Enolate-phosphane ligands providing a tool for the selective substitution of triphenylphosphane by carbon monoxide or trimethylphosphane in complex {Ru(Cp)[η2-P,O-Ph2PCH2C(tBu)=O](PPh 3)}[PF6], and subsequent reactivity towards terminal alkynes

Article abstract of DOI:10.1002/ejic.200501073

The deprotonation under basic conditions of the keto-phosphane ligand in complexes (Ru(Cp)[η¹-P-Ph₂PCH₂C(=O)-tBu] (PPh₃) (L)} [PF₆] (L = CO or PMe₃) that arise from the addition of L to {Ru(Cp)[η²-P,O-Ph₂PCH₂C(tBu)=O](PPh ₃)}[PF₆] generates {Ru⁺(Cp)[η¹-P-Ph₂PCH=C(tBu)O ^-](PPh₃) zwitterionic species, as shown by an X-ray crystal structure determination (L = CO). The removal of the triphenylphosphane ligand is subsequently achieved under thermal activation to afford the neutral derivatives Ru(Cp)[η²-P,O-Ph₂PCH=C-(tBu)O](L). A further protonation step is sufficient to complete the formation of the new complex {Ru(Cp) [η²-P,O-Ph₂PCH₂C(tBu)=O](PMe ₃)}[PF₆], which reacts in methanol at reflux with 1,1-diphenyl-2-propyn-1-ol to afford the six-membered metallacyclic derivative {Ru(Cp) [η²-C,P:C(CH=CPh₂)OC(tBu)=CH-PPh₂](PMe ₃)}[PF₆], as shown by an X-ray single crystal analysis. The synthesis of related η⁵-indenyl ruthenium complexes and of {Ru(Cp)-(=C=CH₂)[Ph₂PCH₂C(=O)tBu](PR ₃)}[PF₆] (PR₃ = PPh₃ or PMe₃) vinylidene complexes is also reported. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Full text of DOI:10.1002/ejic.200501073

FULL PAPER
DOI: 10.1002/ejic.200501073
Enolate-Phosphane Ligands Providing a Tool for the Selective Substitution of
Triphenylphosphane by Carbon Monoxide or Trimethylphosphane in Complex
{Ru(Cp)[η2-P,O-Ph2PCH2C(tBu)=O](PPh3)}[PF6], and Subsequent Reactivity
Towards Terminal Alkynes
Bernard Demerseman*[a] and Loïc Toupet[a]
Keywords: Cyclopentadienyl ligands / Metallacycles / Phosphane ligands / Ruthenium / Vinylidene ligands
The deprotonation under basic conditions of the keto-phos-
phane ligand in complexes {Ru(Cp)[η1-P-Ph2PCH2C(=O)-
tBu](PPh3)(L)}[PF6] (L = CO or PMe3) that arise from the ad-
dition of L to {Ru(Cp)[η2-P,O-Ph2PCH2C(tBu)=O](PPh3)}[PF6]
generates {Ru+(Cp)[η1-P-Ph2PCH=C(tBu)O–](PPh3)(L)} zwit-
Ph2PCH2C(tBu)=O](PMe3)}[PF6], which reacts in methanol
at reflux with 1,1-diphenyl-2-propyn-1-ol to afford the
six-membered
metallacyclic
derivative
{Ru(Cp)[η2-
C,P:C(CH=CPh2)OC(tBu)=CH–PPh2](PMe3)}[PF6], as shown
by an X-ray single crystal analysis. The synthesis of related
terionic species, as shown by an X-ray crystal structure deter- η5-indenyl ruthenium complexes and of {Ru(Cp)-
mination (L = CO). The removal of the triphenylphosphane
ligand is subsequently achieved under thermal activation to
afford the neutral derivatives Ru(Cp)[η2-P,O-Ph2PCH=C-
(tBu)O](L). A further protonation step is sufficient to com-
plete the formation of the new complex {Ru(Cp)[η2-P,O-
(=C=CH2)[Ph2PCH2C(=O)tBu](PR3)}[PF6] (PR3 = PPh3 or
PMe3) vinylidene complexes is also reported.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
Introduction
Enolato-phosphane chelates derived from β-keto-phos-
phanes associate an ancillary phosphorus coordinating cen-
tre with a strongly coordinating but reactive enolate moiety.
Thus, the enolato function had been shown to interfere in
the 1-alkyne to vinylidene rearrangement when coordina-
tion of 1-alkynes at a ruthenium centre was additionally
instigated. As depicted on Scheme 1, carbon–carbon bond
formation occurred and resulted in cationic metallacyclic
derivatives A and B.[1–3]
On the other hand, protonation of the enolato function
under acidic conditions converted the chelate into a hemi-
labile β-keto-phosphane one, where the oxygen atom might
compare to a weakly coordinating ketone.[4–6] Taking ad-
vantage of the hemilabile property of β-keto-phosphanes in Scheme 1. Carbon–carbon coupling reactions leading to ruthena-
cycles A–C.
related cyclopentadienyl ruthenium complexes, the synthe-
sis of allenylidene ruthenium derivatives had been achieved
(Scheme 1).[7] A further deprotonation of the η1-P-coordi-
late, or generated in situ under basic conditions from η1-P-
nated keto-phosphane still resulted in a formal carbon–car-
coordinated keto-phosphane. We wish to report now (i) an
bon coupling reaction between an enolate moiety and the
allenylidene ligand to afford a neutral ruthenaphosphacy-
clobutane derivative (C).
These results emphasised the nucleophilic character of
the enolate moiety from functional enolato-phosphane che-
ligand-exchange reactions, and (iii) the formation of a ru-
unusual η1-P coordination mode of an enolate-phosphane
ligand in new zwitterionic cyclopentadienyl ruthenium
complexes, (ii) the reactivity of the uncoordinated anionic
enolate moiety, which provides a new tool to cleanly achieve
thenaoxophosphacyclohexadiene ring, which may be for-
mally summarised as an oxygen–carbon coupling reaction
between an allenylidene ligand and an η1-P-coordinated
enol-phosphane.
[a] Institut de Chimie de Rennes, UMR-CNRS 6509, Organomé-
talliques et Catalyse, Université de Rennes 1,
35042 Rennes Cedex, France
Fax: +33-223236939
E-mail: bernard.demerseman@univ-rennes1.fr
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Results and Discussion
The hemilabile property of the β-keto-phosphane in the
cyclopentadienyl ruthenium complex {Ru(Cp)[η2-P,O-
Ph2PCH2C(tBu)=O](PPh3)}[PF6] (1a) allowed the entrance
not only of 1-alkynols or carbon monoxide as reported pre-
viously,[7] but also of phosphorus ligands such as trimeth-
ylphosphane or trimethyl phosphite [Equation (1)].
(2)
value of 27.1 Hz and assigned to the PCH= proton,
whereas the 13C{1H} NMR resonance of the corresponding
carbon nucleus displayed usual features (δ = 60.6 ppm, 1JPC
= 70.9 Hz). Further characterisation of 3b was obtained
from an X-ray crystal structure determination. An ORTEP
drawing of 3b is shown in Figure 1, and selected bond
lengths and angles are given in the caption.
(1)
The new complexes 2c,d were thus isolated as yellow sol-
ids in a nearly quantitative yield and were characterised by
1
a combination of H, 13C{1H}, 13C and 31P{1H} NMR, IR
1
spectroscopy, and elemental analysis. The H and 31P{1H}
NMR spectra accounted for the coordination of the phos-
phorus ligands besides the cyclopentadienyl one while IR
spectroscopy indicated the η1-P-coordination mode of the
keto-phosphane.[7] Attempts to achieve a similar entrance
of triphenylphosphane failed. Indeed, steric congestion
in the putative expected complex {Ru(Cp)[η1-P-
Ph2PCH2C(=O)tBu](PPh3)2}[PF6] was believed to be re-
sponsible for the easy synthesis of 1a, by reacting the keto-
phosphane Ph2PCH2C(=O)tBu with RuCl(Cp)(PPh3)2 and
NH4PF6 in methanol as solvent.[7] The loss of steric con-
straints in complexes 2b–d provided thermal stability and
complexes 2b–d remained unchanged when they were
heated in toluene at reflux. Unfortunately, such thermal sta-
bility precluded a removal of the triphenylphosphane ligand
in 2b–d and thus an easy recovery of the chelate coordina-
tion mode of the keto-phosphane.
