Ruthenium acetate complexes as versatile probes of metal-ligand interactions: Insight into the ligand effects of vinylidene, carbene, carbonyl, nitrosyl and isocyanide

Article abstract of DOI:10.1002/ejic.201100931

Reaction of cis-Ru(²-OAc)₂(PPh₃) ₂ with two-electron donor ligands L results in the formation of complexes trans-[Ru(¹-OAc)(²-OAc)L(PPh₃) ₂] (L = CO, NO⁺, CNtBu). Vinylidene complexes (L = C=CHR) may be prepared from the corresponding reaction with terminal alkynes HC=CR, and species containing hydroxyvinylidene ligands (L = C=CHCR¹R ²{OH}) may be prepared from related reactions with propargyl alcohols HC=CCR¹R²{OH}. Treatment of cis-Ru(κ²- OAc)₂(PPh₃)₂ with ω-alkynols HC=C(CH ₂)_nOH (n = 2-4) results in the formation of oxacyclocarbene complexes [L = CCH₂(CH₂)_nO]. An analysis of the spectroscopic data and the structural metrics (as determined by X-ray crystallography) of this series of complexes allows for the relative donor/acceptor properties of the ligand L to be evaluated. This comparison indicates that the vinylidene ligand behaves in a similar fashion to the isocyanide ligand. The complex cis-[Ru(²-OAc)₂(PPh ₃)₂] acts as a precursor for the formation of the complexes trans-[Ru(¹-OAc)(²-OAc)L(PPh₃) ₂] where L is a two-electron donor, σ-donor/π-acceptor ligand. The structural and spectroscopic data of these species provide insight into the relative electron demand of the ligands L.

Full text of DOI:10.1002/ejic.201100931

FULL PAPER
DOI: 10.1002/ejic.201100931
Ruthenium Acetate Complexes as Versatile Probes of Metal–Ligand
Interactions: Insight into the Ligand Effects of Vinylidene, Carbene, Carbonyl,
Nitrosyl and Isocyanide
Christine E. Welby,[a] Thomas O. Eschemann,[a] Christopher A. Unsworth,[a]
Elizabeth J. Smith,[a] Robert J. Thatcher,[a] Adrian C. Whitwood,[a] and Jason M. Lynam*[a]
Keywords: Ruthenium / Vinylidene ligands / Carbene ligands / Carbonyl ligands / Nitrosyl ligands / Isocyanide ligands /
Ligand effects
Reaction of cis-Ru(κ2-OAc)2(PPh3)2 with two-electron donor
ligands L results in the formation of complexes trans-[Ru(κ1-
OAc)(κ2-OAc)L(PPh3)2] (L = CO, NO+, CNtBu). Vinylidene
complexes (L = C=CHR) may be prepared from the corre-
sponding reaction with terminal alkynes HCϵCR, and spe-
Ru(κ2-OAc)2(PPh3)2 with ω-alkynols HCϵC(CH2)nOH (n = 2–
4) results in the formation of oxacyclocarbene complexes [L
= CCH2(CH2)nO]. An analysis of the spectroscopic data and
the structural metrics (as determined by X-ray crystallogra-
phy) of this series of complexes allows for the relative donor/
acceptor properties of the ligand L to be evaluated. This com-
parison indicates that the vinylidene ligand behaves in a sim-
ilar fashion to the isocyanide ligand.
cies
containing
hydroxyvinylidene
ligands
(L
=
C=CHCR1R2{OH}) may be prepared from related reactions
with propargyl alcohols HCϵCCR1R2{OH}. Treatment of cis-
mechanism.[7] In addition, 1 is able to catalyse the addition
of carboxylic acids to propargyl alcohols to give β-oxoprop-
yl ethers.[8]
Introduction
An understanding of metal–ligand interactions is crucial
for developing structure/activity relationships in transition-
metal chemistry. A popular method to probe the electronic
properties of a given ligand (or series of ligands) is to study
the changes in the IR spectrum of a suitable metal–carbonyl
complex.[1] The sensitivity of the C–O stretching frequency
to the environment of the metal ensures that this is a versa-
tile indicator of the electronic properties of the ligand in
question. One important aspect of this approach is to have
a consistent metal scaffold that will allow for facile incorpo-
ration of suitable ligands and allow a direct comparison of
their properties. For phosphane and N-heterocyclic carbene
ligands a number of frameworks have been employed in-
cluding [Ni(CO)3L],[1,2] [MCl(CO)2L] (M = Rh,[3] Ir[4]) and
Ir(η5-C5H5)(CO)L.[5]
We have previously demonstrated that the ruthenium
bis(acetate) complex cis-[Ru(κ2-OAc)2(PPh3)2] (1), which
contains mutually cis phosphane ligands, is a versatile pre-
cursor for the preparation of complexes containing vinyl-
idene ligands.[6] Reaction of 1 with, for example, HCϵCPh
results in the formation of vinylidene complexes under ex-
tremely mild conditions and a theoretical study demon-
strated that a key step in this process was an acetate-medi-
ated deprotonation/reprotonation of the alkyne, for which
we coined the term Ligand-Assisted Proton Shuttle (LAPS)
Given that 1 appears to react selectively with alkynes to
give vinylidene complexes and also with CO to give the
carbonyl complex trans-[Ru(κ1-OAc)(κ2-OAc)(CO)(PPh3)2]
(2),[6,9] we anticipated that it might be able to act as a versa-
tile precursor for complexes containing a range of σ-donor/
π-acceptor ligands. Furthermore, it was anticipated that,
given the presence of a considerable number of characteris-
tic spectroscopic features in the NMR and IR spectra, com-
plexes based on the trans-[Ru(κ1-OAc)(κ2-OAc)L(PPh3)2]
framework might act as potential probes for the nature of
the metal–ligand interactions.
We now report on the preparation of a series of com-
pounds of the general type trans-[Ru(κ1-OAc)(κ2-OAc)-
L(PPh3)2], where L = CO, NO+, CNtBu, vinylidene or carb-
ene. An analysis of the structural and spectroscopic param-
eters of these species enables the relative electron demands
of these ligands to be assessed.
Results and Discussion
Reaction of 1 with Two-Electron Donor Ligands
The reactions of 1 with two-electron donor, σ-donor/π-
acceptor ligands CO, NO+ and CNtBu all proceeded in a
similar fashion (Scheme 1). It has previously been reported
that treatment of a CH2Cl2 solution of 1 with CO for ca.
20 min results in the exclusive formation of trans-[Ru(κ1-
[a] Department of Chemistry, University of York,
York, YO10 5DD, UK
Fax: +44-1904-322516
E-mail: jason.lynam@york.ac.uk
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OAc)(κ2-OAc)(CO)(PPh3)2] (2), although prolonged carb- of a linear NO ligand in 3+ and the fact that the uncoordi-
onylation does result in the formation of [Ru(κ1-OAc)2- nated oxygen atom of the κ1-acetate exhibits a close interac-
(CO)2(PPh3)2].[6,8,9] As shown by single-crystal X-ray dif- tion with the nitrogen atom of this ligand: O(4)–N(1)
fraction and NMR spectroscopy, complex 2 contains two 2.773(3) Å. In the case of 2 this interaction is weaker [O(4)–
mutually trans PPh3 ligands. The κ1- and κ2-acetate ligands C(5) 2.840(2) Å], which may simply reflect the more electro-
undergo rapid exchange on the NMR timescale at room philic nature of the nitrogen in the nitrosyl ligand.
1
temperature: the H NMR spectrum of 2 exhibits a singlet
resonance for the methyl groups of the acetate ligands. On
cooling to 195 K this single peak undergoes decoalescence
and separate peaks for the methyl groups of the κ1- and κ2-
acetate are observed. All of the complexes prepared only
show a single resonance for the two acetate environments
at room temperature, which, in some examples, separate on
cooling. An analysis of this behaviour is presented later.
Scheme 1. (i) + CO(g), CH2Cl2, 20 min, room temp.; (ii) + NO[BF4],
CH2Cl2, 60 min, room temp.; (iii) + CNtBu, CH2Cl2, 30 min, room
temp.
The formation of the trans isomer of 2 contrasts with
the report by Robinson on the related complexes cis-[Ru(κ1-
O2CR)(κ2-O2CR)(CO)(PPh3)2] (R
= p-C6H4Cl or p-
C6H4NO2). These are prepared from the addition of the
appropriate carboxylic acid to [RuH2(CO)(PPh3)3] in boil-
ing 2-methoxyethanol (125 °C), which contains mutually
cis-phosphane ligands.[10] However, it should be noted that
prolonged heating of a sample of 2 for 50 d at 50 °C does
result in the formation of some cis-2. Notably, cis-2 is char-
acterised by a broad singlet resonance in the 31P{1H} NMR
spectrum at δP = 47.8 ppm, which resolved into two dou-
blets at δP = 45.7 and 49.0 ppm (2JPP = 25.0 Hz) when co-
oled to 235 K.
Figure 1. Molecular structures of (a) 2, (b) cation 3+ and (c) 4.
Thermal ellipsoids where shown are at the 50% probability level,
hydrogen atoms are omitted for clarity. The κ1-acetate ligand in 4
is disordered over two sites with an 82.4(2):17.6(2) occupancy, the
minor form being represented with hatched bonds.
The reaction of a CH2Cl2 solution of 1 with NO[BF4]
afforded
trans-[Ru(κ1-OAc)(κ2-OAc)(NO)(PPh3)2][BF4]
(3[BF4]), which is isoelectronic with 2. The pertinent fea-
1
tures in the H NMR and 31P{1H} NMR spectra displayed
by 2 are also exhibited by 3[BF4]. Notably a temperature-
invariant singlet resonance in the 31P{1H} NMR spectrum
The IR spectra of 3[BF4] recorded as a KBr disc exhib-
is consistent with a change in geometry of the phosphane ited many of the expected features, including a band at
ligands from cis in 1 to trans. This was confirmed by a sin- 1865 cm–1 confirming the presence of an NO ligand adopt-
gle-crystal X-ray diffraction study (Figure 1b), which dem- ing a linear geometry:[11] asymmetric and symmetric
onstrated that the cation 3+ possessed an essentially iden- stretches for an acetate ligand coordinated in a κ1-fashion
tical topology to that of 2. Although a more comprehensive were also observed. However no bands that could be as-
discussion of the structural metrics within this class of com- signed to an acetate ligand bound in κ2-fashion could be
plexes is presented later, it is important to note the presence observed.
