Isomerization Processes on Organoruthenium Complexes Bearing κ2(P,C)-Bidentate Ligands Generated Through Nucleophilic Addition to Coordinated Alkenyl Phosphanes

Article abstract of DOI:10.1002/ejic.201800895

Nucleophilic attack on complex [RuCl(η⁶-C₁₀H₁₄){κ³(P,C,C)-Ph₂PCH₂CH=CH₂}][BPh₄] (2) takes place, either to the metal or to the coordinated olefin depending on the nucleophile and the reaction conditions. The nucleophilic attack of phosphanes on the coordinated olefin leads diastereoselectively to complexes [RuCl(η⁶-C₁₀H₁₄){?²(P,C)-Ph₂PCH₂CH(PR₃)CH₂}]⁺ bearing κ²(P,C)-ligands obtained as a racemic mixture of the enantiomers R_RuSc/S_RuR_C. These kinetically stable isomers, undergo an isomerization process leading to the thermodynamically stable products isolated as the diastereoisomer R_RuR_C/S_RuS_C. ³¹P{¹H} NMR monitoring experiments on the isomerization processes have been carried out.

Full text of DOI:10.1002/ejic.201800895

A Journal of
Accepted Article
Title: ISOMERIZATION PROCESSES ON ORGANORUTHENIUM
COMPLEXES BEARING κ2(P,C)- BIDENTATE LIGANDS
GENERATED THROUGH NUCLEOPHILIC ADDITION TO
COORDINATED ALKENYL PHOSPHANES
Authors: Isaac García de la Arada, Josefina Díez, Pilar Gamasa, and
Elena Lastra
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201800895
Link to VoR: http://dx.doi.org/10.1002/ejic.201800895

10.1002/ejic.201800895
European Journal of Inorganic Chemistry
FULL PAPER
ISOMERIZATION PROCESSES ON ORGANORUTHENIUM
COMPLEXES BEARING κ2P,C- BIDENTATE LIGANDS
GENERATED THROUGH NUCLEOPHILIC ADDITION TO
COORDINATED ALKENYL PHOSPHANES
Isaac García de la Arada, Josefina Díez, M. Pilar Gamasa and Elena Lastra*.
Abstract: Nucleophilic attack on complex [RuCl(η6-C10H14){κ3P,C,C-
Ph2PCH2CH=CH2}][BPh4] (2) takes place, either to the metal or to
the coordinated olefin depending on the nucleophile and the reaction
conditions. The nucleophilic attack of phosphanes on the
coordinated olefin leads diastereoselectively to complexes [RuCl(η6-
nucleophiles upon coordinated olefins reported in the literature
might be the catalytic synthesis of azacyclobutanes.4 This
process occurs through the attack of amines to non-activated
olefins, which can happen either in an intermolecular4,5 or
intramolecular way.6
C10H14){κ2P,C-Ph2PCH2CH(PR3)CH2}]+
bearing
κ2P,C-ligands
On the other hand, hemilabile alkenylphosphane ligands are
able to coordinate diastereoselectively to a metal as a chelate
3(P,C,C), as it has been reported for some examples.7 This
coordination mode has led to interesting reactivities involving the
C-C double bond and resulting in one single diastereoisomer.8
We have previously reported the synthesis of new half-sandwich
obtained as a racemic mixture of the enantiomers RRuSc/SRuRC.
These kinetically stable isomers, undergo an isomerization process
leading to the thermodynamically stable products isolated as the
diastereoisomer RRuRC/SRuSC. 31P{1H} NMR monitoring experiments
on the isomerization processes have been carried out.
ruthenium(II)
complexes
bearing
the
hemilabile
allyldiisopropylphosphane (ADIP) and explored their behaviour
in nucleophilic addition reactions which occur in all cases in a
diastereoselective way.9 In particular, thiolates as anionic S-
donor nucleophiles perform two nucleophilic attacks, both to the
olefin and the metal centre, giving rise to novel and
unprecedented ligands coordinated 3(P,S,C). On the other
hand, tertiary phosphanes as neutral P-donor nucleophiles led to
the formation of new ruthenaphosphacycles coordinated 2(P,C).
