,
and the ETH Zurich for support, as well as the Johnson
Matthey organization for the loan of ruthenium salts.
A.A. thanks MURST for a grant (PRIN 2004).
16.2 Hz, tolyl methyl groups, 9), 29.2 (d, JPC = 52.5 Hz,
Ca), 29.3 (d, JPC = 52.5 Hz, Cb), 85.1 (C2), 87.2 (C4), 87.3
(C3), 97.1 (C1), 97.7 (C5Me5). 31P{1H}NMR (202 MHz,
CD2Cl2, 0 °C) d (ppm): 25.3 10, 26.1 9. Mass spectrometry:
m/z: 421 [M+] 9, 541 [RuCp*P(o-tol)3]+, 657 [RuCp*(P(p-
tol)3)(CH2–CH–CH–Ph)]+, 803 [RuCp*g6-C5H5ACH@
CHACH2P(o-tol)3](PF6)+.
References
[1] A. Hejl, O.A. Scherman, R.H. Grubbs, Macromolecules 38 (2005)
7214–7218;
[RuCp*(tris ortho xenyl phosphite)(CH3CN)2]PF6 (13).
A solution of tris ortho xenyl phosphite (233.2 mg,
0.433 mmol) in 3 mL acetone was added to a solution of
[RuCp*(CH3CN)3]PF6 (104.0 mg, 0.206 mmol) in 4 mL ace-
tone. The yellow reaction mixture was stirred for 2 h at room
temperature after which time the solvent was removed under
vacuum. The resulting crude product was washed with
diethyl ether to afford 124.6 mg of a yellow solid. Crystals
of the pure monosubstituted phosphite complex were
obtained by dissolving 50 mg of the yellow solid in acetone,
R.H. Grubbs, Tetrahedron 60 (2004) 7117–7140;
M.S. Sanford, J.A. Love, R.H. Grubbs, J. Am. Chem. Soc. 123
(2001) 6543–6554.
[2] R. Noyori, Adv. Synth. Catal. 345 (2003) 15–32;
R. Noyori, Angew. Chem., Int. Ed. Engl. 41 (2002) 2008–2022.
[3] S. Rigaut, D. Touchard, P.H. Dixneuf, Coord. Chem. Rev. 248
(2004) 1585–1601;
R. Castarlenas, I. Alaoui-Abdallaoui, D. Semeril, B. Mernari, S.
Guesmi, P.H. Dixneuf, New J. Chem. 27 (2003) 6–8;
S. Derien, P.H. Dixneuf, J. Organomet. Chem. 689 (2004) 1382–1392;
C. Bruneau, P.H. Dixneuf, Acc. Chem. Res. 32 (1999) 311–323.
[4] (a) B.M. Trost, M.T. Rudd, J. Am. Chem. Soc. 127 (2005) 4763–
4776;
1
layering with diethyl ether and cooling to ꢀ40 °C (%). H
NMR (250 MHz, acetone-d6, room temperature) d (ppm):
1.21 (d, JPC = 2.3 Hz, 15H, C5Me5), 2.38 (s, 6H, 2MeCN),
7.07–7.70 (m, 27H, tris ortho xenyl phosphite protons).
31P{1H}NMR (101 MHz, acetone-d6, room temperature) d
(ppm): 136.4. Elemental Anal. Calc. for C50H48N2O3F6-
P2Ru: C, 59.94; H, 4.83; N, 2.80. Found: C, 60.13; H, 5.00;
N, 2.53%. Mass spectrometry: m/z: 775 [M+ꢀ2CH3CN],
857 [M+], 1313 [M+ꢀ2CH3CN + tris ortho xenyl phosphite].
[RuCp*(tris(2,4-di-tert-butylphenyl)phosphite) (CH3-
CN)2]PF6 (14). A solution of tris(2,4-di-tert-butylphe-
nyl)phosphite (149.5 mg, 0.231 mmol) in 3 mL acetone was
added to a solution of [RuCp*(CH3CN)3]PF6 (106.0 mg,
0.210 mmol) in 3 mL acetone. The yellow reaction mixture
was stirred for 2 h at room temperature after which time
the solvent was removed under vacuum. The crude product
was washed with hexane and dried under vacuum to yield
the yellow monosubstituted phosphite complex. Yield:
50.0 mg (21%). 1H NMR (300 MHz, acetone-d6, room tem-
perature) d (ppm): 1.28 (s, 27H, tBu), 1.40 (s, 27H, tBu), 1.63
(d, JPC = 2.7 Hz, 15H, C5Me5), 2.45 (s, 6H, 2MeCN), 7.16
(b) B.M. Trost, M.T. Rudd, J. Am. Chem. Soc. 125 (2003) 11516–
11517;
(c) B.M. Trost, M.T. Rudd, J. Am. Chem. Soc. 123 (2001) 8862–
8863;
(d) B.M. Trost, A.B. Pinkerton, J. Am. Chem. Soc. 122 (2000) 8081–
8082;
(e) B.M. Trost, C.M. Older, Organometallics 21 (2002) 2544–2546.