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Ruthenium Acetate Complexes as Probes of Metal–Ligand Interactions
The reaction of 1 with CNtBu followed a similar pattern β-carbon at ca. δ = 110 ppm (3JPC ≈ 4 Hz). Triplet reso-
1
to that described for CO and NO+. The formation of trans- nances are observed in the H NMR spectrum for the pro-
[Ru(κ1-OAc)(κ2-OAc)(CNtBu)(PPh3)2] (4) was observed to ton attached to the β-carbon of the vinylidene ligand. The
occur over the course of ca. 30 min (as shown by a charac- chemical shift, however, exhibited a dependence on the na-
teristic colour change from orange to yellow). The structure ture of the functional group present.
of 4 was also confirmed by single-crystal X-ray diffraction
The structure of 6c was confirmed by single-crystal X-
(Figure 1c), which exhibited the expected trans disposition ray diffraction and, since our initial report, we have now
of the phosphane ligands and the presence of a linear obtained a satisfactory solution for a structure of complex
CNtBu ligand [Ru–C(5)–N(1) 175.6(2) °]. In contrast to 2 6b. The molecular structures of these two compounds in the
and 3[BF4] there is no close contact between the uncoordi- solid state are shown in Figure 2. The complexes exhibited
nated oxygen atom of the κ1-bound acetate ligand and the short ruthenium–carbon and carbon–carbon bond lengths
isocyanide ligand. As this is a weak interaction, crystal for the vinylidene ligand and demonstrated that the acetate
packing effects cannot be discounted. However, it would ligands are present in both κ2- and κ1-coordination modes.
also be expected that the metal-bound carbon of the iso-
cyanide would be less electrophilic than the carbonyl car-
bon in 2 and the nitrogen of the NO+ ligand in 3+. The IR
spectra of 4 in both CH2Cl2 solution and as a KBr disc
exhibit two bands in the region associated with the CϵN
stretch of the isocyanide ligand. Although the appearance
of two bands may be due to the occurrence of two different
conformations of the complex, Fermi resonance cannot be
excluded.[12]
Reaction of 1 with Terminal Alkynes
We have previously reported that the reaction of 1 with
the terminal alkynes HCϵCR [R = Ph (5a), R = CO2Me
(5b)] results in the formation of vinylidene complexes trans-
[Ru(κ1-OAc)(κ2-OAc)(=C=CH{R})(PPh3)2] [R = Ph (6a),
R = CO2Me (6b)].[6] The corresponding reaction of 1 with
propargyl alcohols, HCϵCCR1R2(OH) [R1 = R2 = Ph (7a),
R1 = R2 = Me (7b)], allow for the formation of hydroxy-
substituted
vinylidene
complexes
[Ru(κ1-OAc)(κ2-
OAc)(=C=CHCR1R2{OH})(PPh3)2] [R1 = R2 = Ph (8a),
R1 = R2 = Me (8b)]. The reaction of 1 with a number of
different terminal alkynes was investigated in order to ex-
plore the scope of this reaction with regard to functional
group tolerance and to investigate the potential effects of
different substitution on metal–ligand interactions.[13]
The reaction of
HCϵCSiMe3 (5d) results in the formation of vinylidene
complexes
[Ru(κ1-OAc)(κ2-OAc)(=C=CH{pyrene})-
1 with HCϵC(pyrene) (5c) or
(PPh3)2] (6c) and [Ru(κ1-OAc)(κ2-OAc)(=C=CHSiMe3)-
(PPh3)2] (6d), respectively (Scheme 2). The vinylidene com-
plexes exhibited a common set of spectroscopic features in-
cluding low-field triplet resonances for the α-carbon of the
vinylidene ligand at ca. δ = 350 ppm (2JPC ≈ 16 Hz) and the
Figure 2. Molecular structures of (a) 6b and (b) 6c. Thermal ellip-
soids where shown are at the 50% probability level, hydrogen atoms
(except for those attached to the vinylidene ligand) are omitted for
clarity.
The reaction of
1
with propargyl alcohols
HCϵCCR1R2(OH) (7) resulted, in all cases, in the rapid
formation of hydroxyvinylidene complexes 8, regardless of
the substituents employed (Scheme 3). This proved to be
the case even when substituted steroid ethisterone (7i) was
employed. As in the case of the simpler vinylidene com-
plexes 6, characteristic resonances were observed in the 13C
1
NMR and H NMR spectra of these species. Notably low-
field resonances for the α-carbon were observed again at ca.
δ = 350 ppm.
Scheme 2. Reaction of 1 with 5a–d. (i) CH2Cl2 solution, room
temp.,1 h.
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Scheme 3. Reaction of 1 with 7a–i. (i) CH2Cl2 solution, room
temp.,1 h.
The structures of complex 8e and 8f (Figure 3a and b)
were also confirmed by single-crystal X-ray diffraction. The
structures of these complexes again conform to the general
type showing κ1- and κ2-bound acetate ligands and two
PPh3 ligands in a mutually trans arrangement. The Ru–C
and C–C bond lengths within the vinylidene ligands are
typical.
In contrast to the solid structure of 8a, which exhibits an
intramolecular hydrogen bond between the OH group of
the hydroxyvinylidene ligand and the uncoordinated oxygen
atom of the κ1-acetate ligand, the structure of 8e appears
to show an OH–π interaction with one of the aromatic rings
of a PPh3 ligand.
The solid-state structure of 8f shows a further motif in
which the OH group of the hydroxyvinylidene ligand is en-
gaged in intermolecular hydrogen bonding with the uncoor-
dinated oxygen atom of the κ1-acetate ligand of a neigh-
bouring molecule [intermolecular distance O(5)–H(5)···O(4)
2.802(3) Å]. Additional weaker interactions are observed
between the CH2Cl2 of crystallisation and both the OH
group of the hydroxyvinylidene [O(5)–C(48) 3.243(4) Å] and
an oxygen atom of the κ2-acetate on a second molecule of
Figure 3. Molecular structures of (a) 8e and (b) 8f. Thermal ellip-
soids where shown are at the 50% probability level, hydrogen atoms
(except for those attached to the vinylidene ligand) are omitted for
clarity. (c) Solid-state hydrogen bonding motif observed in 8f.
8e [O(2)–C(48) 3.241(4) Å]. The net result of these effects is be the carbonyl complex 2 and alkenes H2C=CR1R2 (9)
to produce a one-dimensional polymer in the solid state, (Scheme 4). The stoichiometric[15] and catalytic[16] conver-
the structure of which is illustrated in Figure 3c.
sion of propargyl alcohols to alkenes has been reported pre-
The elimination of water from hydroxyvinylidene com- viously and alkenes have been observed as side products in
plexes to afford species containing allenylidene, other catalytic transformations of these substrates.[17] In the
M=C=C=CR1R2, ligands is
a well-established reac- case of complexes 8 the only significant difference in behav-
tion.[13f,14] All of the complexes with structure 8 were meta- iour is in the time required for this reaction to come to
stable, the ultimate products from these reactions proved to completion. In the case of complex 8c, in which the hy-
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Ruthenium Acetate Complexes as Probes of Metal–Ligand Interactions
droxyvinylidene ligand only contains hydrogen substituents, contrast, the treatment of 1 with HCϵC(CH2)4OH under
the generation of 2 and ethene is complete in 48 h. In con- identical conditions resulted in a much slower reaction: 11c
trast to the case of ethisterone-containing 8i this reaction was observed to be formed over a period of 24 h, although
required three weeks to reach completion. Indeed, the time no intermediates could be detected. As shown in Scheme 5,
for this reaction to achieve completion broadly correlates the generally accepted mechanism[19] for such a process in-
with the steric demands of the substituents on the vinyl- volves the initial formation of a vinylidene complex with a
idene.
pendant alcohol, which then undergoes nucleophilic attack
at the vinylidene α-carbon.
The spectroscopic data for complexes 11a–c support the
assignment of these species as oxacyclocarbene complexes.
For example, the 13C{1H} NMR spectra of the complexes
2
exhibited resonances at δ = 304.7 (t, JPC = 11.8 Hz), δ =
2
2
306.8 (t, JPC = 11.7 Hz) and δ = 311.0 ppm (t, JPC
=
11.8 Hz) for 11a, 11b and 11c, respectively. An analysis of
the chemical shift of a number of oxacyclocarbene ligands
(Table 1) demonstrates that this trend of increasing chemi-
cal shift with increasing ring size appears to be present in a
number of species of this type.[20]
Table 1. Comparison of carbene carbon chemical shifts in oxacy-
clocarbene ligands.
[M]
13C NMR:
13C NMR:
13C NMR:
δCα
δCα
δCα
[M]=C4H6O [M]=C5H8O [M]=C6H10
O
[Ru(OAc2)2(PPh3)2][a]
[RuTp(PPh2iPr)]Cl[b][21]
[RuTp(PPh3)]Cl[b][21]
304.7
313.2
314.4
296.3
295.1
300.3
296.8
293.4
306.8
318.3
320.2
302.5
302.5
308.1
303.9
303.0
311.0
323.7
325.0
306.8
306.7
312.5
307.5
310.8
[Ru(Ind)(PPh3)2][c][22]
[Ru(Ind)(PMe2Ph)2][c][22]
[Ru(Ind)(dppm)][c][22]
[Ru(Ind)(PPh3)(PMe3)][c][22]
[23]
[Re(triphos)(CO)2]BF4
[a] This work. [b] Tp = tris(pyrazolyl)borate. [c] Ind = η5-C9H7;
Scheme 4. (i) CH2Cl2, room temperature.
triphos = MeC(CH2PPh2)3.
Reaction of 1 with ω-Alkynols
The structures of complexes 11a–c were also confirmed
by single-crystal X-ray diffraction: the molecular structures
are presented in Figure 4. In all three cases the structure
determinations demonstrated that the complexes contained
two mutually trans-PPh3 ligands. In the case of 11a and 11c,
the ruthenium was also shown to be bound to a κ1- and a
κ2-OAc ligand with the remaining coordination site being
occupied by the oxacyclocarbene ligand. The structure of
11b is somewhat different from those of the other com-
plexes reported. It crystallised in the orthorhombic space
group Aba2 with the asymmetric unit constituting half the
complex. The acetate ligand in this complex is bound for-
mally in a κ1-fashion, although the distance of the uncoor-
dinated oxygen atom O(2) to the ruthenium is somewhat
shorter [2.748(2) Å] than in (for example) 11a [2.908(4) Å],
perhaps representing a weak interaction. In solution, the
1H NMR spectrum of 11b recorded at a low temperature
demonstrated that two inequivalent OAc groups were pres-
ent and the IR spectra recorded in CH2Cl2 solution or as a
KBr disc showed the presence of both κ1- and κ2-coordina-
tion modes. These data led to the conclusion that the con-
formation of the acetate ligands observed in the X-ray dif-
fraction experiment was not representative of the solution-
state behaviour.
Given that the reaction of 1 with terminal alkynes has
proven to be a selective method for the preparation of vinyl-
idene ligands, the corresponding reactions with ω-alkynols
HCϵC(CH2)nOH [n = 2 (10a), n = 3 (10b), n = 4 (10c)]
were investigated. In the case where n = 2 and 3 essentially
identical behaviour was observed: treatment of a CD2Cl2
solution of 1 with the appropriate alkyne at room tempera-
ture resulted in the rapid formation of the corresponding
oxacyclocarbene complexes 11a and 11b (Scheme 5).[18] In
Scheme 5.
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structurally-characterised oxacyclocarbene ligands based
on five- and six-membered rings, to the best of our knowl-
edge only one other example of a crystallographically char-
acterised complex containing a seven-membered ring has
been reported. The complex [Ru(=C6H10O)(η5-C9H7)-
(PPh3)2]PF6 has been prepared and exhibits a Ru=C dis-
tance of 1.89(1) Å.[22]
Comparison of Structural Properties of Complexes based on
the trans-[Ru(κ1-OAc)(κ2-OAc)(L)(PPh3)2] Framework
All of the complexes reported have the same core struc-
ture, which is shown, with an appropriate labelling scheme,
in Figure 5. Having such a range of isostructural com-
pounds in hand allows for the effects of the ligands L on
various metal–ligand interactions to be evaluated. Key crys-
tallographic parameters are presented in Tables 2 and 3, IR
data in Table 4 and NMR spectroscopic data in Tables 5
and 6.
Figure 5. Labelling scheme for complexes of the general type trans-
[Ru(κ1-OAc)(κ2-OAc)(L)(PPh3)2].