Figure 1. ORTEP drawing of 3b·CH2Cl2 showing 50% probability
thermal ellipsoids. The CH2Cl2 molecule is omitted for clarity. Se-
lected bond lengths [Å] and angles [°]: Ru1–C6 1.858(5), Ru1–P1
2.339(1), Ru1–P2 2.370(1), C7–C8 1.379(5), C8–C9 1.561(6), C8–
O2 1.271(5), P2–C7 1.759(4); C7–C8–C9 120.1(4), C7–C8–O2
124.1(4), C8–C7–P2 123.7(3), C9–C8–O2 115.8(4), C7–P2–Ru1
120.7(1), C6–Ru1–P1 90.5(1), C6–Ru1–P2 91.3(1), P1–Ru1–P2
99.19(4).
The generation of an enolate anion might be expected to
enhance the reactivity of the oxygen atom from the keto-
Complex 3b disclosed a classical piano-stool geometry
phosphane when involved as an η1-P-coordinated ligand, involving an η5-cyclopentadienyl ruthenium moiety. One
but such a formation would require basic conditions. No carbon monoxide ligand and two phosphorus atoms com-
reaction was detected when an excess of KOH was added to plete the coordination of a formal Ru+ centre. Moreover,
a stirred solution of 2b in methanol. However, a subsequent the two Ru–P bond lengths are close [Ru1–P1: 2.339(1),
complete removal of volatiles under prolonged vacuum at Ru1–P2: 2.370(1) Å], thus providing straightforward evi-
room temperature resulted in the formation of the new eno- dence for a normal coordination of the functionalised phos-
late-phosphane complex 3b [Equation (2)].
phane. The C7–C8 and C8–O2 bond lengths [1.379(5) and
Complex 3b was isolated in 79% yield as orange crystals 1.271(5) Å, respectively] clearly indicated a marked double
that were found to be stable in air and could be kept at bond character, as expected for an anionic enolate frag-
room temperature. IR spectroscopy indicated the retention ment. Therefore, complex 3b is best described as a zwitter-
of a carbon monoxide ligand (ν = 1959 cm–1) and the con- ionic compound. Remarkably, the O2 oxygen atom lies in a
˜
version of the keto-function into an enolate one (ν = cis position relative to the P2 phosphorus atom, thus in a
˜
1489 cm–1). The 31P{1H} NMR spectrum of 3b indicated favourable position for a subsequent coordination of the
the coordination of two phosphorus atoms with a normal oxygen atom.
coupling constant value (2JPP = 26.7 Hz). More noteworthy
The removal of the triphenylphosphane ligand in 3b was
was the observation by 1H NMR spectroscopy of a doublet achieved by heating at reflux a solution of 3b in THF moni-
at δ = 3.66 ppm exhibiting a high JPH coupling constant tored by 31P{1H} NMR spectroscopy as having a new sing-
2
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A Tool for Selective Ligand Substitution
FULL PAPER
let resonance at δ = 61.4 ppm, besides a singlet resonance,
Further emphasising the usefulness of the hemilabile
as might be expected from the presence of free tri- property of the keto-phosphane ligand to conveniently al-
phenylphosphane [Equation (3)].
low the entrance of an additional ligand, complexes 1a,c
reacted with ethyne under very mild conditions (1 atm,
room temperature) to afford the new vinylidene complexes
5a,c [Equation (5)].
(3)
Attempts to separate the enolato-phosphane derivative
4b from free triphenylphosphane by generating under
acidic
conditions
a
less
soluble
cationic
{Ru(Cp)[Ph2PCH2C(tBu)=O](CO)}+ species immediately
showed the additional coordination of triphenylphosphane
leading to the recovery of cationic 2b. The addition of ICH3
to convert the free phosphane into the corresponding phos-
phonium salt was more successful. The neutral complex 4b
was then selectively extracted with diethyl ether and isolated
as orange-yellow crystals in 72% yield. Of interest is the
comparison of the 1H and 13C{1H} NMR spectra of 4b
and 3b, which showed in the case of 4b the PCH= proton
resonance as a doublet at δ = 4.85 ppm with a normal 2JPH
coupling constant value of 4.1 Hz, while the corresponding
(5)
1
13C{1H} NMR resonance (δ = 74.0 ppm, JPC = 61.9 Hz)
Complexes 5a,c were isolated as yellow-brown crystals in
93% and 92% yield, respectively, and fully characterised by
1H, 13C{1H}, 13C and 31P{1H} NMR spectroscopy, and ele-
mental analysis. Several unsubstituted vinylidene ruthenium
complexes have been reported previously,[8] but the almost
quantitative formation of 5a,c using ethyne under mild con-
ditions, and avoiding any formation of by-product, is note-
worthy. Under the same experimental conditions, the parent
complex RuCl(Cp)(PMe2Ph)2 reacted with ethyne in the
presence of TlBF4 to afford the η2-ethyne complex
Ru(Cp)(η2-C2H2)(PMe2Ph)2, from which the 1-alkyne to
vinylidene rearrangement needed a thermal activation to
occur.[9] Similar observations were made starting from
RuCl(Cp)(PMe3)2,[10] and the mechanism of the isomeris-
ation has been fully investigated.[11] The 13C{1H} NMR
spectra of 5a,c showed a very low-field resonance at δ =
346.6 and 345.5 ppm, respectively, and thus unambiguously
provided evidence for the presence of a vinylidene ligand.
Furthermore, complexes 5a,c easily added primary amines
such as isopropylamine to afford amino-carbene derivatives,
as emphasised by the formation of complex 6a [Equa-
tion (5)]. Like the vinylidene ruthenium complexes 5a,c, the
amino-carbene derivative 6a was a robust compound, which
could be kept in air at room temperature.
appeared moderately low-field shifted, relative to 3b.
The study of the reaction between 2c (L = PMe3) and
KOH in methanol as solvent under similar experimental
conditions was disappointing, as the 31P{1H} NMR spec-
trum of the crude product showed a major presence of un-
reacted 2c. However, a new set of resonances might indicate
a partial formation of the expected zwitterionic intermedi-
ate and thus suggested that more drastic experimental con-
ditions would allow completion of the reaction. Indeed, the
enolato-diphenylphosphane complex 4c was straightfor-
wardly obtained when NaH was used as a base in THF at
reflux [Equation (4)]. A subsequent treatment under acidic
conditions (addition of anhydrous HCl and NH4PF6 in
methanol as solvent) led to the new cationic derivative
{Ru(Cp)[Ph2PCH2C(tBu)=O](PMe3)}[PF6] (1c) [Equa-
tion (4)].
(4)
The labile keto-oxygen ligand in complexes 1a,c also al-
With the addition of trimethylphosphane to 1a to gener- lowed the entrance of 1-alkynols and the synthesis of the
ate 2c, as a supplementary step, the whole process achieved allenylidene derivative {Ru(Cp)(=C=C=CPh2)[Ph2PCH2C-
the selective substitution of the triphenylphosphane ligand (=O)tBu](PPh3)}[PF6] by reacting 1a with 1,1-diphenyl-2-
in 1a by a trimethylphosphane one, to afford 1c in 73% propyn-1-ol in methanol at reflux has already been re-
yield. NMR and IR spectroscopy, and elemental analysis ported.[7] By contrast, a distinct complex 7c was selectively
accounted for the structure of the stable complexes 4c and formed when the same alkynol was treated with 1c under
1c.
similar experimental conditions (Scheme 2).
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Figure 2 displays a piano-stool geometry where a car-
bene and two phosphorus ligands complete the coordina-
tion of a formal cationic η5-cyclopentadienyl ruthenium
fragment. One phosphorus and the (carbene)-carbon atoms
are involved in a six-membered metallacycle that is closely
planar, as monitored by a sum of internal angles of 717.1°,
close to 720°. Furthermore, the ruthenacycle compares with
a 1,4-cyclohexadiene ring wherein the Ru1–P1–C6 and C7–
O1–C15 fragments are linked through two short C6–C7 and
Ru1–C15 double bonds [1.319(4) and 1.924(3) Å, respec-
tively].