In this work we have now extended those studies to half-
sandwich ruthenium complexes containing the phosphane
allyldiphenylphosphane (ADPP) ligand. As a consequence, we
are able to stablish a comparison in the hemilability and
reactivity of the complexes bearing ADPP and ADIP
allylphosphanes, due to their different properties of basicity and
size, being the ADIP bulkier and more basic than the ADPP.
Furthermore, we report a closer study to the diastereoselectivity
observed in those additions of phosphanes to κ3P,C,C
coordinated allylphosphanes, which allows, in some cases, to
control the formation of the kinetically stable or the
thermodynamically stable diastereoisomer for complexes
[RuCl(η6-C10H14){κ2P,C-R2PCH2CH(PR3)CH2}][BPh4].
Introduction
Prochiral alkenes are very useful in enantioselective synthesis.1
Most of the current examples are based in complexes with
enantiopure ligands, however the study of transition metal-
fragments bearing a stereogenic centre also plays an important
role in activating asymmetric olefins towards the addition of
nucleophiles in a stereoselective manner.2 These metal centres
usually have a pseudooctaedral geometry3 that might induce the
selective coordination of the prochiral olefins through one of their
enantiotopic faces (see Figure 1). Moreover, providing that
rotation around the C=C bond is allowed, two different rotamers
can exist for each of the two isomers.
Figure 1. Rotamers and configurational diastereomers generated upon the
coordination of prochiral alkenes.
Results and Discussion
Synthesis of [RuCl2(η6-C10H14){κ1P-Ph2PCH2CH=CH2}] (1) and
[RuCl(η6-C10H14){κ3P,C,C-Ph2PCH2CH=CH2}][BPh4] (2). The
reaction of the dimeric complex [RuCl(μ-Cl)(η6-C10H14)]2 with a
stoichiometric amount of allyldiphenylphosphane (ADPP) in
dichloromethane, led to the neutral complex [RuCl2(η6-
C10H14){κ1P-Ph2PCH2CH=CH2}] (1) as an air-stable orange solid.
Treatment with NaBPh4 of a methanol suspension of complex 1
resulted in the abstraction of the chloride ligand and coordination
of the olefin to the metal center, leading to the cationic complex
[RuCl(η6-C10H14){κ3P,C,C-Ph2PCH2CH=CH2}][BPh4] (2) which
was isolated as an air-stable yellow solid (See Scheme 1).
In those cases, the prochiral face selectivity and orientation of
olefins are important governing factors that decide the
stereochemistry of the product.
A
relevant example of nucleophilic attacks of neutral
Dr. I García de la Arada, Prof. J. Díez, Prof. M. P. Gamasa and Prof.
E. Lastra
Departamento de Quimica Organica e Inorganica. Universidad de
Oviedo, 33006 Oviedo, Principado de Asturias, Spain. Fax: 34-
985103446
E-mail for corresponding author: elb@uniovi.es
Supporting information for this article is given via a link at the end of
the document.
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10.1002/ejic.201800895
European Journal of Inorganic Chemistry
FULL PAPER
Scheme 1. Synthesis of complexes [RuCl2(η6-C10H14){κ1P-Ph2PCH2CH=CH2}]
(1) and [RuCl(η6-C10H14){κ3P,C,C-Ph2PCH2CH=CH2}][BPh4] (2).
Both products were fully characterized by elemental analysis
and spectroscopy techniques,10 which confirm the coordination
mode of the allylphosphane as κ1P for complex 1 and κ3P,C,C
for complex 2. In particular, IR spectrum for complex 1 shows
an absorption corresponding to the non-coordinate C=C double
bound at 1629 cm-1, while complex 2 shows the (C=C)
absorption at 1478 cm-1 due to the interaction with the
ruthenium. 31P{1H} NMR spectra at room temperature also
indicate the effect of the olefin coordination, showing the signal
for the allylphosphane shifted towards higher field ( = -63.4
ppm for 2) with respect to that of the corresponding κ1P
precursor ( = 24.6 ppm for 1).
Figure 2. Molecular structure and atom-labeling scheme for the complex
[RuCl2(η6-C10H14){κ1P-Ph2PCH2CH=CH2}] (1). Hydrogen atoms except those of
the olefin have been omitted for clarity. Non-hydrogen atoms are represented
by their 20% probability ellipsoids. C* = centroid of the η6-C10H14 ligand.