An examination of the geometric parameters for the
trans-[Ru(κ1-OAc)(κ2-OAc)(PPh3)2] framework demon-
strate that a series of systematic changes are present that
may be rationalised on the basis of the different electronic
demands of the ligand L. Considering, for example, the
series 2, 3[BF4] and 4, it is generally accepted that the π-
acceptor
ability
decreases
in
the
sequence
NO+ ϾCOϾCNtBu with the ability of the ligand to act as
a σ-donor exhibiting the opposite trend.[24,25] Therefore, it
would be expected that the bond lengths between the ruthe-
nium and π-donor ligands would increase for the series
3[BF4]Ͻ2Ͻ4, whereas π-acceptor ligands would exhibit
the opposite trend. This is indeed what is observed. The
O(2)–Ru bond lengths (i.e. in a position trans to the ligand
L) increase in the sequence 3[BF4] [2.0744(19) Å]Ͻ2
[2.1897(11) Å]Ͻ4 [2.2465(16) Å], consistent with the pre-
dicted trend, as does the Ru–O(3) bond length. In contrast,
the Ru–P distances for this class of compounds exhibit the
opposite trend (mean bond lengths 3[BF4] [2.4401(1) Å]Ͻ2
[2.3967(6) Å]Ͻ4 [2.3536(8)]Å), which, as the PPh3 ligands
Figure 4. Molecular structures of (a) 11a, (b) 11b and (c) 11c. Ther- are the only other π-acceptor ligands present in the coordi-
mal ellipsoids where shown are at the 50% probability level, hydro-
nation sphere of the metal after L, is again as expected.
gen atoms are omitted for clarity. For the structure of 11b only
Furthermore, the bite angle of the κ2-acetate ligand
confirmation of the disordered carbene ligand is shown. The κ1-
ˆ
[O(1)–C(1)–O(2)] also shows a correlation with the type of
acetate ligand in 11c is disordered over two sites with an
82.2(4):17.8(4) occupancy, the minor form being represented with
hatched bonds.
ligand L that is present. In the case of complex 3[BF4], this
angle is 61.55(8)° decreasing to 60.42(4)° for 2 and 59.80(6)°
for 4. Also, the O(2)–Ru–X angle increases in the series 4
[158.95(9)°]Ͻ2 [164.49(6)°]Ͻ3[BF4] [168.00(9)°]. Again
The structure determinations for all three of the com- they may be rationalised on the basis of both σ- and π-
plexes confirm the presence of the oxacyclocarbene ligands, effects, but it is clear that the structural metrics within the
with Ru–C bond lengths of 1.878(6) Å (11a), 1.865(3) Å trans-[Ru(κ1-OAc)(κ2-OAc)(L)(PPh3)2] framework are sen-
(11b) and 1.902(3) Å (11c). Although there are a number of sitive to the electronic properties of the ligand L.
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Ruthenium Acetate Complexes as Probes of Metal–Ligand Interactions
Table 2. Summary of pertinent bond lengths [Å] for complexes reported (n.a. = not applicable). In the case of complexes with disorded
acetate ligands only the major conformer is considered.
Complex
Ru–X
X–XЈ
Ru–O(1)
Ru–O(2)
Ru–O(3)
Ru–P(1)
Ru–P(2)
2
1.8318(17)
1.739(2)
1.882(2)
1.786(3)
1.766(6)
1.7863(16)
1.8027(15)
1.7959(18)
1.805(3)
1.878(6)
1.865(3)
1.902(3)
1.146(2)
1.137(3)
1.159(3)
1.318(4)
1.296(8)
1.325(2)
1.312(2)
1.316(2)
1.297(4)
n.a.
2.1466(11)
2.1336(19)
2.1352(16)
2.1139(17)
2.102(4)
2.1116(11)
2.1100(11)
2.1141(13)
2.1119(19)
2.204(4)
2.1897(11)
2.0744(19)
2.2465(16)
2.2863(18)
2.282(4)
2.2465(12)
2.2588(11)
2.2620(13)
2.3259(19)
2.355(4)
2.0365(11)
1.9966(19)
2.056(2)
2.0699(17)
2.063(4)
2.0160(11)
2.0344(11)
2.0179(12)
2.088(2)
2.4060(4)
2.4336(8)
2.3592(6)
2.3853(7)
2.3788(14)
2.4195(5)
2.4178(4)
2.4040(5)
2.3734(7)
2.3840(14)
2.3734(5)
2.3891(8)
2.3873(4)
2.4466(8)
2.3479(6)
2.3910(7)
2.3762(14)
2.3720(5)
2.3652(4)
2.3757(5)
2.3850(7)
2.3642(14)
n.a.
3[BF4]
4
6a
6b
6c
8a
8e
8f
11a
11b
11c
2.058(4)
2.104(2)
2.086(2)
n.a.
n.a.
n.a.
2.126(2)
n.a.
2.325(2)
2.3591(8)
Table 3. Summary of pertinent bond angles [°] for complexes re- oxacyclocarbene complexes show the largest differences in
ported (n.a. = not applicable). In the case of complexes with dis-
frequency between the symmetric and asymmetric stretch
orded acetate ligands only the major conformer is considered.
of all of the complexes reported and have the most acute
Ru–X–XЈ
O(1)–Ru–X
O(2)–Ru–X
O(3)–Ru–X
acetate bite angles. These data point to the Fischer carbene
ligands being better net donor ligands to the metal than
either NO+, CO or CNtBu.
2
175.02(15)
176.5(2)
175.6(2)
176.5(2)
173.6(5)
174.72(14)
175.16(13)
178.10(16)
178.2(3)
n.a.
104.71(6)
106.75(9)
99.46(9)
97.81(9)
97.5(2)
101.92(6)
101.35(6)
103.64(6)
98.99(10)
96.6(2)
164.49(6)
168.00(9)
158.95(9)
155.65(9)
154.7(2)
161.77(6)
161.05(6)
162.68(6)
155.45(10)
151.5(2)
n.a.
99.45(6)
102.25(10)
89.13(10)
93.90(9)
94.1(2)
102.72(6)
101.59(6)
104.95(7)
92.52(10)
92.4(2)
3[BF4]
4
6a
6b
6c
8a
8e
8f
The relative π-acidity of vinylidene ligands has been
probed by analysis of the IR spectra in the series of com-
pounds [Mn(η5-C5H5)(CO)2(=C=CHR)].[26] This study re-
vealed that in this case the vinylidene ligand is a better π-
acceptor than CO. However, in 2002 Werner reported that
the CO ligand is a better π-acceptor, but poorer σ-donor
ligand than the vinylidene ligand based on DFT, IR and
Raman spectroscopic studies of the square-planar complex
[Rh(X)(L)(PiPr3)2] (X = halogen; L = CO, =C=CH2).[27]
An examination of the available O(2)–Ru bond lengths for
the vinylidene and hydroxy-substituted vinylidene complex
vary from 2.2465(12) Å for complex 6c to 2.2863(18) Å for
6a. For the purposes of this discussion the O(2)–Ru bond
length in 8f is not considered as O(2) appears to be involved
11a
11b
11c
n.a.
n.a.
95.45(7)
98.29(11)
n.a.
89.40(12)
157.19(11)
P(1)–Ru–P(2)
O(1)–Ru–O(2) O(1)–Ru–O(3)
O(2)–Ru–O(3)
2
176.545(15)
176.05(2)
173.30(2)
178.89(3)
178.20(6)
174.126(15)
173.647(14)
177.844(17)
178.45(3)
173.69(5)
178.60(4)
175.91(3)
60.42(4)
61.55(8)
59.80(6)
59.08(6)
58.78(14)
59.86(4)
59.79(4)
59.78(5)
58.45(7)
56.40(15)
n.a.
155.62(5)
150.64(9)
170.17(8)
168.17(7)
168.40(15)
154.87(5)
156.68(4)
151.04(5)
168.47(7)
170.95(16)
169.10(13)
170.96(9)
95.71(5)
89.64(8)
111.25(7)
109.09(7)
109.67(15)
95.49(4)
97.36(4)
92.05(5)
110.09(7)
114.74(16)
n.a.
3[BF4]
4
6a
6b
6c
8a
8e
8f
in hydrogen bonding to the CH2Cl2 of crystallisation. The
2
ˆ
bite angle of the κ -acetate ligand [O(1)–C(1)–O(2)] varies
from 59.86(4)° in 6c to 59.08(6)° in 6a (again ignoring 8f).
Once more these values are similar to that observed in the
isocyanide complex 4, as are the differences in frequency
observed between the symmetric and asymmetric stretch of
the κ2-acetate ligand in all cases. This therefore indicates
that in this series of compounds[28] the vinylidene and isocy-
anide ligands have similar net donor/acceptor properties.
The NMR spectroscopic data for these complexes exhibit
a few common features worthy of note. For example, the
chemical shift of the two PPh3 ligands within the complexes
fall into a very narrow region (Table 5) from δ = 41.8 ppm
for 4 to δ = 33.8 ppm for 6c: complex 1 (in which the phos-
phane ligands are mutually cis) exhibits a resonance at δ =
63.1 ppm.
11a
11b
11c
58.92(8)
113.25(8)
An examination of the structural metrics of complexes
11 provided insight into the relative donor/acceptor proper-
ties of these Fischer-type carbene complexes. One would
expect there to be less metal–ligand π back-donation occur-
ring in this instance, which is consistent with the observed
structural metrics. For example, the O(2)–Ru distance is
2.355(4) Å (11a) and 2.325(2) Å (11c), notably longer than
those observed in complexes 2, 3[BF4] and 4. The Ru–P
bonds in this series are not as short as those observed in 4,
although with the introduction of a carbene ligand steric
In all cases, at room temperature a singlet resonance was
factors cannot be ignored. The bite angles of the κ2-acetate observed for the six protons of the two acetate ligands, dem-
in 11a and 11c are 56.40(15)° and 58.92(8)°, respectively, onstrating that these ligands undergo an exchange process
with O(2)–Ru–X angles of 151.5(2)° and 157.19(11)°, that is rapid on the NMR timescale. In some instances, it
respectively. The IR data for the complexes of the general has been possible to observe the decoalescence of the two
type trans-[Ru(κ1-OAc)(κ2-OAc)(L)(PPh3)2] also support environments upon cooling, the low-temperature limiting
these changes to the binding of the κ2-acetate ligand as the regime was not obtained in most cases, therefore, the ob-
Eur. J. Inorg. Chem. 2012, 1493–1506
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1499

J. M. Lynam et al.
FULL PAPER
Table 4. IR data [cm–1] from KBr discs for complexes reported (n.a. = not applicable; n.d. = not determined).
Complex
C=C
κ1-OCOsym
κ1-OCOasym
κ1-Δυ
κ2-OCOsym
κ2-OCOasym
κ2-Δυ
2
n.a.
n.a.
n.a
1368
1364
1366
1360
1365
1366
1366
1378
1362
1372
1369
1361
1364
1366
1367
1374
1359
1368
1375
1382
1607
1636
1627
1595
1600
1590
1616
1595
1619
1595
1592
1601
1590
1591
1597
1620
1597
1616
1615
1608
239
272
261
235
235
224
250
217
257
223
223
240
226
225
230
246
238
248
240
225
1466
n.d.
1520
n.d.
54
n.d.
67
75
69
68
72
62
73
76
83
78
78
80
71
74
80
94
103
96
3[BF4]
4
1462
1459
1466
1462
1459
1465
1460
1457
1454
1458
1458
1458
1463
1456
1457
1447
1446
1450
1529
1534
1535
1530
1531
1527
1533
1533
1537
1536
1536
1538
1534
1530
1537
1541
1549
1546
6a
6b
6c
6d
8a
8b
8c
8d
8e
8f
1635
1684
1607
1636
1654
1648
1655
1648
1649
1654
1646
1636
1649
1651
n.a.
8g
8h
8i
8j
11a
11b
11c
n.a.
n.a.
Table 5. Selected NMR spectroscopic data in CD2Cl2 solutions for complexes reported (n.a. = not applicable; n.d. = not determined).
Complex
1H NMR
31P NMR
13C NMR
δH
4JHP [Hz]
δP PPh3
δC [Ru]=C=C
2JCP [Hz]
δC [Ru]=C=C
3JCP [Hz]
[Ru]=C=CH
2
n.a.
n.a.
n.a.
5.14
5.41
6.20
3.74
4.73
4.32
4.56
4.14
4.56
4.38
4.39
4.11
4.48
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
3.70
3.22
3.63
3.73
3.93
3.87
3.75
3.79
3.85
3.84
3.74
3.67
3.66
n.a.
n.a.
n.a.
39.1
34.7
41.8
34.1
34.8
33.8
35.5
34.0
34.1
33.9
34.9
34.3
34.3
34.4
35.1
35.5
35.9
35.4
34.2
207.4
n.a.
161.9
355.6
345.2
n.d.
337.6
347.6
352.0
349.3
345.1
350.4
352.0
352.2
345.7
352.0
304.7
306.8
311.0
13.2
n.a.
n.d.