The formation of 7c was strongly dependent on the na-
ture of the solvent and became almost negligible when the
reaction between 1c and 1,1-diphenyl-2-propyn-1-ol was
conducted in dichloromethane at room temperature. As
monitored by 31P{1H} NMR spectroscopy, the complete
consumption of 1c in dichloromethane as solvent was vir-
tually achieved after 20 h and the reaction mixture dis-
closed a major presence (ca. 85% as determined by 1H
NMR spectroscopy) of the hydroxy-vinylidene complex 8c
(Scheme 2). Complex 8c then gradually disappeared, leav-
ing the allenylidene ruthenium complex 9c as the final prod-
uct after 3 days; no further change was detected after 10
days. Complex 9c can be rapidly synthesised by reacting 1c
and the alkynol in THF at reflux. The structure of com-
Scheme 2. Reactivity of complex 1c towards 1,1-diphenyl-2-pro-
pyn-1-ol: (i) in CH2Cl2 as solvent, (ii) in MeOH as solvent (room
temperature), (iii) in CH2Cl2 as solvent and in the presence of aque-
ous K2CO3.
Such a formation of 7c in methanol also occurred at
room temperature but the completion of the reaction
needed 10 days instead of 1 h under reflux conditions. The
stable complex 7c was isolated in 69% yield as dark-red
crystals. The 31P{1H} NMR spectrum of 7c indicated the
retention of two coordinating phosphorus centres, while 1H
NMR and IR spectroscopy both indicated the transforma-
tion of the keto-phosphane into an enolate-phosphane.
Furthermore, the 13C{1H} NMR spectrum of 7c exhibited
a very low-field resonance at δ = 286.1 ppm and thus sug-
gested that a carbene ligand completed the coordination of
the ruthenium centre. Finally, an X-ray crystal structure de-
termination of 7c showed a vinyl-carbene ligand to formally
arise from an addition at the Cα position of an allenylidene
ligand of the enol form of an η1-P-coordinated keto-phos-
phane. An ORTEP drawing of 7c is shown in Figure 2, and
selected bond lengths and angles are given in the caption.
1
plexes 8c and 9c was inferred from H, 13C{1H}, 13C and
1
31P{1H} NMR spectroscopic studies. Thus, the H NMR
spectrum of 8c showed two additional resonances relative
4
to the spectrum of 9c, at δ = 3.19 (s) and 5.25 (dd, JPH
=
2.5 and 1.6 Hz) ppm, which might reasonably be assigned
to the OH and Ru=C=CH protons, respectively.[12,13]
The
formation
of
the
allenylidene
complex
[Ru(Cp)(=C=C=CPh2)(PMe3)2][PF6] similarly involved a
hydroxy-vinylidene intermediate when RuCl(Cp)(PMe3)2
was treated with 1,1-diphenyl-2-propyn-1-ol.[14] Moreover,
several hydroxy-vinylidene complexes have been later iso-
lated and characterised as pentamethylcyclopentadienyl ru-
thenium derivatives.[12,13]
The formation of the isomeric complexes 7c and 9c, in
methanol and in dichloromethane as solvent, respectively,
was intriguing. Two supplementary experiments were signif-
icantly informative. First, a mixture of 8c and 9c in an ap-
proximately 1:1 molar ratio was formed in dichloromethane
and the solvent was evaporated under vacuum. The residue
was dissolved in methanol and the solution was stirred at
room temperature for 20 h. The examination of the re-
sulting solution by 31P{1H} NMR spectroscopy surpris-
ingly disclosed a mixture of 7c and 9c, indicating a conver-
sion of 8c into 7c but also a passiveness of the allenylidene
complex 9c (Scheme 2). However, a very slow isomerisation
of 9c into 7c, needing 10 days to complete, was observed to
occur in methanol at ambient temperature.
In the second experiment, a small amount of a 0.07 
K2CO3 aqueous solution was added to a solution of 9c in
dichloromethane. On stirring, the colour of the solution
rapidly (Ͻ1 h) turned from violet to red and although a
deprotonation of the keto-phosphane in 9c under such mild
heterogeneous conditions was unlikely, 7c was observed to
Figure 2. ORTEP drawing of 7c showing 50% probability thermal
ellipsoids. The hydrogen atoms and the PF6 anion are omitted for
clarity. Selected bond lengths [Å] and angles [°]: Ru1–C15 1.924(3),
Ru1–P1 2.2497(7), Ru1–P2 2.3197(8), C6–C7 1.319(4), C7–O1
1.393(3), P1–C6 1.776(3), C15–C16 1.472(4), C16–C17 1.354(4);
C6–P1–Ru1 113.2(1), C7–C6–P1 125.6(2), C6–C7–O1 125.7(3),
C7–O1–C15 128.1(2), O1–C15–Ru1 134.3(2), C15–Ru1–P1
90.21(8), C15–Ru1–P2 89.62(8), P1–Ru1–P2 95.57(3), Ru1–C15–
C16 119.1(2), C15–C16–C17 129.0(3).
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A Tool for Selective Ligand Substitution
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be quantitatively formed by 31P{1H} NMR spectroscopy
(Scheme 2).
These observations suggested that the coupling process
leading to 7c preliminarily required the formation of an in-
termediate that would arise either from 8c in methanol or
from the addition of hydroxide anion to 9c. As depicted in
Scheme 3, a plausible candidate consisted of a neutral alky-
nyl complex arising from a deprotonation (requiring a sol-
vent with proton-acceptor ability such as methanol) of the
vinylidene ligand in 8c, or from the addition of hydroxide
anion at the γ position of the allenylidene ligand in 9c. A
subsequent proton migration from the keto-fragment to the
alkynyl ligand would subsequently lead to 7c. Finally, the
presence of a bulkier triphenylphosphane ligand in 1a
might sufficiently hinder closeness between the keto func-
tion and the alkynyl chain to preclude a similar coupling
process.
Scheme 4. Synthesis of the new complexes 2Јc, 1Јc and 7Јc: (i)
PMe3, CH2Cl2, (ii) NaH, THF, reflux, (iii) HCl, NH4PF6, MeOH,
(iv) HCϵCC(OH)Ph2, MeOH, reflux.
Conclusions
The deprotonation of an η1-P-coordinated β-keto-phos-
phane in cyclopentadienyl or indenyl ruthenium complexes
was achieved under basic conditions and was observed to
enhance the affinity of the oxygen atom to coordinate the
metal centre. Subsequent removal of a triphenylphosphane
ligand was facilitated and allowed the chelate coordination
mode of the functionalised phosphane. Thus, using the β-
keto-phosphane as a tool, the substitution of a tri-
phenylphosphane ligand by a less sterically demanding li-
gand such as carbon monoxide or trimethylphosphane was
achieved. Furthermore, such a synthesis offered an oppor-
tunity to compare two analogous complexes but with dis-
tinct steric constraints. The presence of the hemilabile β-
keto-phosphane not only allowed an easy additional coor-
dination of ethyne but also facilitated further rearrange-
ment into vinylidene derivatives. The coordination of 1-al-
kynols similarly led to allenylidene complexes, but the pres-
ence of a reactive functionalised phosphane might interfere
in the process to afford new metallacyclic complexes.
Scheme 3. Rationale accounting (i) for the formation of 7c in meth-
anol and (ii) for the isomerisation of 9c into 7c catalysed by hydrox-
ide anions.
Experimental Section
The reactions allowing the synthesis of the trimeth-
General Comments: The reactions were performed under inert ar-
ylphosphane derivatives 2c, 1c and 7c tolerated the presence gon according to Schlenk-type techniques. THF, diethyl ether and
dichloromethane were distilled after drying according to conven-
tional methods. NMR spectra were recorded at 297 K with an AC
300 Bruker instrument and referenced internally to the solvent
peak. IR spectra were recorded as Nujol mulls with Bruker IFS28.
Elemental analyses were performed by the “Service de Microana-
lyse du CNRS”, Vernaison, France. Complexes 1a (as its dichloro-
methane adduct) and 1Јa were prepared as described previously.[7]
of an indenyl ligand instead of the cyclopentadienyl one. As
summarised in Scheme 4, the indenyl ruthenium precursor
complex {Ru(Ind)[η2-P,O-Ph2PCH2C(tBu)=O](PPh3)}[PF6]
(1Јa) (Ind = η5-C9H7)[7] easily added trimethylphosphane to
afford 2Јc, which was isolated as orange-red crystals, in
89% yield. Treatment of 2Јc with NaH in THF under reflux
and subsequent work under acidic conditions (HCl +
NH4PF6) led to 1Јc, which was isolated as orange crystals,
in 77% yield. Finally, complex 1Јc reacted with 1,1-di-
phenyl-2-propyn-1-ol in methanol at reflux to afford 7Јc
isolated as deep-red crystals, in 71% yield. The 1H,
13C{1H}, 13C and 31P{1H} NMR spectroscopic data col-
lected for 7Јc unambiguously indicated a similar structure
relative to complex 7c.