Selected bond lengths (Å): Ru(1)-Cl(1) = 2.419(1), Ru(1)-Cl(2) = 2.415(1),
Ru(1)-P(1) = 2.341(1), P(1)-C(11) = 1.849(3), C(11)-C(12) = 1.487(4), C(12)-
C(13) = 1.288(7), Ru(1)-C* = 1.711(1). Selected bond angles (°): Cl(1)-Ru(1)-
Cl(2) = 87.23(2), Cl(1)-Ru(1)-P(1) = 84.74(2), Cl(2)-Ru(1)-P(1) = 87.57(2),
Additionally, the 1H NMR spectrum of 2 shows CH=CH2
resonances which appear at higher fields than those for the
olefin in complex 1 because of the π-coordination.
The structure of complex 1 was determined by single crystal X
ray diffraction analysis. Suitable crystals were obtained by slow
diffusion of hexane into a solution of 1 in CH2Cl2. ORTEP type
representation of the complex is shown in Figure 2 and selected
bond lengths and angles are presented in the caption.
C*-Ru(1)-P(1)
= 130.00(2), C*-Ru(1)-Cl(1) = 127.41(1), C*-Ru(1)-Cl(2) =
125.67(2), C(11)-C(12)-C(13) = 126.20(40).
The molecule exhibits a pseudooctahedral three-legged piano-
stool geometry with the ruthenium atom bonded to the η6-p-
cymene ligand, to the phosphorous atom of the ADPP ligand
and to the two chlorine atoms. Bond distances Ru(1)-P(1)
(2.341(1) Å) and Ru(1)-Cl (2.419(1) and 2.415(1) Å) are in
Complex [RuCl(η6-C10H14){κ3P,C,C-Ph2PCH2CH=CH2}][BPh4] (2)
can react with nucleophiles either by ligand substitution on the
ruthenium center with displacement of the olefin, or by
nucleophilic addition to the coordinated carbon-carbon double
bond of the allylphosphane ligand. Competition between the two
processes depends principally on the nucleophile.
accordance
with those found for ruthenium-phosphane
complexes such as [RuCl2(PPh2(CH2)3aaaaη6-C6H5)]11 (Ru-P:
2.3187 Å; Ru-Cl: 2.4039 and 2.4271 Å), [RuCl2(p-
MeC6H4Me)(DPVP)]12 (Ru-P: 2.3529 Å; Ru-Cl: 2.4065 and
2.4129 Å) or [RuCl2(η6-C10H14)(κ1-(P)-PPh2C4H5N2)]13 (Ru-P:
2.3523 Å; Ru-Cl: 2.4070 and 2.4320 Å). The C(12)-C(13) bond
distance (1.288(7) Å), also agrees with a non-coordinated
carbon-carbon double bond.
Nucleophilic attack to the metal center: Synthesis of
[RuCl(η6-C10H14){κ1P-Ph2PCH2CH=CH2}(L)][BPh4] (L = NCMe
(3), py (4), P(OMe)3 (5a), P(OEt)3 (5b), P(OPh)3 (5c). When
complex [RuCl(η6-C10H14){κ3P,C,C-Ph2PCH2CH=CH2}][BPh4] (2)
is dissolved in acetonitrile, complex
[RuCl(η6-C10H14){κ1P-
For complex 2, the two faces of the alkene coordinated to
ruthenium are diastereotopic.7d, 14 As stated before, the 31P{1H}
NMR spectrum of complex 2 in CD2Cl2 shows one signal ( = -
63.4 ppm) and remains unchanged within a wide range of
temperature (-60 to +25 °C). These NMR data agree with a
highly diastereoselective generation of the chelate ring
[Ru{κ3P,C,C-Ph2PCH2CH=CH2}] as reported by us for the
complexes [RuCl(η6-C10H14){κ3P,C,C-iPr2PCH2CH=CH2}][BPh4],9
Ph2PCH2CH=CH2}(NCMe)][BPh4] (3) is immediately formed. In
the same way, the reaction of complex 2 in THF with one
equivalent of pyridine or phosphites led instantly to complexes
[RuCl(η6-C10H14){κ1P-Ph2PCH2CH=CH2}(L)][BPh4] (L = py (4),
P(OMe)3 (5a), P(OEt)3 (5b), P(OPh)3 (5c)) (Scheme 2). The
synthesis of these complexes are the result of an olefin-
nucleophile exchange and agree with the hemilabile character of
the ADPP ligand in complex 2.