16.8
n.d.
n.d.
15.4
16.2
16.3
16.1
16.2
16.0
16.3
16.5
16.3
16.2
11.8
11.7
11.8
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
4.40
3.90
4.56
3.90
4.67
4.78
4.60
4.72
4.27
4.63
4.73
4.96
4.62
n.a.
n.a.
n.a.
3[BF4]
4
6a
6b
6c
6d
8a
8b
8c
8d
8e
8f
8g
8h
8i
11a
11b
11c
112.1
104.4
109.4
94.0
117.2
118.4
113.7
112.5
117.6
116.3
117.5
106.5
114.4
n.a.
n.a.
n.a.
Table 6. Tc, kcoal and ΔG‡ values of complexes for which decoalesc-
ence is observed. Data from H NMR spectra recorded in CD2Cl2
solution. Rates of exchange are minimum values and free energy
of activation maximum values.
plexes where decoalescence was observed are summarised
in Table 6. These data show that although there is some
variance in the rate of exchange (kcoal), the energy barrier
(ΔG‡) to this exchange for each complex is quite similar.
The highest barrier is observed for the NO-containing com-
plex 3[BF4], which also exhibits the shortest Ru–O(2) dis-
tance.
The NMR spectra of the four vinylidene complexes 6
show a number of similar features. The chemical shifts of
the characteristic resonance for the proton attached to the
vinylidene β-carbon and the metal-bound resonance are in-
fluenced by the nature of the substituent present. This var-
ies from δ = 3.74 ppm in the case of SiMe3-substituted 6d
to δ = 6.20 ppm in the case of the pyrene-containing com-
1
Complex
δv [s–1]
Tc [K]
kcoal [s–1]
ΔG‡ [kJmol–1]
2
173.7
183.9
291.3
270.4
175.8
138.7
203.0
146.5
195
235
215
190
195
195
185
185
385.6
408.3
646.7
600.2
390.2
307.8
451.0
325.4
37.4
45.3
40.5
35.7
37.4
37.8
35.2
35.7
3[BF4]
8a
8d
8f
8h
11a
11b
tained rates of exchange must be viewed as minimum values
and the resulting free energy of activation as maximum val- plex 6c: these complexes also exhibited the lowest and high-
ues. The exchange parameters calculated for those com- est chemical shifts for the PPh3 groups in the 31P NMR
1500
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© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 1493–1506

Ruthenium Acetate Complexes as Probes of Metal–Ligand Interactions
and “apparent quartet”, respectively. Mass spectrometry measure-
ments were performed with a Thermo-Electron Corp LCQ Classic
(ESI), a Bruker instrument or Waters GCT Premier Acceleration
TOF MS (LIFDI). IR spectra were acquired with a Thermo-Nico-
let Avatar 370 FTIR spectrometer using either CsCl solution cells
or as KBr discs. CHN measurements were performed using an Exe-
ter Analytical Inc. CE-440 analyser. The proportion of CH2Cl2 in
samples for elemental analysis was confirmed by recording a 1H
NMR spectrum of the material used for analysis in [D8]toluene.
Relative integration of the peak at δH = 4.31 (CH2Cl2) to that of
spectra, respectively. The hydroxy-substituted vinylidene
complexes show far smaller differences in chemical shift for
these resonances, as might be expected with the site of sub-
stitution being somewhat more remote from the metal. The
vinylidene and hydroxyvinylidene complexes exhibit triplet
resonances between δ = 337.4 (6d) and 355.6 ppm (6a) for
the metal-bound carbon atom. The coupling constants ob-
served between the phosphorus nuclei and these atoms are
2
fairly uniform. The JPC values of the vinylidene (6) and
hydroxyvinylidene (8) complexes are larger than the corre- the vinylidene proton indicated the proportion of DCM in that
sample. Alkynes 5a, 5b, 5d, 7a–g, 7i, 10a–c and NO[BF4] were ob-
tained from Sigma–Aldrich, 8g from Lancaster Synthesis and
CNtBu from Fluka. All were used as supplied without further puri-
fication. Compounds 1,[6,30] 2[6,9] and 5c[31] were prepared as de-
scribed previously.
sponding value for the carbonyl complex 2, which is in turn
larger than the JPC of the oxacyclocarbene complexes 10.
2
This may reflect the fact that the vinylidene ligand is more
tightly bound to the ruthenium centre, as evidenced by the
shorter Ru–C distances observed on structural characterisa-
tion. The resonances for the metal-bound carbon atoms of
the oxacyclocarbene complexes 11 are observed at a lower
chemical shift than the corresponding Cα of the vinylidene
complexes. This is thought to be a result of the stronger
electrophilic character of a vinylidene ligand compared to
a Fischer carbene.[29]
Synthesis of [Ru(κ1-OAc)(κ2-OAc)(NO)(PPh3)2]BF4 (3[BF4]):
Ru(κ2-OAc)(PPh3)2 (0.20 g, 0.27 mmol) was dissolved in CH2Cl2
(15 mL) in a Schlenk tube with a stirrer bar. NOBF4 (31.6 mg,
0.27 mmol, 1 equiv.) was added and the solution was allowed to
stir for 1 h. After this time the solution was concentrated to approx-
imately 5 mL and the product was precipitated by the addition of
toluene (40 mL). The solution was filtered to leave a light-brown
1
powder product that was dried in vacuo. Yield = 0.08 g (50%). H
Conclusions
NMR (CD2Cl2): δ = 0.82 (s, 6 H, OCOCH3), 7.48 (aq, J = 6.6 Hz,
12 H, ortho-H of PPh3), 7.60 (J = 7.7 Hz, 12 H, meta-H of PPh3),
7.71 (J = 7.5 Hz, 6 H, para-H of PPh3) ppm. 31P NMR (CD2Cl2):
δ = 34.7 (PPh3) ppm. 13C NMR (CD2Cl2): δ = 21.1 (s, OCOCH3),
Complex 1 is a versatile substrate for the preparation of
complexes of the general type trans-[Ru(κ1-OAc)(κ2-
OAc)(L)(PPh3)2] in which L is a σ-donor/π-acceptor ligand.
This is either through a direct reaction (as in the case of
CO, NO+ or CNtBu) or through a metal-mediated hydro-
gen-transfer reaction to form vinylidene ligands. A key fea-
ture of this reaction appears to be the change in geometry
of the phosphane ligands from cis in 1 to mutually trans in
the other examples. This may reflect a tendency to place the
better π-acceptor ligand in the same plane as the π-donor
acetate ligands.
An examination of the structural parameters and spec-
troscopic properties of complexes trans-[Ru(κ1-OAc)(κ2-
OAc)(L)(PPh3)2] reveals a number of metrics that may re-
flect the relative electronic demands of the ligand L. These
data indicate that the relative net donor/acceptor properties
of the ligands increase in the series carbene Ͻ vinylidene ≈
CNtBu Ͻ CO Ͻ NO+.
1
3
3
5
122.9 (t, JCP + JCP = 52.0 Hz, PPh3-C1), 129.6 (t, JCP + JCP
10.7 Hz, PPh3-C3), 133.0 (s, PPh3-C4), 134.7 (t, JCP
=
=
2
+
4JCP
10.8 Hz, PPh3-C2) ppm, the resonance for the carbonyl carbon
could not be observed, presumably because it is broadened as a
result of exchange. IR (KBr): ν = 1364 (κ1-OAcsym), 1435 (P–Ph),
˜
1483 (P–Ph), 1636 (κ1-OAcasym), 1865 (NO) cm–1, Δν(uni)
271 cm–1. IR (CH Cl ): ν = 1359 (κ1-OAcsym), 1438 (P–Ph), 1485
=
˜
2
2
(P–Ph), 1636 (κ1-OAcasym), 1874 (NO) cm–1, Δν(uni) = 277 cm–1.
MS (ESI): calcd. for C40H36NO5P2Ru [M]+ m/z = 774.1107, found
m/z = 774.1094. C40H36BF4NO5P2Ru + (1.00CH2Cl2): calcd. C
52.08, H 4.05, N 1.48; found C 51.89, H 4.20, N 1.60.
Synthesis of [Ru(κ1-OAc)(κ2-OAc)(CNtBu)(PPh3)2] (4): [Ru(κ2-
OAc)2(PPh3)2] (0.4 g, 0.54 mmol) was dissolved in CH2Cl2 (25mL)
in a Schlenk tube. tBuNC (60 μL,0.54 mmol, 1 equiv.) was added.
The solution was then stirred for 30 min until the solution changed
from orange-red to green. The solvent was removed in vacuo and
the yellow-green residue was washed with 2ϫ20 mL portions of
pentane. The product was dried in vacuo. Yield = 0.15 g (35.0%).
1H NMR (CD2Cl2): δ = 0.62 [s, 9 H, C(CH3)3] 0.65 (s, 6 H, OC-
OCH3) 7.27–7.33 (m, 18 H, PPh3), 7.40–7.47 (m, 12 H, PPh3) ppm.
31P NMR (CD2Cl2): δ = 41.8 (PPh3) ppm. 13C NMR (CD2Cl2): δ
Experimental Section
General: All experimental procedures were performed under an at-
mosphere of dinitrogen or argon using standard Schlenk Line and
Glove Box techniques. CH2Cl2, pentane and hexane were purified
with the aid of an Innovative Technologies anhydrous solvent engi-
neering system. The CD2Cl2 solution used for the NMR experi-
ments was dried with CaH2 and degassed with three freeze-pump-
thaw cycles. The solvent was then vacuum transferred into NMR
tubes fitted with PTFE Young’s taps. NMR spectra were acquired
with a Bruker AVANCE 500 (Operating Frequencies 1H NMR:
= 22.5 (s, OCOCH3), 30.2 [s, C(CH3)3], 56.9 [s, NC(CH3)3], 127.8
3
(t, JCP
+
5JCP = 9.2 Hz, PPh3-C3), 129.4 (s, PPh3-C4), 132.8 (t,
1JCP + JCP = 44.0 Hz, PPh3-C1), 134.7 (t, JCP + JCP = 12.0 Hz,
3
2
4
PPh3-C2), 161.9 (br., s RuCN), 180.7 (s, RuOCO) ppm. IR (KBr):
ν = 1366 (κ1-OCOsym), 1434 (P–Ph), 1462 (κ2-OCOsym), 1482 (P–
˜
Ph), 1529 (κ2-OCOassym), 1627 (κ1-OCOassym), 2067, 2105
(CN) cm–1, Δν(uni) = 261 cm–1, Δν(chelate) = 67 cm–1. IR (CH2Cl2):
ν = 1374 (κ1-OCOsym), 1434 (P–Ph), 1460 (κ2-OCOsym), 1480 (P–
˜
500.23 MHz, 31P NMR: 202.50 MHz, 13C NMR: 125.77 MHz) at Ph), 1528 (κ2-OCOassym), 1620 (κ1-OCOassym), 2070, 2104 (CN),
298 K, except for the data for complex 11c, which were recorded
Δν(uni) = 246 cm–1, Δν(chelate) = 68 cm–1. MS (ESI): calcd. for
[M + H]+ m/z = 828.1946, found m/z = 828.1939; calcd. for
C45H45N2O2P2Ru [M – OAc + MeCN]+ m/z = 809.1994, found m/z
= 809.1998. C45H45NO4P2Ru (826.87): calcd. C 65.37, H 5.49, N
1.69; found C 64.35, H 5.19, N 1.63.