{Ru(Cp)[Ph2PCH2C(=O)tBu](PPh3)(CO)}[PF6] (2b): In a 125 mL
stainless steel vessel, a solution of 1a (13.8 g, 14.6 mmol) in dichlo-
romethane (70 mL) was stirred for 3 days at room temperature un-
der carbon monoxide pressure (65 atm). The resulting solution was
concentrated under vacuum (Ϸ40 mL) before being covered with
methanol (10 mL) and then diethyl ether (160 mL), to afford le-
mon-yellow crystals. Yield: 11.9 g, 92%. 13C{1H} NMR
(75.47 MHz, CD2Cl2): δ = 25.7 (s, CMe3), 35.9 (d, 1J = 29.4 Hz,
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PCH2), 45.5 (d, J = 1.5 Hz, CMe3), 90.9 (s, Cp), 129.0–135.1 (m,
3
of the crude product after evaporation of the resulting dichloro-
5 Ph groups), 202.5 (t, 2J Ϸ 17.8 Hz, CϵO), 207.6 (d, J = 8.2 Hz, methane solution by 1H and 31P{1H} NMR spectroscopy disclosed
2
C=O) ppm. 1H and 31P{1H} NMR, and IR spectroscopic data were
given elsewhere.[7]
resonances corresponding to unreacted 2c as well as a new set of
resonances arising from the presence of the assumed zwitterionic
complex. 1H NMR (300.13 MHz, CDCl3, available values): δ =
{Ru(Cp)[Ph2PCH2C(=O)tBu](PPh3)(PMe3)}[PF6] (2c):
A 1.0 
2
1.01 (s, 9 H, tBu), 1.44 (d, JPH = 8.6 Hz, 9 H, PMe3), 4.35 (s, 5
solution of trimethylphosphane in THF (8.0 mL, 8.0 mmol) was
added to a stirred solution of 1a (7.04 g, 7.47 mmol) in THF
(40 mL). The mixture was further stirred overnight to obtain a yel-
low precipitate, which was collected by filtration, then washed with
H, Cp) ppm. 31P{1H} NMR (121.50 MHz, CDCl3, the additional
presence of 2c is omitted): δ = –5.3 (t, 2JPP Ϸ 2JPPЈ Ϸ 42 Hz, PMe),
2
2
18.7 (dd, JPP = 42 and 35 Hz), 46.8 (dd, JPP = 42 and 35 Hz)
ppm.
diethyl ether and dried under vacuum. Yield: 7.00 g, 100%. IR: ν
˜
1
= 1699 cm–1, C=O. H NMR (300.13 MHz, CD2Cl2): δ = 0.64 (s,
Ru(Cp)[η2-P,O-Ph2PCH=C(tBu)O](CO) (4b): Crude 3b was ob-
tained from evaporation of the dichloromethane solution as de-
scribed above starting from 2b (13.0 g, 14.7 mmol), and then dis-
solved in THF (70 mL). The solution was heated at reflux for 20 h
and then evaporated. Dichloromethane (60 mL) then methyl iodide
(2.0 mL, 32.1 mmol, an excess) were added and this mixture was
stirred overnight, then evaporated. The residue was extracted with
diethyl ether (100 mL). The solution was filtered and the filtrate
was evaporated to leave crude 4b. Yield: 5.03 g, 72%. Heptane
(60 mL) was added to a solution of crude 4b in dichloromethane
(30 mL) and this solution was slowly concentrated under vacuum
to yield pure 4b as a crystalline yellow powder. Orange-yellow crys-
2
2
9 H, tBu), 1.45 (d, JPH = 8.6 Hz, 9 H, PMe3), 2.99 (dd, JHH
=
2
2
2
16.4, JPH = 8.5 Hz, 1 H, PCH2, Ha), 3.16 (dd, JHH = 16.4, JPH
= 4.0 Hz, 1 H, PCH2, Hb), 4.68 (s, 5 H, Cp), 6.80–7.47 (m, 25 H,
Ph) ppm. 31P{1H} NMR (121.50 MHz, CD2Cl2): δ = –10.4 (t, 2JPP
2
Ϸ
2JPPЈ Ϸ 38 Hz, PMe), 36.9 (t, JPP
Ϸ
2JPPЈ Ϸ 38 Hz), 43.9 (t,
2JPP
Ϸ
2JPPЈ Ϸ 38 Hz) ppm. C44H50F6OP4Ru (933.84): calcd. C
56.59, H 5.40; found C 56.66, H 5.87.
{Ru(Cp)[Ph2PCH2C(=O)tBu](PPh3)[P(OMe)3]}[PF6] (2d): Tri-
methyl phosphite (0.80 mL, 6.78 mmol) was added to a solution of
1a (3.00 g, 3.18 mmol) in dichloromethane (50 mL). After being
stirred overnight, the solution was evaporated to dryness to leave
the crude product. Recrystallisation from dichloromethane (20 mL)
and diethyl ether (110 mL) afforded thin yellow needles that were
tals were also obtained by recrystallisation from hot hexane. IR: ν
˜
= 1494 cm–1, C=CO; 1940 cm–1, CϵO. 1H NMR (300.13 MHz,
collected by filtration. Yield: 3.05 g, 98%. IR: ν = 1703 cm–1, C=O.
2
˜
C6D6): δ = 1.40 (s, 9 H, tBu), 4.45 (s, 5 H, Cp), 4.85 (d, JPH
=
1H NMR (300.13 MHz, CDCl3): δ = 0.55 (s, 9 H, tBu), 2.43 (dd,
4.1 Hz, 1 H, PCH=), 6.99–7.79 (m, 10 H, Ph) ppm. 13C{1H} NMR
(75.47 MHz, CD2Cl2): δ = 29.8 (s, CMe3), 39.3 (d, 3J = 12.1 Hz,
2
3
2JHH = 16.1, JPH = 10.8 Hz, 1 H, PCH2, Ha), 3.71 (d, JPH
=
=
2
CMe3), 74.0 (d, J = 61.9 Hz, PCH=), 84.5 (d, 2J = 1.6 Hz, Cp),
1
10.8 Hz, 10 H, POMe and hidden PCH2, Hb), 4.71 (d, JPH
0.7 Hz, 5 H, Cp), 6.92–7.61 (m, 25 H, Ph) ppm. 31P{1H} NMR
128.6 (d, J = 10.5 Hz, PPh, ortho), 128.6 (d, 2J = 10.8 Hz, PPh,
2
2
ortho), 129.2 (d, 4J = 2.6 Hz, PPh, para), 130.3 (d, 4J = 2.5 Hz,
PPh, para), 130.7 (d, 3J = 11.3 Hz, PPh, meta), 133.3 (d, 3J =
(121.50 MHz, CDCl3): δ = 41.9 (dd, JPP = 63 and 32 Hz, PPh),
45.9 (dd, 2JPP = 63 and 32 Hz, PPh), 144.3 (t, 2JPP Ϸ 2JPPЈ Ϸ 63 Hz,
POMe) ppm. C44H50F6O4P4Ru (981.84): calcd. C 53.83, H 5.13, P
12.62; found C 53.73, H 5.10, P 12.34.
1
10.8 Hz, PPh, meta), 136.9 (d, J = 62.0 Hz, PPh, ipso), 143.4 (d,
1J = 46.8 Hz, PPh, ipso), 202.7 (d, J = 15.5 Hz, =CO), 203.6 (d,
2
Ru+(Cp)[η1-P-Ph2PCH=C(tBu)O–](PPh3)(CO)·CH2Cl2 (3b):
A
2J = 18.9 Hz, CϵO) ppm. 31P{1H} NMR (121.50 MHz, C6D6): δ
mixture consisting of a sample of 2b (3.00 g, 3.39 mmol), KOH = 61.4 (s) ppm. C24H25O2PRu (477.51): calcd. C 60.37, H 5.28;
(0.31 g, 5.54 mmol) and methanol (50 mL) was stirred for 3 days at
room temperature. The resulting pale-yellow slurry was evaporated
under vacuum until an orange colour was observed, and the residue
was extracted with dichloromethane (20 mL). The solution was fil-
tered and the orange filtrate was covered with diethyl ether
(100 mL). The subsequent diffusion of solvents was conducted at
–20 °C to avoid decomposition, and afforded large orange crystals,
found C 60.54, H 5.28.