[Ru(5-C9H7){3P,C,C-Ph2PCH2CH=CH2}(PPh3)][PF6],7f
[Ru(5-C5H5){3P,C,C-Ph2PCH2CH=CH2}(PPh3)][PF6].8d
and
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10.1002/ejic.201800895
European Journal of Inorganic Chemistry
FULL PAPER
Figure 3. Molecular structure and atom-labeling scheme for the cation of
complexes [RuCl(η6-C10H14){κ1P-Ph2PCH2CH=CH2}(NCMe)][BPh4] (3) and
Scheme 2. Synthesis of complexes 3, 4, and 5a-c.
[RuCl(η6-C10H14){κ1P-Ph2PCH2CH=CH2}{P(OMe)3}][BPh4]
(5a).
Hydrogen
atoms (except for the olefin) have been omitted for clarity. Non-hydrogen
atoms are represented by their 30% (3) or 20% (5a) probability ellipsoids.
Complexes 3, 4, and 5a-c have been analytically and
spectroscopically characterized. In particular, it must be noted
that: i) For all complexes, the IR spectra in KBr show the
characteristic (C=C) absorption in the range 1573-1602 cm-1 as
expected for non-coordinated C=C double bond. ii) 31P{1H}NMR
spectra of complexes 3 and 4 show a singlet at 27.6 (3) and
25.7 (4), respectively, clearly shifted to lower fields as expected
for the ADPP coordinated ĸ1P. 31P{1H}NMR spectra of
complexes 5a-c show two doublet signals (2JPP = 80.2-81.4 Hz),
one of them corresponding to the phosphorous atom of the
allylphosphane ADPP coordinated ĸ1P (29.6-30.6 ppm) and the
other corresponding to the phosphorous of the phosphite ligand
at low fields (114.9-119.8 ppm). iii) 1H and 13C{1H}NMR spectra
show the signals due to the olefin, the p-cymene ring and the
phosphite groups (see experimental). iv) Molar conductivity
values in acetone for all complexes are in the range expected for
electrolytes 1:1.15
Nucleophilic attack to the coordinated olefin
Synthesis
Ph2PCH2CH(PR3)CH2}][BPh4] (PR3 = PMe3 (6a), PPh3 (6b),
ADPP (6c), ADIP (6d)). When complex reacts with
of
(RRuSC/SRuRC)-[RuCl(η6-C10H14){κ2P,C-
2
phosphanes, a different behaviour was observed. Thus, the
reaction of complex 2 with the phosphanes PMe3, ADPP and
ADIP in THF at room temperature or PPh3 at -30°C afforded the
complexes
[RuCl(η6-C10H14){κ2P,C-
Ph2PCH2CH(PR3)CH2}][BPh4] (PR3 = PMe3 (6a), PPh3 (6b),
ADPP (6c), ADIP (6d)) (Scheme 3).
For this family of complexes we could observe that the ADIP
ligand has more tendency to form ĸ3P,C,C chelate than the
ADPP. Thus, the synthesis of complex 2 requires 12 h of
reaction, while the ADIP analogue is completed after 2.5 h.
In the same way, complex 3 can be dried at high vacuum, while
the ADIP analogue removes the MeCN molecule to coordinate
the olefin again. Moreover, opening the chelate with pyridine
requires higher temperature for the ADIP than for the ADPP
ligand.9
Slow diffusion of diethyl ether into a solution of 3 in acetonitrile,
and hexane into a solution of 5a in CH2Cl2, allow crystals
suitable for single crystal X ray diffraction analysis. ORTEP type
representations of the complexes are shown in Figure 3 and
selected bond lengths and angles are listed in Table S1 in the
Supporting Information.