1
with a JEOL 400 (Operating Frequencies H NMR: 400.13 MHz,
31P NMR: 161.83 MHz, 13C NMR: 100.53 MHz) at 298 K. 31P
NMR and 13C NMR spectra were recorded with proton decoup-
ling. The abbreviations “at” and “aq” refer to “apparent triplet”
Eur. J. Inorg. Chem. 2012, 1493–1506
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1501

J. M. Lynam et al.
Synthesis of [Ru(κ1-OAc)(κ2-OAc)(=C=CH{py}(PPh3)2)] (6c): 1- resulting powder was isolated by filtration and washed twice more
FULL PAPER
Ethynylpyrene (20.0 mg, 0.09 mmol) was dissolved in CH2Cl2
(7 mL) in a round-bottomed flask. This solution was then transfer-
red by a cannula wire to a Schlenk tube containing 1 (66.7 mg,
0.09 mmol) with a stirrer bar. The mixture was stirred under N2
for 1 h. After this time the solution was concentrated in vacuo and
pentane (25 mL) was added to precipitate the product as a bright-
red powder. The liquid was removed by a filter-tipped cannula and
the product was washed with two further portions of pentane
with pentane or hexane and dried in vacuo. If required, this prod-
uct was recrystallised by slow diffusion of pentane or hexane into
a CH2Cl2 solution of the complex.
Complex 8c: This complex was obtained as a yellow-orange powder
from
1 (0.30 g, 0.40 mmol) and HCϵCCH2OH (22.0 μL,
0.38 mmol) in CH2Cl2 (20 mL). Yield = 0.17 g (53%). 1H NMR
(CD2Cl2): δ = 0.85 (s, 6 H, OCOCH3), 1.26 [t, 3JHH = 5.6 Hz, 1 H,
(Ru)=C=CHC(OH)], 3.88 (3JHH
=
6.5 Hz, at
2
H,
1
(10 mL) before finally drying in vacuo. Yield = 0.035 g (41%). H
4
[Ru]=C=CHCH2), 4.11 (apparent septet, JHP = 3.7 Hz, 1 H,
[Ru]=C=CH), 7.40–7.51 (m, 30 H, PPh3) ppm. 31P NMR (CD2Cl2):
δ = 35.1 (s, PPh3) ppm. 13C NMR (CD2Cl2): δ = 21.8 (s, OCOCH3),
54.9 (s, Ru=C=CH–COH), 106.5 (t, JPC = 4.96 Hz, Ru=C=C),
128.0 (t, JPC + JPC = 9.21 Hz, PPh3-C3), 129.8 (t, JPC + JPC
NMR (CD2Cl2): δ = 0.95 (s, 6 H, OCOCH3), 6.20 (t, 4JHP = 3.6 Hz,
1 H, [Ru]=C=CH), 7.27–7.33 (m, 18 H, PPh3), 7.54–7.58 (m, 12 H,
PPh3), 7.77–7.87 (m, 3 H, pyrene), 7.91–8.00 (m, 4 H, pyrene), 8.09
3
(t, J = 7.6 Hz, 2 H, pyrene) ppm. 31P{1H} NMR (CD2Cl2): δP
=
3
5
1
3
=
=
33.8 (PPh3) ppm. 13C{1H}NMR (CD2Cl2): δ = 22.0 (s, OCOCH3),
2
40.3 Hz, PPh3-C1), 130.1 (s, PPh3-C4), 134.8 (t, JPC
+
4JPC
3
109.4 (t, JPC = 4.56 Hz, Ru=C=CPh), 124.0, 124.2, 124.3, 124.5
2
11.8 Hz, PPh3-C2), 179.7 (s, OCOCH3), 345.7 (t, JPC = 16.3 Hz,
(q), 124.8, 125.2, 125.2 (q), 125.3, 125.5, 125.7, 127.6, 127.9 (t, 3JCP
Ru=C) ppm. IR (KBr): ν = 1372 (κ1-OCOsym), 1433 (P–Ph), 1457
˜
5
1
+ JCP = 9.24 Hz, PPh3-C3), 128.1 (q), 128.7 (q), 129.4 (t, JCP
+
(κ2-OCOsym), 1533 (κ2-OCOasym), 1595 (κ1-OCOasym), 1655 (C=C),
3337 (OH) cm–1, Δν(uni) = 223 cm–1, Δν(chelate) = 76 cm–1. IR
3JCP = 43.1 Hz, PPh3-C1), 130.0 (s, PPh3-C4), 131.4, 131.8, 134.9
2
4
(t, JCP + JCP = 10.9 Hz, PPh3-C2), 179.8 (s, OCOCH3) (q) ppm.
(CH Cl ): ν = 1368 (κ1-OCOsym), 1434 (P–Ph), 1456 (κ2-OCOsym),
˜
IR (KBr): ν = 1360 (κ1-OAcsym), 1434 (P-Ph), 1458 (κ2-OAcsym),
2
2
˜
1538 (κ2-OCOasym), 1605 (κ1-OCOasym), 1651 (C=C), 3573
(OH) cm–1, Δν(uni) = 237 cm–1, Δν(chelate) = 82 cm–1. MS (ESI):
calcd. for C43H41O5P2Ru [M + H]+ m/z = 801.1473, found m/z =
801.1502. MS (LIFDI): m/z = 798 [M – 2H]+. Elemental analysis
could not be obtained because of rapid conversion to 2 and ethene.
1536 (κ2-OAcasym), 1587 (κ1-OAcasym), 1610 (C=C) cm–1, Δν(uni)
=
227 cm–1, Δν(chelate) 78 cm–1. IR (CH2Cl2):
ν = 1366
˜
(κ1-OAcsym), 1434 (P–Ph), 1462 (κ2-OAcsym), 1530 (κ2-OAcasym),
1590 (κ1-OAcasym), 1607 (C=C) cm–1, Δν(uni) = 224 cm–1, Δν(chelate)
= 68 cm–1. MS (ESI): calcd. for [M + H]+ m/z = 971.1988, found
m/z = 971.1968; calcd. for C58H46NO2P2Ru [M – OAc + MeCN]+
Complex 8d: This complex was obtained as a pale-yellow powder
from 1 (0.20 g, 0.27 mmol) and HCϵCC(OH)(Ph)(H) (32.7 μL,
0.27 mmol) in CH2Cl2 (15 mL). Yield = 0.16 g (70%) 1H NMR
(CD2Cl2): δ = 0.86 (s, 6 H, OCOCH3), 2.87 [br. s, 1 H,
m/z
= 952.2042, found m/z = 952.2034. C58H46O4P2Ru +
(0.30CH2Cl2): calcd. C 70.34, H 4.72; found C 69.89, H 4.82.
Synthesis of [Ru(κ1-OAc)(κ2-OAc)(=C=CH{SiMe3})(PPh3)2]BF4
(6d): Complex 1 (200 mg, 0.27 mmol) was dissolved in CH2Cl2
(10 mL) and HCϵCSiMe3 (38.0 μL, 0.27 mmol, 1 equiv.) was then
added. The mixture was stirred for 1 h at room temperature. The
solvent was evaporated and the solid was washed with three por-
tions of pentane (10 mL). After drying in vacuo, the desired yellow
(Ru)=C=CHCH(OH)Ph], 4.14 [dt, 4JHP = 3.8, 3JHH = 6.4 Hz, 1 H,
3
(Ru)=C=CHCH(OH)Ph], 5.44 [d, JHH
= 6.34 Hz, 1 H,
(Ru)=C=CHCH(OH)Ph], 6.83 (d, J = 7.3 Hz, 2 H, H2-Ph), 7.09 (J
= 7.5 Hz, 2 H, H3-Ph), 7.14 (tt, J = 7.2 Hz, J = 1.4 Hz, 1 H, H4-
Ph), 7.41 (at, J = 7.3 Hz, 12 H, H3-PPh3), 7.48 (t, J = 7.2 Hz, 6 H,
H4-PPh3), 7.53 (m, 12 H, H2-PPh3) ppm. 31P NMR (CD2Cl2): δ =
34.9 (s, PPh3) ppm. 13C NMR (CD2Cl2): δ = 21.8 (s, OCOCH3),
product (134 mg, 59%) was obtained. 1H NMR (CD2Cl2): δ =
4
–0.43 (s, 9 H, SiMe3), 0.74 (s, 6 H, OCOCH3), 3.74 (t, JPH
=
3
3.7 Hz, 1 H, Ru=C=CHSiMe3) ppm. 31P NMR (CD2Cl2): δ = 35.5
67.0 (s, Ru=C=CH–COH), 112.5 (t, JPC = 4.72 Hz, Ru=C=C),
(s, PPh3) ppm. 13C NMR (CD2Cl2): δ = 0.44 (SiMe3), 22.2 (OC-
126.3 [s, Ru=C=C–C(Ph–C3)], 126.6 [s, Ru=C=C–C(Ph–C4)], 127.8
[s, Ru=C=C–C(Ph–C2)], 128.1 (t, 3JPC + 5JPC = 9.25 Hz, PPh3-C3),
3
OCH3), 94.0 (Ru=C=C), 127.9 (t, JCP
+
5JCP = 10.2 Hz, PPh3-
129.7 (t, 1JPC + 3JPC = 42.4 Hz, PPh3-C1), 130.2 (s, PPh3-C4), 134.9
1
3
C3), 129.9 (s, PPh3-C4), 130.2 (t, JCP + JCP = 40.8 Hz, PPh3-C1),
2
+
4JCP = 11.2 Hz, PPh3-C2), 179.6 (s, OCOCH3),
(t, JPC
+
4JPC = 12.2 Hz, PPh3-C2), 144.9 [Ru=C=C-C(Ph-C1)],
2
135.0 (t, JCP
–12
337.6 (t, JCP = 15.3 Hz, Ru=C=C) ppm. IR (KBr): ν = 1361 (κ1-
2
179.9 (s, OCOCH3), 345.1 (t, cm
J
PC
= 16.2 Hz, Ru=C) ppm. IR
˜
(KBr): ν = 1369 (κ1-OCOsym), 1435 (P–Ph), 1454 (κ2-OCOsym),
OCOsym), 1433 (P–Ph), 1463 (κ2-OCOsym), 1521 (κ2-OCOasym),
1611 (κ1-OCOasym), 1633 (C=C) cm–1, Δν(uni) = 250 cm–1, Δν(chelate)
˜
1537 (κ2-OCOasym), 1592 (κ1-OCOasym), 1648 (C=C) cm–1, Δν(uni)
=
223 cm–1, Δν(chelate) 83 cm–1; IR (CH2Cl2):
= ν = 1373
˜
= 58 cm–1. IR (CH Cl ): ν = 1366 (κ1-OCOsym), 1433 (P–Ph), 1459
˜
2
2
(κ1-OCOsym), 1435 (P–Ph), 1455 (κ2-OCOsym), 1538 (κ2-OCOasym),
1596 (κ1-OCOasym), 1647 (C=C) cm–1, Δν(uni) = 223 cm–1, Δν(chelate)
= 83 cm–1. MS (LIFDI): m/z = 876 [M]+. C49H44O5P2Ru +
(1.60CH2Cl2): calcd. C 60.07, H 4.70; found C 60.20, H 5.00.
(κ2-OCOsym), 1531 (κ2-OCOasym), 1617 (κ1-OCOasym), 1636
(C=C) cm–1, Δν(uni) = 250 cm–1, Δν(chelate) = 72 cm–1. MS (ESI):
calcd. for C45H46NaO4P2RuSi [M + Na]+ m/z = 866.1582, found
m/z = 865.1608; calcd. for C45H47O4P2RuSi [M + H]+ m/z =
843.1757, found m/z = 843.1791; calcd. for C45H46NO2P2RuSi [M –
OAc + NCMe]+ m/z = 824.1817, found m/z = 824.1828; calcd. for
C43H43O2P2RuSi [M – OAc]+ m/z = 783.1546, found m/z =
783.1551; calcd. for C27H32O4PRuSi [M + H – PPh3]+ m/z =
581.0851, found m/z = 581.0849; calcd. for C24H24O4PRuSi [M +
2H – PPh3 – SiMe3]+ m/z = 509.0456, found m/z = 509.0459. On
crystallisation, small quantities of dark-red crystals of 1 were re-
formed in addition to the bright-yellow crystals of 5d, which pre-
cluded an accurate elemental analysis.
Complex 8e: This complex was obtained as a bright-yellow powder
from the reaction of 1a (0.15 g, 0.20 mmol) and
HCϵCC(OH)(Ph)(Me) (0.03 g, 0.20 mmol) in CH2Cl2 (10 mL).