[5] K. Abdur-Rashid, A.J. Lough, R.H. Morris, Organometallics 20
(2001) 1047–1049;
C.J.A. Daley, S.H. Bergens, J. Am. Chem. Soc. 124 (2002) 3680–
3691.
[6] J. Zhao, J.F. Hartwig, Organometallics 24 (2005) 2441–2446.
[7] D.A. Alonso, P. Brandt, S.J.M. Nordin, P.G. Andersson, J. Am.
Chem. Soc. 121 (1999) 9580–9588;
D.A. Alonso, S.J.M. Nordin, P. Roth, T. Tarnai, P.G. Andersson, J.
Org. Chem. 65 (2000) 3116–3122.
[8] J.W. Faller, P.P. Fontaine, Organometallics 24 (2005) 4132–4138;
J.W. Faller, D.G. D’Alliessi, Organometallics 22 (2003) 2749–2757;
J.W. Faller, J. Parr, Organometallics 19 (2000) 1829.
[9] J.C. Conrad, G.P.A. Yap, D.E. Fogg, Organometallics 22 (2003)
1986–1988;
S.D. Drouin, H.M. Foucault, G.P.A. Yap, D.E. Fogg, Can. J. Chem.
83 (2005) 748–754.

H. Caldwell et al. / Journal of Organometallic Chemistry 692 (2007) 4043–4051
4051
[10] E.C. Burger, J.A. Tunge, Chem. Commun. (2005) 2835–2837.
[11] V. Cadierno, J. Diez, S.E. Garcia-Garrido, J. Gimeno, Chem.
Commun. (2004) 2716–2717.
[12] C.P. Casey, T.E. Vos, S.W. Singer, I.A. Guzei, Organometallics 21
(2002).
[13] A. Doppiu, A. Salzer, Eur. J. Inorg. Chem. (2004) 2244–2252.
[14] Y.R.S. Laxmi, J.E. Ba¨ckvall, Chem. Commun. (2000) 611–612;
A. Aranyos, G. Csjernyik, K. Szabo, J.E. Ba¨ckvall, Chem. Commun.
(1999) 3352–3451.
[15] H. Nagashima, H. Kondo, T. Hayashida, Y. Yamaguchi, M. Gondo,
S. Masuda, K. Miyazaki, K. Matsubara, K. Kirchner, Coord. Chem.
Rev. 245 (2003) 177–190;
[24] H. Brunner, R. Oeschey, B. Nuber, Organometallics 15 (1996) 3616–
3624.
[25] L.A. Huxham, E.L.S. Cheu, B.O. Patrick, B.R. James, Inorg. Chim.
Acta 352 (2003) 238–246.
[26] J. Davenport, D.L. Davies, J. Fawcett, S.A. Garratt, D.R. Russell, J.
Chem. Soc., Dalton Trans. (2000) 4432–4441.
[27] C.J. den Reijer, D. Drago, P.S. Pregosin, Organometallics 20 (2001)
2982–2989;
C.J. den Reijer, P. Dotta, P.S. Pregosin, A. Albinati, Can. J. Chem.
79 (2001) 693–704;
C.J. den Reijer, M. Worle, P.S. Pregosin, Organometallics 19 (2000)
309–316;
H. Aneetha, M. Jimenez-Tenorio, M.C. Puerta, P. Valerga, V.N.
Sapunov, R. Schmid, K. Kirchner, K. Mereiter, Organometallics 21
(2002) 5334–5346.
C.J. den Reijer, H. Ruegger, P.S. Pregosin, Organometallics 17 (1998)
¨
5213–5215.
[28] T.J. Geldbach, P.S. Pregosin, Eur. J. Inorg. Chem. (2002) 1907–
1918.
[29] Y. Yamamoto, R. Sato, F. Matsuo, C. Sudoh, T. Igoshi, Inorg.
Chem. 35 (1996) 2329–2336.
[30] M.S. Roethlisberger, A. Salzer, H.B. Buergi, A. Ludi, Organometal-
lics 5 (1986) 298–302.