Scheme 3. Synthesis of complexes 6a-d
Complex 6c can be also obtained as the chloride salt through
the reaction of the dimeric complex [RuCl(μ-Cl)(η6-C10H14)]2 with
an excess of allyldiphenylphosphane (ADPP) in methanol for
two hours at room temperature (Scheme 4). The first step for
this process must be the formation of the cation of complex 2 in
solution and nucleophilic attack of the free ADPP, in the same
fashion as it occurs with the analogous product with ADIP
ligand.9
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10.1002/ejic.201800895
European Journal of Inorganic Chemistry
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Scheme
4.
Synthesis
of
[RuCl(η6-C10H14){κ2P,C-
Ph2PCH2CH(Ph2PCH2CH=CH2)CH2}][Cl].
The complexes 6a-d are isolated as their tetraphenylborate salts
in good yields as yellow stable solids. For all compounds, molar
conductivity values in acetone are in the range expected for
electrolytes 1:115 and the analyses and electrospray mass
spectra agree with the proposed stoichiometries.
Figure 4. Molecular structure and atom-labeling scheme for the cation of
complex
The complexes have been fully spectroscopically characterized.
Significantly, 31P{1H} NMR spectra are indicative of the
coordination mode of the allylphosphane and the
diastereoselectivity of this reaction since these spectra show two
doublets (3JPP = 68.1-85.2 Hz) according with the two different
phosphorous atoms in the molecule at  = 71.7 and 26.6 (6a),
72.7 and 26.0 (6b), 72.5 and 25.9 ppm (6c) and 71.8 and 37.7
(6d) ppm for the phosphane and phosphonium moieties,
respectively.
[RuCl(ƞ6-C10H14){ĸ2(P,C)-Ph2PCH2CH(PMe3)CH2}][BPh4]·MeOH
(6a·MeOH). Hydrogen atoms (except for the ruthenaphosphacycle) have been
omitted for clarity. Non-hydrogen atoms are represented by their 10%
probability ellipsoids. C* = centroid of the η6-p-cymene ligand. Selected bond
lengths (Å): Ru(1)−Cl(1) = 2.432(1), Ru(1)−P(1) = 2.277(1), Ru(1)−C(13) =
2.146(3), Ru(1)-C* = 1.738(1), P(1)−C(11) = 1.833(3), C(11)−C(12) = 1.532(4),
C(12)−C(13) = 1.556(4), C(12)-P(2) = 1.817(3). Selected bond angles (deg):
Cl(1)−Ru(1)−P(1) = 84.63(3), Cl(1)-Ru(1)-C(13) = 84.24(8), P(1)-Ru(1)-C(13) =
80.20(8), C*−Ru(1)−Cl(1)
=
124.88(3), C*−Ru(1)−P(1)
129.21(8), Ru(1)−C(13)−C(12)
110.78(19), C(11)−C(12)−C(13) = 113.80(20), P(2)-
=
135.98(2),
118.69(18),
C*−Ru(1)−C(13)
=
=
=
P(2)−C(12)−C(13)
The 1H and 13C{1H} NMR spectra also show the signals
corresponding to a sole diastereoisomer and agree with the
proposed structure (See Experimental).
C(12)-C(11) = 110.34(19).
The structure of complex 6a was determined by single-crystal X-
ray diffraction analysis. Suitable crystals were obtained by slow
diffusion of diethyl ether into a solution of compound 6a in
methanol. ORTEP type representation of the complex is shown
in Figure 4 and selected bond lengths and angles are presented
in the caption.
The most remarkable feature in this pseudooctahedral structure
is the presence of the ruthenaphosphacycle with the
trimethylphosphonium substituent. The bond distance C(12)-
P(2) of 1.817(3) Å is typical of a phosphorous-carbon single
bond, and the carbon atoms C(11), C(12), and C(13) in the
ruthenaphosphacycle present sp3 hybridization, as shown by the
bond angles around them close to 109°.
The formation of complexes 6a-d is diastereoselective, since
only one diastereoisomer is detected by NMR spectroscopy.
31P{1H} NMR spectra at low temperature (-60°C) were carried
out to discard the existence of dynamic processes for these
complexes.