Pentane (40 mL) was used to precipitate the product, and it was
washed further with 2ϫ15 mL portions of pentane. Yield = 0.12 g
1
(67%) H NMR (CD2Cl2): δ = 0.81 (s, 6 H, OCOCH3), 1.10 [s, 3
H, HCϵCC(CH3)], 2.79 [br. s, 1 H, (Ru)=C=CHC(OH)], 4.56 (t,
4JHP
= 3.9 Hz, 1 H, [Ru]=C=CH), 6.96–7.10 [m, 5 H,
HCϵCC(Ph)], 7.37–7.50 (m, 31 H, PPh3) ppm. 31P NMR
(CD2Cl2): δ = 34.3 (s, PPh3) ppm. 13C NMR (CD2Cl2): δ = 21.8 (s,
OCOCH3), 33.6 [s, Ru=C=C–C(CH3)], 71.1 (s, Ru=C=CH–COH),
General Procedure for Complexes 8 and 11: In a typical experiment,
ca. 1 equiv. of the appropriate alkyne was added to a Schlenk vessel
containing a solution of 1 in CH2Cl2. After stirring for 1 h the
product was precipitated by addition of pentane or hexane. The
3
117.6 (t, JPC = 4.3 Hz, Ru=C=C), 124.9 [s, Ru=C=C–C(Ph–C3)],
125.8 [s, Ru=C=C–C(Ph–C4)], 127.7 [s, Ru=C=C–C(Ph–C2)], 128.0
1502
www.eurjic.org
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 1493–1506

Ruthenium Acetate Complexes as Probes of Metal–Ligand Interactions
3
1
(t, JPC
+
5JPC = 9.55 Hz, PPh3-C3), 129.4 (t, JPC
+
+
3JPC
4JPC
=
=
PPh3) ppm. 31P NMR (CD2Cl2): δ = 33.9 (s, PPh3) ppm. 13C NMR
(CD2Cl2): δ = 21.8 (s, OCOCH3), 77.1 (s, Ru=C=CH–COH), 113.6
(t, JPC = 4.58 Hz, Ru=C=C), 119.3 (s, CH), 124.1 (s, CH), 127.7,
2
43.2 Hz, PPh3-C1), 130.1 (s, PPh3-C4), 135.0 (t, JPC
3
11.6 Hz, PPh3-C2), 150.4 (Ru=C=C-CPh-C1), 179.6 (s, OCOCH3),
350.4 (t, JPC = 16.0 Hz, Ru=C) ppm. IR (KBr): ν = 1361 (κ1-
(s, CH) 127.9 (s, CH) 128.0 (t, JPC
+
5JPC = 9.2 Hz, PPh3-C3),
2
3
˜
OCOsym), 1434 (P–Ph), 1458 (κ2-OCOsym), 1536 (κ2-OCOasym),
129.2 (t, 1JPC + 3JPC = 41.6 Hz, PPh3-C1), 130.2 (s, PPh3-C4), 135.0
1601 (κ1-OCOasym), 1649 (C=C), 3366 (OH) cm–1, Δν(uni)
=
(t, 2JPC + 4JPC = 11.5 Hz, PPh3-C2), 138.6 (s, C), 150.3, (s, C) 179.6
240 cm–1, Δν(chelate) = 78 cm–1. IR (CH Cl ): ν = 1367 (κ1-OCOsym), (s, OCOCH3), 349.3 (t, JPC = 16.1 Hz, Ru=C) ppm. IR (KBr): ν
2
˜
˜
= 1367 (κ1-OCOsym), 1433 (P–Ph), 1463 (κ2-OCOsym), 1534 (κ2-
OCOasym), 1597 (κ1-OCOasym), 1636 (C=C), 3403 (OH) cm–1,
2
2
1434 (P–Ph), 1463 (κ2-OCOsym), 1533 (κ2-OCOasym), 1601 (κ1-
OCOasym), 1652 (C=C), 3565 (OH) cm–1, Δν(uni) = 234 cm–1,
Δν(chelate)
=
70 cm–1. MS (ESI): calcd. for C50H45O4P2Ru
Δν(uni) = 230 cm–1, Δν(chelate) = 71 cm–1; IR (CH Cl ): ν = 1367
˜
2 2
[M – OH]+ m/z = 873.1831, found m/z = 873.2074. C50H46O5P2Ru
(κ1-OCOsym), 1435 (P–Ph), 1463 (κ2-OCOsym), 1531 (κ2-OCOasym),
1606 (κ1-OCOasym), 1646 (C=C), 3554 (OH) cm–1, Δν(uni)
+ (0.40CH2Cl2) : calcd. C 65.52, H 5.11; found C 65.75, H 5.21.
=
239 cm–1, Δν(chelate) = 68 cm–1. MS (ESI): calcd. for C55H46NO3-
P2Ru [M – OAc + MeCN]+ m/z = 932.1996, found m/z = 932.1995.
C55H46O5P2Ru·1.20CH2Cl2: calcd. C 64.17, H 4.64; found C 64.33,
H 4.66.
Complex 8f: This complex was obtained as a bright pink-orange
powder from 1 (0.25 g, 0.34 mmol) and 1-ethynylcyclopentanol
(40.0 μL, 0.35 mmol) in CH2Cl2 (15 mL). Yield = 0.28 g (84%). 1H
NMR (CD2Cl2): δ = 0.83 (s, 6 H, OCOCH3), 1.00 (m, 2.0 H), 1.24
(m, 4 H), 1.35 [br. s, 1.0 H, (Ru)=C=CHC(OH)], 1.50 (m, 2 H),
Complex 8i: This complex was obtained as a bright-yellow powder
from 1 (0.30 g, 0.40 mmol) and ethisterone (0.16 g, 0.50 mmol) in
CH2Cl2 (30 mL). The solvent was removed completely in vacuo
before the product was washed with 3ϫ30 mL portions of pentane.
4
4.38 (t, JHP = 3.8 Hz, 1.0 H, [Ru]=C=CH), 7.39–7.51 (m, 32 H,
PPh3) ppm. 31P NMR (CD2Cl2): δ = 34.3 (s, PPh3) ppm. 13C NMR
(CD2Cl2): δ = 21.9 (s, OCOCH3), 23.5 (CH2), 23.6 (CH2), 41.5
1
3
Yield = 0.21 g (50%). H NMR (CD2Cl2): δ = 0.37–0.67 (m, 3 H,
(CH2), 42.5 (CH2), 70.7 (s, Ru=C=CH–COH), 116.3 (t, JPC
4.63 Hz, Ru=C=C), 128.0 (t, JPC
=
+
5JPC = 9.50 Hz, PPh3-C3),
3
–CH–, –CH2–), 0.71 (s, 3 H, CH3), 0.75 (s, 6 H, OCOCH3), 1.13
(s, 3 H, CH3), 1.20–2.04 (m, 12 H, –CH–, –CH2–), 2.16 (s, 1 H,
129.1 (t, 1JPC + 3JPC = 42.3 Hz, PPh3-C1), 130.0 (s, PPh3-C4), 134.9
4
2
4
OH), 2.19 –2.47 (m, 4 H, –CH–, –CH2–), 4.48 (t, JHP = 3.7 Hz, 1
(t, JPC + JPC = 12.3 Hz, PPh3-C2), 179.6 (s, OCOCH3), 352.0 (t,
2JPC = 16.3 Hz, Ru=C) ppm. IR (KBr): ν = 1364 (κ1-OCOsym),
H, [Ru]=C=CH), 5.70 (br. s, 1 H, =CH–), 7.41 (J = 7.1 Hz, 12 H,
H3-PPh3), 7.45–7.51 (m, 18 H, H2-PPh3 and H4-PPh3) ppm. 31P
NMR (CD2Cl2): δ = 35.5 (s, PPh3) ppm. 13C NMR (CD2Cl2): δ =
13.3 (s, CH3), 17.1 (s, CH3), 20.5 (s, CH2), 21.7 (s, OCOCH3), 24.1
(s, CH2), 31.5 (s, CH2), 31.8 (s, CH2), 32.9 (s, CH2), 34.2 (s, CH2),
35.8 (s, CH2), 36.1 (s, C), 38.3 (s, CH), 38.7 (s, CH2), 46.5 (s, C),
˜
1434 (P–Ph), 1458 (κ2-OCOsym), 1536.2 (κ2-OCOasym), 1590 (κ1-
OCOasym), 1654 (C=C), 3370 (OH) cm–1, Δν(uni) = 226 cm–1,
Δν(chelate) = 77 cm–1; IR (CH Cl ): ν = 1364 (κ1-OCOsym), 1431
˜
2
2
(P–Ph), 1479 (κ2-OCOsym), 1532 (κ2-OCOasym), 1624 (κ1-OCOasym),
1656 (C=C), 3569 (OH) cm–1, Δν(uni) = 260 cm–1, Δν(chelate)
=
53 cm–1. MS (ESI): calcd. for C47H45O4P2Ru [M – OH]+ m/z =
837.1837, found m/z = 837.18. C47H46O5P2Ru + (1.40CH2Cl2):
calcd. C 59.76, H 5.06; found C 59.67, H 5.07.
48.7 (s, CH), 52.4 (s, CH), 81.6 (s, Ru=C=CH–COH), 114.4 (t,
3
3JPC = 4.6 Hz, Ru=C=C), 123.5 (s, =CH–), 128.1 (t, JPC + 5JPC
=
9.26 Hz, PPh3–C3), 129.4 (t, 1JPC + 3JPC = 42.4 Hz, PPh3-C1), 130.1
2
(s, PPh3-C4), 135.1 (t, JPC
+
4JPC = 10.8 Hz, PPh3-C2), 171.8 (s,
2
Complex 8g: This complex was obtained as a pale-orange powder
from 1 (0.50 g, 0.67 mmol) and 1-ethynylcyclohexanol (90.0 μL,
0.70 mmol) in CH2Cl2 (15 mL). Pentane (25 mL) was used to pre-
cipitate the product, and it was washed further with 2ϫ15 mL por-
tions of pentane. Yield = 0.25 g (43%). 1H NMR (CD2Cl2): δ =
C), 179.5 (s, OCOCH3), 199.1 (s, CO), 352.0 (t, JPC = 16.2 Hz,
Ru=C) ppm. IR (KBr): ν = 1374 (κ1-OCOsym), 1433 (P–Ph), 1456
˜
(κ2-OCOsym), 1530 (κ2-OCOasym), 1620 (κ1-OCOasym), 1649 (C=C),
3573 (OH) cm–1, Δν(uni) = 246 cm–1, Δν(chelate) = 74 cm–1. IR
(CH Cl ): ν = 1372 (κ1-OCOsym), 1433 (P–Ph), 1458 (κ2-OCOsym),
˜
2
2
1538 (κ2-OCOasym), 1616 (κ1-OCOasym), 1652 (C=C), 3564
(OH) cm–1, Δν(uni) = 244 cm–1, Δν(chelate) = 80 cm–1. MS (ESI):
calcd. for C61H64NaO6P2Ru [M + Na]+ m/z = 1079.3119, found
m/z = 1079.3098; calcd. for C61H65NO4P2Ru [M – OAc +
MeCN]+ m/z = 1039.3432, found m/z = 1039.3. C61H64O5P2Ru +
(0.10CH2Cl2): calcd. C 68.93, H 6.08; found C 68.59, H 6.18.