Ru(Cp)[η2-P,O-Ph2PCH=C(tBu)O](PMe3) (4): The slow concen-
tration under vacuum of a solution of crude 4c in methanol, the
preparation of which is detailed below (see synthesis of 1c), allowed
the formation of orange crystals of analytical purity. IR: ν =
˜
1492 cm–1, C=CO. 1H NMR (300.13 MHz, C6D6): δ = 0.91 (d, 2JPH
= 9.0 Hz, 9 H, PMe3), 1.42 (s, 9 H, tBu), 4.21 (s, 5 H, Cp), 4.95
which were washed with hexane (20 mL). Yield: 2.20 g, 79%. IR:
2
(d, JPH = 1.3 Hz, 1 H, PCH=), 6.98–7.74 (m, 10 H, Ph) ppm.
1
ν = 1489 cm–1, C=CO; 1959 cm–1, CϵO. H NMR (300.13 MHz,
˜
31P{1H} NMR (121.50 MHz, C6D6): δ = 6.8 (d, JPP = 42 Hz,
2
2
CD2Cl2): δ = 1.10 (s, 9 H, tBu), 3.66 (d, JPH = 27.1 Hz, 1 H,
2
PMe), 64.8 (d, JPP = 42 Hz, PPh) ppm. C26H34OP2Ru (525.58):
PCH=), 4.98 (s, 5 H, Cp), 7.00–7.65 (m, 25 H, Ph) ppm. 13C{1H}
calcd. C 59.42, H 6.52, P 11.79; found C 59.72, H 6.71, P 12.12.
NMR (75.47 MHz, CD2Cl2): δ = 29.6 (s, CMe3), 40.7 (d, 3J =
1
10.7 Hz, CMe3), 60.6 (d, J = 70.9 Hz, PCH=), 90.4 (s, Cp), 127.8
{Ru(Cp)[Ph2PCH2C(tBu)=O](PMe3)}[PF6] (1): A mixture con-
sisting of a sample of 2c (6.13 g, 6.56 mmol), an excess of NaH
(0.89 g, 37.1 mmol) and THF (80 mL) was heated at reflux for 20 h.
The resulting mixture was filtered and the orange-yellow filtrate
was evaporated to dryness to leave crude 4c as a solid. The solid
was dissolved in hot methanol (50 mL) to obtain an orange solu-
tion that was filtered. NH4PF6 (1.34 g, 8.22 mmol) and a 6  solu-
tion of HCl in diethyl ether (2.0 mL, 12.0 mmol) were added to the
filtrate, and the mixture was further stirred for 10 min. The re-
sulting yellow precipitate was collected by filtration and washed
with diethyl ether (50 mL), and then extracted with dichlorometh-
ane (60 mL). The solution was filtered and the filtrate was covered
with methanol (20 mL) then diethyl ether (160 mL) to afford yellow
(d, 2J = 9.9 Hz, PPh, ortho), 127.8 (d, 2J = 10.8 Hz, PPh, ortho),
128.1 (d, 4J = 2.7 Hz, PPh, para), 128.5 (d, 2J = 9.9 Hz, PPh3,
ortho), 128.7 (d, 4J = 2.7 Hz, PPh, para), 130.6 (d, 4J = 1.8 Hz,
PPh3, para), 131.7 (d, 3J = 9.0 Hz, PPh, meta), 132.6 (d, 3J =
3
10.8 Hz, PPh, meta), 134.0 (d, J = 10.8 Hz, PPh3, meta), 135.3 (d,
1
1J = 48.5 Hz, PPh3, ipso), 140.8 (d, J = 53.0 Hz, PPh, ipso), 141.7
1
2
(d, J = 50.3 Hz, PPh, ipso), 191.9 (s, =CO), 205.6 (dd, J = 19.3
and 15.7 Hz, CϵO) ppm. 13C NMR (75.47 MHz, CD2Cl2, selected
1
1
values): δ = 60.6 (dd, JHC = 158, JPC = 70.5 Hz, PCH=) ppm.
31P{1H} NMR (121.50 MHz, CD2Cl2): δ = 19.5 (d, JPP = 27 Hz),
2
2
47.9 (d, JPP = 27 Hz). C42H40O2P2Ru·CH2Cl2 (824.73): calcd. C
62.62, H 5.13, Cl 8.60, P 7.51; found C 62.36, H 5.10, Cl 7.36, P
7.51.
Ru+(Cp)[η1-P-Ph2PCH=C(tBu)O–](PPh3)(PMe3): A similar treat-
ment of 2c with KOH in methanol was attempted, but examination
crystals. Yield: 3.20 g, 73%. IR: ν = 1603 cm–1, C=O. 1H NMR
˜
2
(300.13 MHz, CD2Cl2): δ = 1.16 (d, JPH = 9.1 Hz, 9 H, PMe3),
1.26 (s, 9 H, tBu), 3.32 (dd, 2JHH = 19.3, 2JPH = 7.2 Hz, 1 H, PCH2,
1578
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 1573–1581

A Tool for Selective Ligand Substitution
FULL PAPER
2
2
Ha), 4.23 (dd, JHH = 19.3, JPH = 10.7 Hz, 1 H, PCH2, Hb), 4.55 C=O), 247.3 (dd, 2J = 16.2 and 11.7 Hz, Ru=C) ppm. 31P{1H}
(s, 5 H, Cp), 6.87–7.64 (m, 10 H, Ph) ppm. 31P{1H} NMR
NMR (121.50 MHz, CD2Cl2): δ = 33.9 (d, JPP = 34 Hz), 51.2 (d,
2
(121.50 MHz, CD2Cl2): δ = 2.3 (d, JPP = 39 Hz, PMe), 67.3 (d, 2JPP = 34 Hz) ppm. C46H52F6NOP3Ru (942.91): calcd. C 58.60, H
2
2JPP = 39 Hz, PPh) ppm. C26H35F6OP3Ru (671.55): calcd. C 46.50,
5.56, N 1.49, P 9.85; found C 58.41, H 5.58, N 1.64, P 9.42.
H 5.25, P 13.84; found C 46.18, H 5.28, P 13.84.
{Ru(Cp)[η2-C,P-:C(CH=CPh2)OC(tBu)=CH–PPh2](PMe3)}[PF6]
{Ru(Cp)(=C=CH2)[Ph2PCH2C(=O)tBu](PPh3)}[PF6]·1/6CH2Cl2 (7c): A solution of 1c (1.52 g, 2.26 mmol) and 1,1-diphenyl-2-pro-
(5a): A solution of 1a (3.90 g, 4.14 mmol) in dichloromethane
(40 mL) was stirred for 2 days under ethyne. The resulting solution
was then covered with diethyl ether (120 mL) to afford orange-
pyn-1-ol (0.60 g, 2.88 mmol) in methanol (30 mL) was heated at
reflux for 1 h. The resulting dark-red mixture was evaporated under
vacuum and the residue was dissolved in dichloromethane (35 mL).