The observed diastereoisomer (RRuSC/SRuRC) is the same as the
one obtained for the complex [RuCl(η6-C10H14){κ2P,C-
iPr2PCH2CH(iPr2PCH2CH=CH2)CH2}][Cl] as shown in our
previous work.9 This fact can be explained through the
diastereoselectivity observed in the formation of the precursor
κ3P,C,C complexes as reported for the analogous complexes
[RuCl(η6-C10H14){κ3P,C,C-iPr2PCH2CHCH2}][BPh4]
which
presents the racemic mixture of absolute configuration RRu and
olefin coordination through the si enantioface, and SRu and olefin
coordination through the re enantioface. Nucleophilic addition to
the open face leads to the obtained diastereoisomer as a
racemic mixture.
The Ru(1)-C(13) bond distance (2.146(3) Å) agree with a
ruthenium-carbon single bond and with those found for complex
[RuCl(η6-C10H14){κ2P,C-
iPr2PCH2CH(iPr2PCH2CH=CH2)CH2}][BPh4] of 2.142(2) Å.9
The behavior of phosphanes resulting in a nucleophilic attack
over the double bond is in contrast with the reactivity shown by
phosphites that lead to an olefin-nucleophile exchange. We
assume this difference could be due to the higher relative
nucleophilicity of phosphanes towards phosphites.16
Synthesis
of
RuCl(η6-C10H14){κ1P-
Ph2PCH2CH=CH2}(PPh3)][BPh4] (7). For complex 6b with the
bulky triphenylphosphane, the opening of the cycle and
nucleophilic attack of the PPh3 to the metal center was observed
at higher temperatures, resulting in the κ1P-ADPP derivative
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10.1002/ejic.201800895
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[RuCl(ƞ6-C10H14){ĸ1(P)-Ph2PCH2CH=CH2}(PPh3)][BPh4] (7). This
complex can be also obtained by treatment of complex 2 with
triphenylphosphane in refluxing THF. For this reaction, the first
step must be the quick initial attack of the phosphane to the
double bond, giving rise to complex 6b (Scheme 5) followed by
the ring opening, since the reaction of 2 to give complex 6b
takes place at much lower temperature.
Complex 7 shows two doublet signals in the 31P{1H} NMR at
19.5 ppm for the PPh3 and at 23.6 ppm for the ADPP ligand
(2JPP = 52.2 Hz), typical for its κ1P coordination mode. Also the
IR, 1H and 13C{1H} NMR agree with the presence of the non-
coordinated olefin moiety. Thus, the more relevant spectroscopic
data are as follow: i) IR spectrum shows an absorption
corresponding to the C=C double bound at 1579 cm-1. ii) olefinic
protons appear as two doublets at 4.36 (3JHH = 16.8 Hz) and
4.63 ppm (3JHH = 10.4 Hz) for the =CH2 group and a multiplet at
4.71 ppm for the =CH. Iii) the corresponding carbons appear as
doublets at 120.5 ppm (3JCP = 9.9 Hz) and 128.6 ppm (2JCP
=
11.5 Hz) respectively.
Figure 5. Molecular structure and atom-labeling scheme for the cationic
complex [RuCl(ƞ6-C10H14){ĸ1(P)-Ph2PCH2CH=CH2}(PPh3)]+ (7). Hydrogen
atoms (except for the olefin) have been omitted for clarity. Non-hydrogen
atoms are represented by their 20% probability ellipsoids.
[RuCl(ƞ6-C10H14){ĸ1(P)-
Isomerization processes. Synthesis of (RRuRC/SRuSC)-
Scheme
5.
Synthesis
of
[RuCl(η6-C10H14){κ2P,C-Ph2PCH2CH(PR3)CH2}][BPh4] (PR3
=
Ph2PCH2CH=CH2}(PPh3)][BPh4] (7).
PPh3 (6b), ADPP (6c)). When the synthesis of complexes 6b
and 6c were carried out using longer reaction times, a different
set of signals appear in the 31P{1H} NMR spectra along with
those due to complexes 6b and 6c. This transformation into the
new complexes 6b’ and 6c’ can be completed and they could be
isolated and characterized. Their analytical data as well as the
1H and 13C{1H} NMR spectroscopy data are exactly the same
than those found for complexes 6b and 6c. The only
differences were found in the 31P{1H} NMR spectra which show
two doublets at  = 66.6 and 25.6 ppm (3JPP = 74.1 Hz) for
complex 6b’ and at  = 68.0 and 27.4 ppm (3JPP = 70.5 Hz) for
complex 6c’. These new complexes can be also obtained by
stirring at room temperature the isolated complexes 6b (72.7
and 26.0, 3JPP = 81.4 Hz), and 6c (72.5 and 25.9, 3JPP = 85.2 Hz)
for 2 h or 7 days, respectively.