0.82 (s, 6 H, OCOCH3), 0.86–1.09 (m, 6 H, CH2), 1.17 [br. s, 1 H,
2
(Ru)=C=CHC(OH)], 1.23–1.35 (m, 4 H, CH2), 4.39 (t, JHP
=
3.7 Hz, 1.0 H, [Ru]=C=CH), 7.40–7.51 (m, 31 H, PPh3) ppm. 31P
NMR (CD2Cl2): δ = 34.4 (s, PPh3) ppm. 13C NMR (CD2Cl2): δ =
21.9 (s, OCOCH3), 22.6 (CH2), 23.2 (CH2), 25.5 (CH2), 39.7 (CH2),
3
39.9 (CH2), 69.6 (s, Ru=C=CH–COH), 117.5 (t, JPC = 4.7 Hz,
Ru=C=C), 128.0 (t, JPC + 5JPC = 9.3 Hz, PPh3-C3), 129.6 (t, JPC
3
1
Synthesis of [Ru(κ1-OAc)(κ2-OAc)(=CO{CH2}3)(PPh3)2] (11a):
Complex 11a (0.04 g, 19.0%) was obtained as a bright-yellow pow-
der from 1 (0.20 g, 0.27 mmol) and HCϵC(CH2)2OH (20.0 μL,
0.26 mmol) in DCM (15 mL). After reducing the volume of the
solution by half in vacuo, pentane (40 mL) was used to precipitate
the product, and it was washed further with 2ϫ20 mL portions of
pentane. Crystals for X-ray diffraction were obtained from a
CH2Cl2/pentane solution. 1H NMR (CD2Cl2): δ = 0.82 (s, 6 H,
2
+
3JPC = 43.0 Hz, PPh3-C1), 130.1 (s, PPh3-C4), 135.0 (t, JPC
+
=
2
4JPC = 11.5 Hz, PPh3-C2), 179.5 (s, OCOCH3), 352.1 (t, JPC
16.5 Hz, Ru=C) ppm. IR (KBr): ν = 1366 (κ1-OCOsym), 1434 (P–
˜
Ph), 1458 (κ2-OCOsym), 1538 (κ2-OCOasym), 1591 (κ1-OCOasym),
1646 (C=C), 3421 (OH) cm–1, Δν(uni) = 225 cm–1, Δν(chelate)
=
80 cm–1; IR (CH Cl ): ν = 1368 (κ1-OCOsym), 1434 (P–Ph), 1461
˜
2
2
(κ2-OCOsym), 1536 (κ2-OCOasym), 1600 (κ1-OCOasym), 1648 (C=C),
3571 (OH) cm–1, Δν(uni) = 232 cm–1, Δν(chelate) = 75 cm–1. MS (ESI):
MS (ESI): calcd. for C48H47O4P2Ru [M – OH]+ m/z = 851.1993,
found m/z = 851.1927. C48H48O5P2Ru·1.20CH2Cl2 : calcd. C 60.93,
H 5.24; found C 61.10, H 5.29.
3
OCOCH3), 0.93 (qn, JHH = 7.5 Hz, 2 H, [Ru]=COCH2CH2CH2),
3
3
2.48 (t, JHH = 7.7 Hz, 2 H, [Ru]=COCH2CH2CH2), 3.90 (t, JHH
= 7.3 Hz, 2 H, [Ru]=COCH2CH2CH2), 7.37 (J = 7.2 Hz, 12 H, H3-
PPh3), 7.42 (t, J = 7.1 Hz, 6 H, H4-PPh3), 7.54 (m, 12 H, 12 H,
H2-PPh3) ppm. 31P NMR (CD2Cl2): δ = 35.9 (s, PPh3) ppm. 13C
Complex 8h: This complex was obtained as a bright-orange powder
from 1 (0.20 g, 0.27 mmol) and 9-ethynyl-9-fluorenol (0.06 mg,
NMR (CD2Cl2):
δ
=
21.9 (s, OCOCH3), 22.6 (s,
0.29 mmol) in CH2Cl2 (15 mL). Yield = 0.12 g, (48%). 1H NMR [Ru]=COCH2CH2CH2), 52.8 (s, [Ru]=COCH2CH2CH2), 79.2 (s,
3
5
(CD2Cl2): δ = 0.82 (s, 6 H, OCOCH3), 2.77 [br. s, 1 H, [Ru]=COCH2CH2CH2), 127.8 (t, JPC + JPC = 9.3 Hz, PPh3-C3),
4
(Ru)=C=CHC(OH)], 4.56 (t, JHP = 3.8 Hz, 1.0 H, [Ru]=C=CH),
6.63–7.26 (m, 8 H, CH of fluorenyl), 7.35–7.47 (m, 34 H,
129.4 (s, PPh3-C4), 132.9 (t, 1JPC + 3JPC = 39.3 Hz, PPh3-C1), 134.4
2
4
(t, JPC + JPC = 11.8 Hz, PPh3-C2), 180.0 (s, OCOCH3), 304.7 (t,
Eur. J. Inorg. Chem. 2012, 1493–1506
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1503

J. M. Lynam et al.
FULL PAPER
2JPC = 11.8 Hz, [Ru]=C) ppm. IR (KBr): ν = 1368 (κ1-OCOsym), [Ru]=COCH2CH2CH2CH2), 72.3 (s, [Ru]=COCH2CH2CH2CH2),
˜
3
1433 (P–Ph), 1481 (κ2-OCOsym), 1541 (κ2-OCOasym), 1616 (κ1-
127.8 (t, JPC
+
5JPC = 9.39 Hz, PPh3–C3), 129.4 (s, PPh3–C4),
1
3
2
4
OCOasym) cm–1, Δν(uni)
=
248 cm–1, Δν(chelate) = 60 cm–1. IR 133.3 (t, JPC + JPC = 39.6 Hz, PPh3–C1), 134.5 (t, JPC + JPC
=
(CH Cl ): ν = 1375 (κ1-OCOsym), 1433 (P–Ph), 1483 (κ2-OCOsym), 11.3 Hz, PPh3–C2), 179.8 (s, OCOCH3), 306.8 (t, JPC = 11.7 Hz,
2
˜
2
2
1540 (κ2-OCOasym), 1615 (κ1-OCOasym) cm–1, Δν(uni) = 240 cm–1, [Ru]=C) ppm. IR (KBr): ν = 1375 (κ1-OCOsym), 1432 (P–Ph), 1481
˜
Δν(chelate) = 57 cm–1. MS (ESI): calcd. for C44H42NO3P2Ru [M –
OAc + MeCN]+ m/z = 796.1683, found m/z = 796.1615; MS
(LIFDI): m/z = 814 [M]+. C44H42O5P2Ru + (0.20CH2Cl2): calcd.
C 63.90, H 5.14; found C 63.90, H 5.14.
(κ2-OCOsym), 1549 (κ2-OCOasym), 1615 (κ1-OCOasym) cm–1,
Δν(uni) = 240 cm–1, Δν(chelate) = 68 cm–1. IR (CH Cl ): ν = 1375
˜
2
2
(κ1-OCOsym), 1434 (P–Ph), 1481 (κ2-OCOsym), 1545 (κ2-OCOasym),
1613 (κ1-OCOasym) cm–1, Δν(uni) = 238 cm–1, Δν(chelate) = 64 cm–1.
MS (ESI): calcd. for C45H44NO3P2Ru [M – OAc + MeCN]+ m/z =
810.1834, found m/z = 810.1825. C45H44O5P2Ru + (1.80CH2Cl2):
calcd. C 57.32, H 4.89; found C 57.60, H 4.90.
Synthesis of [Ru(κ1-OAc)(κ2-OAc)(=CO{CH2}4)(PPh3)2] (11b):
Complex 11b (0.03 g, 11.1%) was obtained as a bright-yellow pow-
der from 1 (0.25 g, 0.33 mmol) and HCϵC(CH2)3OH (32.0 μL,
0.34 mmol) in DCM (30 mL). After reducing the volume of the
solution by half in vacuo, pentane (20 mL) was used to precipitate
the product, and it was washed further with 2ϫ20 mL portions of
pentane. Crystals for X-ray diffraction were obtained from a
Synthesis of [Ru(κ1-OAc)(κ2-OAc)(=CO{CH2}5)(PPh3)2] (11c):
Minor modifications were made to the general procedure for the
preparation of 11c. In this instance the mixture was stirred for 28 h
at room temperature and the CH2Cl2 solvent was entirely removed
1
3
CD2Cl2/pentane solution. H NMR (CD2Cl2): δ = 0.77 (qn, JHH in vacuo before the product was washed with pentane. Complex 11c
= 6.9 Hz, 2 H, [Ru]=COCH2CH2CH2CH2), 0.83 (s, 6 H, OC-
(0.09 g, 52.9%) was obtained as an orange powder from 1 (0.15 g,
OCH3), 1.02 (qn, 3JHH = 6.1 Hz, 2 H, [Ru]=COCH2CH2CH2CH2), 0.19 mmol) and HCϵC(CH2)4OH (21.4 μL, 0.19 mmol) in DCM
3
2.61 (t, JHH = 6.9 Hz, 2 H, [Ru]=COCH2CH2CH2CH2), 3.85 (t, (10 mL). After removing the solvent in vacuo, the product was
3JHH = 5.8 Hz, 2 H, [Ru]=COCH2CH2CH2CH2), 7.38 (J = 7.2 Hz, washed with 3ϫ20 mL portions of pentane. Crystals for X-ray dif-
1
12 H, H3-PPh3), 7.42 (t, J = 7.1 Hz, 6 H, H4-PPh3), 7.56 (m, 12 H, fraction were obtained from a CH2Cl2/pentane solution. H NMR
12 H, H2-PPh3) ppm. 31P NMR (CD2Cl2): δ = 35.4 (s, PPh3) ppm.
13C NMR (CD2Cl2): δ = 17.0 (s, [Ru]=COCH2CH2CH2CH2), 21.6
(CD2Cl2): δ = 0.67 (m, 2 H, CH2), 0.84 (s, 6 H, OCOCH3), 0.91
(m, 2 H, CH2), 1.16 (m, 2 H, CH2), 2.72 (br. s, 2 H, CH2), 3.85 (t,
(s, OCOCH3), 22.6 (s, [Ru]=COCH2CH2CH2CH2), 47.2 (s, J = 4.2 Hz, 2 H, CH2), 7.36–7.43 (m, 18 H, PPh3), 7.59–7.61 (m,
Table 7. Data collection and structural refinement details for single-crystal X-ray diffraction studies of compounds 3[BF4]·2CH2Cl2, 4,
6b·2CH2Cl2, 6c·2CH2Cl2 and 8e.