The solution was filtered and the filtrate was covered with meth-
anol (15 mL), then diethyl ether (130 mL) to afford dark-red crys-
brown crystals. Yield: 3.45 g, 93%. IR: ν = 1632 cm–1, =C=CH ;
˜
2
1703 cm–1, C=O. H NMR (300.13 MHz, CD2Cl2): δ = 0.60 (s, 9
1
2
2
H, tBu), 2.04 (dd, JHH = 17.6, JPH = 11.5 Hz, 1 H, PCH2, Ha),
3.76 (dd, JHH = 17.2, JPH = 2.4 Hz, 1 H, PCH2, Hb), 4.33 (dd, C=CPh2. H NMR (300.13 MHz, CD2Cl2): δ = 0.84 (s, 9 H, tBu),
tals. Yield: 1.34 g, 69 %. IR: ν = 1556 cm–1, C=CO; 1611 cm–1
,
˜
2
2
1
4JPH = 3.1 and 1.7 Hz, 2 H, =CH2), 5.06 (s, 5 H, Cp), 6.98–7.76
(m, 25 H, Ph) ppm. 13C{1H} NMR (75.47 MHz, CD2Cl2): δ = 25.8
(s, CMe3), 32.5 (d, 1J = 29.7 Hz, PCH2), 45.8 (d, 3J = 1.8 Hz,
CMe3), 94.9 (s, Cp), 97.5 (s, =CH2), 128.7–134.9 (m, Ph reso-
nances), 207.4 (d, 2J = 9.9 Hz, C=O), 346.6 (t, 2J Ϸ 15.7 Hz,
Ru=C) ppm. 13C NMR (75.47 MHz, CD2Cl2, selected values): δ =
1.19 (d, JPH = 10.1 Hz, 9 H, PMe3), 5.24 (s, 5 H, Cp), 5.83 (d,
2JPH = 0.8 Hz, 1 H, PCH=), 6.87 (s, 1 H, CH=CPh2), 7.08–7.62
(m, 20 H, Ph) ppm. 13C{1H} NMR (75.47 MHz, CD2Cl2): δ = 21.5
(d, 1J = 34.6 Hz, PMe3), 27.6 (s, CMe3), 39.0 (d, 3J = 7.1 Hz,
CMe3), 85.9 (d, 1J = 55.0 Hz, PCH=), 93.4 (s, Cp), 129.1–133.1 (m,
set of Ph resonances), 138.4 (s, CPh2), 140.2 and 142.1 (2 s, CPh2,
ipso), 142.2 (dd, 1J = 53.9, 3J = 2.7 Hz, PPh, ipso), 142.3 (s,
2
97.5 (t, JHC = 165 Hz, =CH2) ppm. 31P{1H} NMR (121.50 MHz,
1
2
2
CD2Cl2): δ = 38.8 (d, JPP = 27 Hz), 45.7 (d, JPP = 27 Hz) ppm. CHCPh2), 178.3 (d, 2J = 4.5 Hz, OCtBu), 286.1 (dd, 2J = 15.7
C
43H43F6OP3Ru·1/6CH2Cl2 (897.95): calcd. C 57.74, H 4.86, Cl
and 13.9 Hz, Ru=C) ppm. 13C NMR (75.47 MHz, CD2Cl2, selected
1
1
1.32, P 10.35; found C 57.44, H 4.87, Cl 1.13, P 10.06.
values): δ = 85.9 (dd, JHC = 160, JPC = 55.0 Hz, PCH=), 138.4
(d, 2JHC = 2.7 Hz, CPh2), 142.3 (d, 1JHC = 160 Hz, CHCPh2) ppm.
{Ru(Cp)(=C=CH2)[Ph2PCH2C(=O)tBu](PMe3)}[PF6] (5c): A solu-
tion of 1c (2.07 g, 3.08 mmol) in dichloromethane (60 mL) was
stirred for 2 days under ethyne. The resulting solution was then
covered with diethyl ether (130 mL) to afford yellow-brown crys-
31P{1H} NMR (121.50 MHz, CD2Cl2): δ = 5.9 (d, JPP = 36 Hz,
2
2
PMe), 35.5 (d, JPP = 36 Hz, PPh) ppm. C41H47F6OP3Ru (863.81):
calcd. C 57.01, H 5.48, P 10.76; found C 56.88, H 5.37, P 10.37.
tals. Yield: 1.97 g, 92%. IR: ν = 1630 cm–1, =C=CH ; 1706 cm–1,
{Ru(Cp)[=C=CHC(OH)Ph2][Ph2PCH2C(=O)tBu](PMe3)}[PF6]
(8c): An equimolar mixture of 1c and 1,1-diphenyl-2-propyn-1-ol
˜
2
C=O. 1H NMR (300.13 MHz, CD2Cl2): δ = 1.00 (s, 9 H, tBu), 1.22
2
2
2
(d, JPH = 10.5 Hz, 9 H, PMe3), 3.80 (dd, JHH = 17.6, JPH
=
was dissolved in CD2Cl2 in an NMR tube and the solution was
9.7 Hz, 1 H, PCH2, Ha), 4.02 (dd, JPH = 2.7 and 2.0 Hz, 2 H, kept at room temperature. H and 31P{1H} NMR spectra were re-
4
1
2
2
=CH2), 4.07 (dd, JHH = 17.6, JPH = 5.8 Hz, 1 H, PCH2, Hb),
corded after 20 h and showed 8c to be the major compound
5.35 (s, 5 H, Cp), 7.26–7.52 (m, 10 H, Ph) ppm. 13C{1H} NMR (Ϸ85%). 1H NMR (300.13 MHz, CD2Cl2, the presence of residual
(75.47 MHz, CD2Cl2): δ = 21.2 (d, 1J = 35.9 Hz, PMe3), 26.4 (s,
1c and of 9c is omitted): δ = 0.93 (s, 9 H, tBu), 1.10 (d, JPH
=
2
CMe3), 39.9 (d, 1J = 33.1 Hz, PCH2), 46.1 (d, 3J = 2.5 Hz, CMe3), 10.6 Hz, 9 H, PMe3), 3.19 (s, 1 H, OH), 3.81 (dd, JHH = 17.8,
2
92.8 (s, Cp), 95.1 (s, =CH2), 129.1 (d, 2J = 10.8 Hz, PPh, ortho),
2JPH = 9.1 Hz, 1 H, PCH2, Ha), 4.21 (dd, JHH = 17.8, JPH
=
2
2
129.4 (d, 2J = 10.8 Hz, PPh, ortho), 131.5 (d, 4J = 2.7 Hz, PPh, 6.1 Hz, 1 H, PCH2, Hb), 5.25 (dd, JPH = 2.5 and 1.6 Hz, 1 H,
4
para), 131.7 (d, 4J = 2.7 Hz, PPh, para), 132.6 (d, 3J = 10.8 Hz, =CH), 5.35 (s, 5 H, Cp), 7.26–7.61 (m, 20 H, Ph) ppm. 31P{1H}
PPh, meta), 132.9 (d, 3J = 10.8 Hz, PPh, meta), 133.9 (dd, 1J =
NMR (121.50 MHz, CD2Cl2): δ = 8.9 (d, 2JPP = 33 Hz, PMe), 38.4
51.2, 3J = 1.8 Hz, PPh, ipso), 135.4 (d, 1J = 50.3 Hz, PPh, ipso), (d, JPP = 33 Hz, PPh) ppm. The conversion of 8c into 9c was
2
2
2
209.0 (d, J = 6.9 Hz, C=O), 345.5 (t, J Ϸ 15.3 Hz, Ru=C) ppm. almost complete after 75 h.
13C NMR (75.47 MHz, CD2Cl2, selected values): δ = 95.1 (t, JHC
1
{Ru(Cp)(=C=C=CPh2)[Ph2PCH2C(=O)tBu](PMe3)}[PF6] (9c): A
= 164 Hz, =CH2) ppm. 31P{1H} NMR (121.50 MHz, CD2Cl2): δ
solution of 1c (2.51 g, 3.74 mmol) and 1,1-diphenyl-2-propyn-1-ol
(1.15 g, 5.52 mmol) in THF (40 mL) was heated at reflux for 2 h.
The resulting solution was evaporated under vacuum and the resi-
due was washed with diethyl ether to obtain a violet powder.
Recrystallisation from dichloromethane (40 mL) and diethyl ether
(130 mL) afforded a dark-green crystalline powder, but an obvious
minor presence of orange crystals (presumably 7c) precluded ele-
mental analysis. Yield: 2.68 g, Ϸ83 %. 1H NMR (300.13 MHz,
2
2
= 7.4 (d, JPP = 31 Hz, PMe), 38.0 (d, JPP = 31 Hz, PPh) ppm.
C28H37F6OP3Ru (697.58): calcd. C 48.21, H 5.35, P 13.32; found
C 48.00, H 5.46, P 13.08.