[31] P. Steenwinkel, S.L. James, R.A. Gossage, D.M. Grove, H. Kooj-
man, W.J.J. Smeets, A.L. Spek, G. van Koten, Organometallics 17
(1998) 4680–4693.
[16] M. Althaus, C. Bonaccorsi, A. Mezzetti, F. Santoro, Organometallics
25 (2006) 3108–3110;
D. Huber, P.G.A. Kumar, P.S. Pregosin, I.S. Mikhel, A. Mezzetti,
Helv. Chim. Acta 89 (2006) 1696–1715.
[17] P.W. Cyr, S.J. Rettig, B.O. Patrick, B.R. James, Organometallics 21
(2002) 4672–4679;
A.M. Joshi, I.S. Thorborn, S.J. Rettig, B.R. James, Inorg. Chim.
Acta 198–200 (1992) 283–296;
T. Geldbach, A.B. Chaplin, K.D. Ha¨nni, R. Scopelleti, P.J. Dyson,
Organometallics 24 (2005) 4974–4980.
[18] (a) R. Hermatschweiler, I. Fernandez, P.S. Pregosin, F. Breher,
Organometallics 25 (2006) 1440–1447;
[32] I. Fernandez, R. Hermatschweiler, F. Breher, P.S. Pregosin, L.F.
Veiros, M.J. Calhorda, Angew. Chem., Int. Ed. 45 (2006) 1–6.
[33] (a) T. Albright, Org. Magn. Reson. 8 (1976) 489–499;
(b) T. Albright, W.J. Freeman, E.E. Schweitzer, J. Am. Chem. Soc.
97 (1975) 2946.
[34] E. Ruba, W. Simanko, K. Mauthner, K.M. Soldouzi, C. Slugovc, K.
Mereiter, R. Schmid, K. Kirchner, Organometallics 18 (1999) 3843–
3850.
(b) I. Fernandez, R. Hermatschweiler, P.S. Pregosin, A. Albinati, S.
Rizzato, Organometallics 25 (2006) 323–330;
(c) R. Hermatschweller, P.S. Pregosin, A. Albinati, S. Rizzato, Inorg.
Chim. Acta 354 (2003) 90–93;
(d) A. Schmid, H. Piotrowski, T. Lindel, Eur. J. Inorg. Chem. (2003)
2255–2263;
(e) S.P. Nolan, K.L. Martin, D. Buzatu, M.L. Trudell, E.D. Stevens,
P.J. Fagan, Struct. Chem. 4 (1993) 367–375.
[35] Several of the mass spectra reveal that the salts have reacted with the
matrix, 3-hydroxypicolinic acid (HPA), to form a new salt. For
example, in the mass spectrum of 13 one finds a signal at m/z = 912
(RuCp*(12)(HPA)).
[19] E. Becker, C. Slugovc, E. Ruba, C. Standfest-Hauser, K.
Mereiter, R. Schmid, K. Kirchner, J. Organomet. Chem. 649
(2002) 55–63.
[20] B.E. Mann, B.F. Taylor, 13C NMR Data for Organometallic
Compound, Academic Press, London, 1981.
[21] J. Bank, O. Gevert, W. Wolfsberger, H. Werner, Organometallics 14
(1995) 4972–4974.
[22] M.A. Bennett, Z. Lu, X. Wang, M. Brown, D.C.R. Hockless, J. Am.
Chem. Soc. 120 (1998) 10409–10415;
[36] A.X.S. Bruker, SAINT, Integration Software, Bruker Analytical X-ray
Systems, Madison, WI, 1995.
[37] G.M. Sheldrick, SADABS, Program for Absorption Correction, Uni-
versity of Go¨ttingen, Go¨ttingen, Germany, 1996.
[38] G.M. Sheldrick, SHELX-97. Structure Solution and Refinement Pack-
age, Universita¨t Go¨ttingen, 1997.
[39] A.J.C. Wilson (Ed.), International Tables for X-ray Crystallography,
Vol. C, Kluwer Academic Publisher, Dordrecht, The Netherlands,
1992.
M.A. Bennett, A.J. Edwards, J.R. Harper, T. Khimyak, A.C. Willis,
J. Organomet. Chem. 629 (2001) 7–18.
[23] S. Bhambri, D.A. Tocher, Polyhedron 15 (1996) 2763–2770.
[40] H.D. Flack, Acta Crystallogr., Sect. A 39 (1983) 876.
[41] L.J. Farrugia, J. Appl. Crystallogr. 32 (1999) 837.
[42] L.J. Farrugia, J. Appl. Crystallogr. 30 (1997) 565.