3[BF4]·2CH2Cl2
4
6b·2CH2Cl2
6c·2CH2Cl2
8e
Empirical formula
Mr [gmol–1]
T [K]
C42H40BCl4F4NO5P2Ru
1030.37
110(2)
C45H45NO4P2Ru
826.83
110(2)
C46H44Cl4O6P2Ru
997.62
110(2)
C60H50Cl4O4P2Ru
1139.81
110(2)
C50H46O5P2Ru
889.88
110(2)
Wavelength [Å]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
0.71073
monoclinic
P21/n
14.592(4)
20.189(6)
15.770(5)
90
100.348(6)
90
4570(2)
4
0.71073
monoclinic
P21/c
23.2257(5)
16.0087(3)
10.42840(18)
90
94.5276(18)
90
3865.32(13)
4
1.421
0.533
1712
0.71073
0.71073
0.71073
triclinic
triclinic
triclinic
¯
¯
¯
P1
P1
P1
11.1010(14)
13.9967(17)
15.1277(19)
105.694(3)
92.102(2)
97.559(3)
2236.8(5)
2
13.5902(10),
13.9934(10),
16.6038(8)
98.866(5),
106.633(5),
115.860(7)
2576.1(3)
2
11.6253(5)
13.3991(6)
15.2933(6)
87.3510(10)
68.0190(10)
71.9900(10)
2094.27(15)
2
α [°]
β [°]
γ [°]
V [Å3]
Z
ρcalcd [Mgm–3]
μ [mm–1]
F(000)
1.498
0.707
2088
1.481
0.708
1020
1.469
0.623
1168
1.411
0.499
920
Crystal size [mm]
θ range for data collection [°] 1.74 to 28.36
Index ranges
0.24ϫ0.17ϫ0.06
0.13ϫ0.11ϫ0.07
2.93 to 29.15
–31ՅhՅ17
–20ՅkՅ20
–12ՅlՅ14
16216
0.14ϫ0.05ϫ0.04
1.40 to 28.42
–14ՅhՅ14
–18ՅkՅ18
–20ՅlՅ20
22964
0.24ϫ0.17ϫ0.13
3.02 to 32.15
–20ՅhՅ19
–19ՅkՅ16
–23ՅlՅ19
25341
0.11ϫ0.10ϫ0.04
2.19 to 29.99
–16ՅhՅ16
–18ՅkՅ18
–21ՅlՅ21
23951
19ՅhՅ19
–26ՅkՅ26
–21ՅlՅ20
46131
Measured reflections
Unique reflections
11370
8830
11014
16076
11837
[R(int) = 0.0377]
99.6 (to 28.36)
[R(int) = 0.0243]
99.6 (to 26.32)
[R(int) = 0.0706]
97.8 (to 28.42)
[R(int) = 0.0206]
99.3 (to 30.0)
[R(int) = 0.0201]
96.5 (to 30.03)
Completeness to θ
Absorption correction
Max., min. transmission
Refinement method
Data/restraints/parameters
GoF on F2
semiempirical from equivalents
0.972, 0.742
0.958, 0.748
0.963, 0.949
0.955, 0.908
1.00, 0.851
full-matrix least squares on F2
11014/4/533
11370/33/593
1.029
8830/3/497
1.086
16076/12/649
1.044
11837/0/527
1.033
1.007
Final R indices
[IϾ2σ(I)]
R indices
R1 = 0.0433
wR2 = 0.1080
R1 = 0.0625
wR2 = 0.1187
1.317/–0.743
R1 = 0.0385
R1 = 0.0722
R1 = 0.0337
wR2 = 0.0750
R1 = 0.0415
wR2 = 0.0802
1.290/–0.944
R1 = 0.0332
wR2 = 0.0777
R1 = 0.0449
wR2 = 0.0830
1.094/–0.847
wR2 = 0.0812
R1 = 0.0500
wR2 = 0.0873
1.097/–0.943
wR2 = 0.1620
R1 = 0.1345
wR2 = 0.1884
1.373/–1.625
(all data)
Δρmax/min [eÅ–3]
1504
www.eurjic.org
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 1493–1506

Ruthenium Acetate Complexes as Probes of Metal–Ligand Interactions
12 H, PPh3) ppm. 31P NMR (CD2Cl2): δ = 34.2 (s, PPh3) ppm. 13
NMR (CD2Cl2): δ = 20.4 (s, CH2), 22.5 (s, OCOCH3), 28.4 (s, tion for complexes 3[BF4], 6b, 8e, 8f, 11a and 11b was conducted
C
Details of X-ray Diffraction Experiments: Structural characterisa-
CH2), 29.2 (s, CH2), 50.8 (s, [Ru]=CCH2), 74.6 (s, [Ru]=COCH2),
127.7 (t, JPC + JPC = 9.2 Hz, PPh3-C3), 129.4 (s, PPh3-C4), 133.2
using a Bruker Smart Apex diffractometer with Mo-Kα radiation
(λ = 0.71073 Å) with a SMART CCD camera. Diffractometer con-
trol, data collection and initial unit cell determination were per-
formed using the SMART program.[36] Frame integration and unit-
cell refinement software were carried out with the program
3
5
1
2
(t, JPC
+
3JPC = 38.8 Hz, PPh3-C1), 134.5 (t, JPC
+
4JPC
=
2
11.5 Hz, PPh3-C2), 179.6 (s, OCOCH3), 311.0 (t, JPC = 11.8 Hz,
[Ru]=C) ppm. IR (KBr): ν = 1382 (κ1-OCOsym), 1433 (P–Ph), 1450
˜
(κ2-OCOsym), 1546 (κ2-OCOasym), 1608 (κ1-OCOasym) cm–1, Saint+.[37] Absorption corrections were applied by SADABS (v
Δν(uni) = 225 cm–1, Δν(chelate) = 96 cm–1. IR (CH Cl ): ν = 1382
2.03, Sheldrick).[38] Structures were solved by direct methods using
SHELXS-97, and refined by full-matrix least-squares using
SHELX-97.[39] All non-hydrogen atoms were refined anisotropi-
cally. Hydrogen atoms were placed using a riding model and in-
cluded in the refinement at calculated positions.
˜
2
2
(κ1-OCOsym), 1433 (P–Ph), 1452 (κ2-OCOsym), 1548 (κ2-OCOasym),
1607 (κ1-OCOasym) cm–1, Δν(uni) = 225 cm–1, Δν(chelate) = 96 cm–1.
MS (ESI): calcd. for C46H47O5P2Ru [M + H]+ m/z = 843.1942,
found m/z = 843.1936. C46H46O5P2Ru + (0.30CH2Cl2): calcd. C
64.11, H 5.42; found C 64.17, H 5.50.
Diffraction data for complexes 4, 11c and 6c, were collected at
110 K on an Oxford Diffraction SuperNova diffractometer with
Mo-Kα radiation (λ = 0.71073 Å) using an EOS CCD camera. The
crystal was cooled with an Oxford Instruments Cryojet. Dif-
fractometer control, data collection, initial unit cell determination,
frame integration and unit-cell refinement were carried out with
the program Crysalis.[40] Face-indexed absorption corrections were
applied using spherical harmonics, implemented by the SCALE3
ABSPACK scaling algorithm.[41] OLEX2[42] was used for overall
structure solution, refinement and preparation of computer graph-
ics and publication data. Within OLEX2, the algorithms used for
General Procedure for Monitoring the Degradation of Complexes
8a–i to Alkenes 9 by NMR Spectroscopy: Complex 1 (ca. 20 mg)
was added to an NMR tube fitted with a Young’s Tap and dis-
solved in approximately 0.5 mL CD2Cl2. The appropriate alkyne
(1 equiv.) was then added to the sample to generate 8 in situ. NMR
spectra were recorded soon after addition, and were re-recorded
over a number of days until the conversion was judged to have
gone to completion, although in some cases a trace amount of 8
remained. The alkenes 9a, 9b, 9c, 9d,[32] 9e,[33] 9f,[32] 9g,[32] 9h[34]
and 9i[35] were identified by comparison to literature data.
Table 8. Data collection and structural refinement details for single-crystal X-ray diffraction studies of compounds 8f·2CH2Cl2,
11a·2CH2Cl2, 11b·2CH2Cl2 and 11c.
8f·CH2Cl2
11a·2CH2Cl2
11b·2CH2Cl2
11c
Empirical formula
C48H48Cl2O5P2Ru
938.77
C46H46O5P2Cl4Ru
983.64
C47H48Cl4O5P2Ru
997.66
C46H46O5P2Ru
841.84
Mr [gmol–1]
T [K]
Wavelength [Å]
110(2)
0.71073
110(2)
0.71073
110(2)
0.71073
110(2)
0.71073
Crystal system
Space group
monoclinic
P21/n
monoclinic
P21/n
orthorhombic
Aba2
monoclinic
P21/c
a [Å]
b [Å]
c [Å]
α [°]
14.2578(11)
20.5627(15)
15.1557(11)
90
14.328(2)
21.311(3)
15.088(2)
90
18.2165(18)
16.3759(16)
15.0598(15)
90
23.3069(7)
15.8366(3)
10.6439(2)
90
β [°]
104.8250(10)
90
4295.4(6)
4
1.452
0.611
105.083(3)
90
4448.4(12)
4
1.469
0.710
90
90
4492.5(8)
4
1.475
92.537(2)
90
3924.85(15)
4
1.425
0.528
γ [°]
V [Å3]
Z
ρcalcd [Mgm–3]
μ [mm–1]
0.704
F(000)
1936
2016
2048
1744
Crystal size [mm]
θ range for data collection [°]
Index ranges
0.14ϫ0.08ϫ0.03
2.48 to 28.24
–19ՅhՅ19
–27ՅkՅ27
–19ՅlՅ20
43320
0.21ϫ0.06ϫ0.03
1.69 to 25.03
–17ՅhՅ17
–25ՅkՅ25
–17ՅlՅ17
34027
0.31ϫ0.25ϫ0.10
2.15 to 28.31
–24ՅhՅ24
–21ՅkՅ21
–20ՅlՅ20
22618
0.23ϫ0.17ϫ0.08
3.11 to 30.04
–32ՅhՅ28
–20ՅkՅ20
–6ՅlՅ14
16799
Measured reflections
Unique reflections
10665
7825
5538
9876
[R(int) = 0.0441]
99.9 (to 28.24)
[R(int) = 0.0891]
99.8 (to 25.00)
[R(int) = 0.0168]
99.9 (to 28.31)
[R(int) = 0.0367]
99.4 (to 27.45)
Completeness to θ
Absorption correction
Max., min. transmission
Refinement method
Data/restraints/parameters
GoF on F2
semiempirical from equivalents
0.932, 0.799
1.00, 0.611
1.00, 0.84
1.00, 0.730
full-matrix least squares on F2
10665/6/538
1.016
7825/1/529
1.011
5538/4/317
1.055
9876/3/500
1.043
Final R indices
[IϾ2σ(I)]
R indices
R1 = 0.0435
wR2 = 0.1022
R1 = 0.0732
wR2 = 0.1178
2.094/–0.670
R1 = 0.0566
wR2 = 0.1217
R1 = 0.1045
wR2 = 0.1431
1.279/–0.772
R1 = 0.0293
wR2 = 0.0693
R1 = 0.0309
wR2 = 0.0705
0.423/–1.230
R1 = 0.0481
wR2 = 0.0989
R1 = 0.0739
wR2 = 0.1054
1.139/–1.818
(all data)
Δρmax/min [eÅ–3]
Eur. J. Inorg. Chem. 2012, 1493–1506
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1505

J. M. Lynam et al.
FULL PAPER
asa, J. Gimeno, Eur. J. Inorg. Chem. 2001, 571; e) S. Rigaut, D.
Touchard, P. H. Dixneuf, Coord. Chem. Rev. 2004, 248, 1585;
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map”. Refinement was by full-matrix least-squares using the
SHELXL-97[39] algorithm within OLEX2. All non-hydrogen atoms
were refined anisotropically. Hydrogen atoms were placed using a
riding model and included in the refinement at calculated positions,
except for the O–H hydrogen atom in 8f, which was found by a
difference map.
[15] a) E. Bustelo, P. H. Dixneuf, Adv. Synth. Catal. 2005, 347, 393;
b) E. Bustelo, P. H. Dixneuf, Adv. Synth. Catal. 2007, 349, 933.
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Details of data collection and structure refinement are presented in
Tables 7 and 8. CCDC-842583 (3[BF4]·2CH2Cl2), -842584 (4),
-842585 (6b·2CH2Cl2), -842586 (6c·2CH2Cl2), -842587 (8e),
-842588
(8f·2CH2Cl2),
-842589
(11a·2CH2Cl2),
-842590
(11b·2CH2Cl2) and -842591 (11c) contain the supplementary crys-
tallographic 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.
[21] S. Pavlik, K. Mereiter, M. Puchberger, K. Kirchner, J. Or-
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2007, 26, 6576.
Acknowledgments
We are grateful to the EPSRC (DTA studentship to C. E. W) and the
University of York (Summer Studentship to C. A. U) for funding. Pro-
fessors Robin Perutz (Univeristy of York) and Paul Raithby (Univer-
sity of Bath) are thanked for insightful comments on this work.
[26] A. B. Antonova, N. E. Kolobova, P. V. Petrovsky, B. V. Lok-
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[28] The nature of the metal fragment will also influence the nature
of the interaction with the ligand, this effect is more noticeable
for π back-bonding. See G. Frenking, K. Wichmann, N.
Fröchlich, J. Grobe, W. Golla, D. Le Van, B. Krebs, M. Läge,
Organometallics 2002, 21, 2921 and references therein.[24]
[29] For a relationship between the electrophilicity of Fischer carb-
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[32] Data compared to that found for the appropriate compound
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Published Online: December 21, 2011
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