{Ru(Cp)(=CMeNHiPr)[Ph2PCH2C(=O)tBu](PPh3)}[PF6] (6a): Iso-
propylamine (1.00 mL, 11.7 mmol) was added to a solution of 5a
(3.02 g, 3.36 mmol) in dichloromethane (40 mL) and the mixture
was stirred for 20 h. The resulting green solution was evaporated
under vacuum. The residue was dissolved in dichloromethane
(30 mL) and the solution was covered with diethyl ether (140 mL)
2
CD2Cl2): δ = 0.74 (s, 9 H, tBu), 1.25 (d, JPH = 10.3 Hz, 9 H,
PMe3), 3.65 (dd, 2JHH = 17.6, 2JPH = 9.7 Hz, 1 H, PCH2, Ha), 3.96
to afford yellow crystals. Yield: 2.85 g, 90 %. 1 H NMR
(dd, JHH = 17.6, JPH = 4.4 Hz, 1 H, PCH2, Hb), 5.37 (s, 5 H,
2
2
3
(300.13 MHz, CD2Cl2): δ = 0.80 (s, 9 H, tBu), 1.10 (d, JHH
=
Cp), 7.22–7.81 (m, 20 H, Ph) ppm. 13C{1H} NMR (75.47 MHz,
6.8 Hz, 3 H, CHMe), 1.13 (d, JHH = 6.5 Hz, 3 H, CHMe), 2.36 CD2Cl2): δ = 22.1 (d, 1J = 34.5 Hz, PMe3), 26.1 (s, CMe3), 40.7 (d,
3
(s, 3 H, RuCMe), 2.53 (dd, 2JHH = 17.9, 2JPH = 4.4 Hz, 1 H, PCH2,
1J = 30.9 Hz, PCH2), 45.6 (d, 3J = 1.7 Hz, CMe3), 92.1 (s, Cp),
Ha), 3.64 (dd, JHH = 17.9, JPH = 12.3 Hz, 1 H, PCH2, Hb), 4.15 128.9 (d, J = 10.8 Hz, PPh, ortho), 129.2 (d, 2J = 10.8 Hz, PPh,
2
2
2
(m, 1 H, CHMe2), 4.46 (s, 5 H, Cp), 6.69–7.48 (m, 25 H, Ph), 10.4
ortho), 129.7 (s, =CPh2, ortho), 130.7 (s, =CPh2, meta), 131.1 (d, 4J
(broad s, 1 H, NH) ppm. 13C{1H} NMR (75.47 MHz, CD2Cl2): δ = 2.7 Hz, PPh, para), 131.5 (d, 4J = 2.7 Hz, PPh, para), Ϸ132.3
= 21.3 (s, CHMe), 21.6 (s, CHMe), 26.7 (s, CMe3), 38.0 (s,
RuCMe), 42.3 (d, 1J = 17.5 Hz, PCH2), 45.4 (s, CMe3), 51.6 (s,
and 132.2 (d, PPh, meta, and s, =CPh2, para), 132.9 (d, 3J = 9.9 Hz,
1
3
PPh, meta), 134.1 (dd, J = 49.4, J = 1.8 Hz, PPh, ipso), 136.1 (d,
1J = 47.6 Hz, PPh, ipso), 144.3 (s, =CPh2, ipso), 158.4 (t, 4J Ϸ
2
CHMe2), 88.0 (s, Cp), 128.5–145.8 (m, Ph), 215.0 (d, J = 4.5 Hz,
Eur. J. Inorg. Chem. 2006, 1573–1581
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1579

B. Demerseman, L. Toupet
FULL PAPER
3
0.9 Hz, =CPh2), 208.8 (dd, J = 2.7 and 1.3 Hz, Ru=C=C), 208.9
(0.78 g, 32.5 mmol) and THF (60 mL) was heated at reflux for 20 h.
The resulting mixture was filtered and the dark-orange filtrate was
evaporated to dryness. Methanol (50 mL) was added to the residue
and this mixture was stirred to obtain a red-orange slurry. NH4PF6
(0.60 g, 3.68 mmol) and then a 6  solution of HCl in diethyl ether
(2.0 mL, 12 mmol) were added to the slurry. The mixture was
stirred for 10 min and the resulting orange precipitate was collected
by filtration and washed with diethyl ether (50 mL). The solid was
extracted with dichloromethane (25 mL), the solution was filtered
and the filtrate was covered with methanol (10 mL) then diethyl
(d, 2J = 7.2 Hz, C=O), 293.2 (dd, 2J = 18.4 and 16.6 Hz, Ru=C)
ppm. 31P{1H} NMR (121.50 MHz, CD2Cl2): δ = 9.6 (d, JPP
=
2
2
36 Hz, PMe), 41.2 (d, JPP = 36 Hz, PPh).
Isomerisation of 9c into 7c: A solution of a sample of 9c in meth-
anol was stirred at room temperature and the isomerisation of 9c
into 7c was monitored by 31P{1H} NMR spectroscopy. Completion
of the reaction was reached after 15 days. A 0.07  aqueous solu-
tion of K2CO3 (2.0 mL, 0.14 mmol) was added to a solution of 9c
(1.80 g, 2.08 mmol) in dichloromethane (40 mL) and the mixture
was stirred for 1 h. Examination of the resulting orange-red solu-
tion by 31P{1H} NMR spectroscopy showed the isomerisation of
9c into 7c to be complete.
ether (120 mL) to afford orange crystals. Yield: 1.70 g, 77%. IR: ν
˜
= 1607 cm–1, C=O. H NMR (300.13 MHz, CD2Cl2): δ = 0.94 (d,
1
2
2JPH = 9.0 Hz, 9 H, PMe3), 1.19 (s, 9 H, tBu), 3.34 (dd, JHH
=
2
2
2
19.4, JPH = 7.6 Hz, 1 H, PCH2, Ha), 4.10 (dd, JHH = 19.4, JPH
= 10.9 Hz, 1 H, PCH2, Hb), 4.28 (m, 1 H, Ind), 4.61 (m, 1 H, Ind),
4.73 (m, 1 H, Ind), 6.82–7.62 (m, 14 H, Ph and Ind) ppm. 31P{1H}
NMR (121.50 MHz, CD2Cl2): δ = 0.9 (d, 2JPP = 38 Hz, PMe), 75.2
{Ru(Ind)[Ph2PCH2C(=O)tBu](PPh3)(PMe3)}[PF6] (2Јc): A 1.0 
solution of trimethylphosphane in THF (8.0 mL, 8.0 mmol) was
added to a solution of {Ru(Ind)[Ph2PCH2C(tBu)=O](PPh3)}[PF6]
(1Јa) (6.00 g, 6.61 mmol) in dichloromethane (50 mL). The mixture
was stirred overnight and then evaporated to dryness to leave the
crude product that was recrystallised from dichloromethane
(35 mL) and diethyl ether (140 mL) to afford orange-red crystals.
2
(d, JPP = 38 Hz, PPh) ppm. C30H37F6OP3Ru (721.61): calcd. C
49.93, H 5.17, P 12.88; found C 50.20, H 5.20, P 12.84.
{Ru(Ind)[η2-C,P-:C(CH=CPh2)OC(tBu)=CH–PPh2](PMe3)}[PF6]
(7Јc): Starting from 1Јc instead of 1c, the procedure detailed for the
synthesis of 7c was used and similarly yielded 7Јc as dark-purple
Yield: 5.78 g, 89 %. IR: ν = 1705 cm– 1 , C=O. 1 H NMR
(300.13 MHz, CD2Cl2): δ = 0.63 (s, 9 H, tBu), 1.46 (d, JPH
˜
2
=
1
crystals (71%). H NMR (300.13 MHz, CD2Cl2): δ = 0.70 (s, 9 H,
8.5 Hz, 9 H, PMe3), 3.11 (m, 2 H, PCH2), 4.51 (s, broad, 1 H, Ind),
5.44 (s, broad, 1 H, Ind), 5.57 (m, 1 H, Ind), 6.80–7.45 (m, 29 H,
Ph and Ind) ppm. 31P{1H} NMR (121.50 MHz, CD2Cl2): δ = –
2
2
tBu), 1.11 (d, JPH = 10.0 Hz, 9 H, PMe3), 4.46 (d, JPH = 1.6 Hz,
1 H, PCH=), 4.57 (m, 1 H, Ind), 5.68 (m, 1 H, Ind), 5.72 (s, 1 H,
CH=CPh2), 5.90 (m, 1 H, Ind), 6.29–7.61 (m, 24 H, Ph and Ind)
ppm. 13C{1H} NMR (75.47 MHz, CD2Cl2): δ = 20.1 (d, 1J =
10.5. (t, 2JPP Ϸ 2JPPЈ Ϸ 33 Hz, PMe), 42.8 (t, 2JPP Ϸ 2JPPЈ Ϸ 33 Hz),
2
45.0 (t, JPP
Ϸ
2JPPЈ Ϸ 33 Hz) ppm. C48H52F6OP4Ru (983.90):
3
34.1 Hz, PMe3), 27.4 (s, CMe3), 38.8 (d, J = 7.1 Hz, CMe3), 80.0
calcd. C 58.60, H 5.33, P 12.59; found C 58.51, H 5.34, P 12.64.
1
(s, Ind), 85.1 (d, J = 58.5 Hz, PCH=), 87.0 (s, Ind), 96.7 (s, Ind),
{Ru(Ind)[Ph2PCH2C(tBu)=O](PMe3)}[PF6] (1Јc): A mixture con-
sisting of a sample of 2Јc (3.00 g, 3.05 mmol), an excess of NaH
109.4 (d, 2J = 6.3 Hz, Ind), 120.2 (s, Ind), 120.7–133.3 (m, set of
4
Ph and Ind resonances), 137.9 (d, J = 2.7 Hz, CHCPh2), 139.3 (s,
Table 1. Crystallographic data for complexes 3b·CH2Cl2 and 7c.
Complex
3b·CH2Cl2
7c
Empirical formula
Molecular weight [gmol–1]
Crystal size [mm]
Crystal system
Space group
a [Å]
C43H42Cl2O2P2Ru
824.68
0.48×0.35×0.32
monoclinic
P21/c
10.7595(1)
28.0871(3)
13.6725(2)
109.5282(5)
3894.19(8)
4
C41H45F6OP3Ru
861.75
0.45×0.35×0.35
monoclinic
P21/n
11.8729(1)
25.8064(2)
13.2105(1)
96.4906(3)
4021.71(6)
4
b [Å]
c [Å]
β [°]
V [Å3]
Z
Density [gcm–3]
Temperature [K]
F(000)
1.407
293(2)
1696
1.423
293(2)
1768
Mo-Kα radiation, λ [Å]
Absorption coefficient [mm–1]
θ range [°]
0.71073
0.658
1.74–27.48
0 Ͻ h Ͻ 13
0 Ͻ k Ͻ 36
–17 Ͻ l Ͻ 16
33970
0.71073
0.568
2.70–27.48
0 Ͻ h Ͻ 15
0 Ͻ k Ͻ 33
–17 Ͻ l Ͻ 17
54682
Index ranges
Reflections collected
Independent reflections
Reflections I Ͼ 2σ(I)
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
8841 (Rint = 0.033)
6496
8841/0/447
1.014
R1 = 0.0593
wR2 = 0.1581
R1 = 0.0851
wR2 = 0.1769
1.786 and –1.618
9180 (Rint = 0.035)
7134
9180/0/470
1.019
R1 = 0.0437
wR2 = 0.1140
R1 = 0.0614
wR2 = 0.1250
0.869 and –0.840
R indices (all data)
Largest diff. peak/hole [eÅ–3]
w = 1/[σ2(Fo2) + (0.0949P)2 + 5.7242P] (3b), 1/[σ2(Fo2) + (0.0680P)2 + 2.4890P] (7c), where P = (Fo + 2Fc )/3
2
2
1580
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Eur. J. Inorg. Chem. 2006, 1573–1581

A Tool for Selective Ligand Substitution
CPh2), 140.2 and 140.6 (2 s, CPh2, ipso), 141.8 (dd, 1J = 55.7, J =
FULL PAPER
[2] B. Demerseman, B. Guilbert, C. Renouard, M. Gonzalez, P. H.
Dixneuf, D. Masi, C. Mealli, Organometallics 1993, 12, 3906–
3917.
[3] B. Guilbert, B. Demerseman, P. H. Dixneuf, C. Mealli, J.
Chem. Soc., Chem. Commun. 1989, 1035–1037.
[4] P. Braunstein, F. Naud, Angew. Chem. Int. Ed. 2001, 40, 680–
699.
[5] A. Bader, E. Lindner, Coord. Chem. Rev. 1991, 108, 27–110.
[6] J. C. Jeffrey, T. B. Rauchfuss, Inorg. Chem. 1979, 18, 2658–
2666.
3
2
2
2.7 Hz, PPh, ipso), 178.1 (d, J = 3.6 Hz, OCtBu), 285.4 (dd, J =
16.2 and 12.6 Hz, Ru=C) ppm. 13C NMR (75.47 MHz, CD2Cl2,
1
selected values): δ = 85.1 (dd, JHC = 160, 1JPC = 58.5 Hz, PCH=),
137.9 (d, 1JHC = 160 Hz, CHCPh2), 139.3 (d, 2JHC = 2.7 Hz, CPh2)
2
ppm. 31P{1H} NMR (121.50 MHz, CD2Cl2): δ = 1.6 (d, JPP
=
2
31 Hz, PMe), 42.5 (d, JPP = 31 Hz, PPh) ppm. C45H49F6OP3Ru
(913.87): calcd. C 59.14, H 5.40, P 10.17; found C 58.29, H 5.17,
Cl 0.73, P 10.34. The presence of chlorine indicated a slight reten-
tion of dichloromethane, which is likely responsible for the low
carbon value.
[7] P. Crochet, B. Demerseman, M. I. Vallejo, M. P. Gamasa, J.
Gimeno, J. Borge, S. García-Granda, Organometallics 1997, 16,
5406–5415.
X-ray Crystallography: Selected crystals of 3b·CH2Cl2 and 7c were
studied with a NONIUS Kappa CCD diffractometer with graphite
monochromator. Crystallographic data are given in Table 1. The
cell parameters were obtained with Denzo and Scalepack,[15] and
data collection with NONIUS KappaCCD Software.[16] Data re-
duction was carried out with Denzo and Scalepack.[15] The struc-
tures were solved with SIR-97, which revealed the non-hydrogen
atoms.[17] After anisotropic refinement, many hydrogen atoms may
be found with Fourier difference calculations. The whole structures
were refined with SHELXL97 by full-matrix least-squares methods
on F2 (x, y, z, βij for Ru, P, Cl, O and C atoms; x, y, z in riding mode
for H atoms).[18] ORTEP views were prepared with PLATON98.[19]
Thermal ellipsoids for some atoms in the C30 ring in 7c might
suggest a disorder problem. Calculations to split these atoms in
two positions to improve the structural model were unsuccessful,
probably because this defect is not symmetrical relative to the
phenyl ring axis.
[8] M. C. Puerta, P. Valerga, Coord. Chem. Rev. 1999, 193–195,
977–1025.
[9] J. R. Lomprey, J. P. Selegue, J. Am. Chem. Soc. 1992, 114,
5518–5523.
[10] R. M. Bullock, J. Chem. Soc., Chem. Commun. 1989, 165–166.
[11] I. de los Ríos, M. J. Tenorio, M. C. Puerta, P. Valerga, J. Am.
Chem. Soc. 1997, 119, 6529–6538.
[12] E. Bustelo, M. Jiménez-Tenorio, M. C. Puerta, P. Valerga, Or-
ganometallics 1999, 18, 4563–4573.
[13] E. Bustelo, M. Jiménez-Tenorio, M. C. Puerta, P. Valerga, Or-
ganometallics 1999, 18, 950–951.
[14] J. P. Selegue, Organometallics 1982, 1, 217–218.
[15] Processing of X-ray diffraction data collected in oscillation
mode: Z. Otwinowski, W. Minor, Macromol. Crystallogr. A
1997, 276, 307–326.
[16] NONIUS KappaCCD Software, Nonius BV, Delft, The Nether-
lands, 1999.
[17] SIR-97 – A New Tool for Crystal Structure Determination and
Refinement: A. Altomare, M. C. Burla, M. Camalli, G. Cas-
carano, C. Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G.
Polidori, R. Spagna, J. Appl. Crystallogr. 1998, 31, 74–77.
[18] G. M. Sheldrick, SHELXL97 – Program for the Refinement of
Crystal Structures, University of Göttingen, Germany, 1997.
[19] A. L. Spek, PLATON – A Multipurpose Crystallographic Tool,
University of Utrecht, The Netherlands, 1998.
Received: December 1, 2005
CCDC-291347 (for 3b) and -291348 (for 7c) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[1] P. Crochet, B. Demerseman, Organometallics 1995, 14, 2173–
2176.
Published Online: February 21, 2006
Eur. J. Inorg. Chem. 2006, 1573–1581
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1581