Finally, the structure was studied by single-crystal X-ray
diffraction analysis. Suitable crystals were obtained by slow
diffusion of hexane into a solution of 7 in acetone. An ORTEP
type representation of the cationic complex is shown in Figure 5,
and selected bond lengths and angles are listed in Table S1 in
the Supporting Information. Bond distances Ru(1)-P(1) and
Ru(2)-P(2) of 2.378(1) and 2.356(1) Å are typical of ruthenium-
phosphorous single bonds, while the distance C(12)-C(13) of
1.245(6) Å undoubtedly shows the presence of the non-
coordinated olefin. The figure represents the enantiomer with
absolute configuration S for the metal center, although both
enantiomers (S and R) are present in the crystal as the racemic
mixture.
According to this finding and to the spectroscopic data obtained
for the new complexes 6b’ and 6c’, these can be proposed as
the result of the isomerization from the kinetically obtained
diasteroisomers
(RRuSC/SRuRC)
6b
and
6c
to
the
thermodynamically more stable (RRuRC/SRuSC) diasteroisomers
6b’ and 6c’.
For complexes 6a and 6d no isomerization was observed and
they were found to be stables even in refluxing THF. Based on
the chemical shift on the 31P{1H} NMR spectra of the
phosphorous bonded to the ruthenium (Ru-PPh2) of these
complexes (71.7 (6a) and 71.8 (6d)), we conclude it is the
kinetic product that is formed. These chemical shifts are in
agreement with the data obtained for the kinetic products 6b
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10.1002/ejic.201800895
European Journal of Inorganic Chemistry
FULL PAPER
(72.7 ppm) and 6c (72.5 ppm) and different from the values
obtained for the thermodynamic products (66.6 ppm for complex
6b’ and 68.0 ppm for complex 6c’).
temperature and under refluxing THF conditions, as reported
here for the analogous complex 6a.
Table 1 shows the 31P{1H} NMR data for both diastereoisomers
of the complexes bearing ADIP. The thermodynamically stable
RRuRC/SRuSC diasteroisomers were obtained as pure complexes
after stirring at room temperature for 30 min (PPh3), overnight
(ADPP) or refluxing overnight (ADIP).
Slow diffusion of hexane into a solution of compound 6c’ in
dichloromethane allows suitable crystals for X-ray diffraction
analysis. Figure 6 shows an ORTEP-type view of the enantiomer
with absolute configuration S in the ruthenium and S for the
stereogenic carbon C(12). However, both enantiomers (SRuSC
and RRuRC) are present in the crystal in equal proportion, as the
crystal belongs to the centric space group P21/c. Selected
bonding data are collected in the caption.
The bond distances and angles found for complex 6c’ are
comparable to those obtained for the kinetically stable isomer of
complex 6a and no significant differences can be observed for
the two diastereoisomers.
Table 1. 31P{1H} NMR data for complexes complexes [RuCl(η6-
C10H14){κ2P,C-iPr2PCH2CH(PR3)CH2}][BPh4] bearing ADIP.a
PR3
PPh3
ADPP
ADIP
RRuSC/SRuRC
RRuRC/SRuSC
85.5 and 25.3 (74.1 Hz)
86.1 and 24.0 (68.0 Hz)
86.6 and 36.5 (63,2 Hz)
81.0 and 26.0 (68.0 Hz)
81.4 and 26.5 (64.4 Hz)
80.6 and 36.9 (58.3 Hz)
[a] Values in ppm. 3JPP in Hz.
As shown, the isomerization processes depend largely on the
size of the phosphonium group and the PR2 moiety bonded to
the metal center. Thus, the complexes with the phosphonium
with the smallest cone angle (PMe3) do not undergo
isomerization. However, the complexes with the large PPh3,
evolve readily to the thermodynamically controlled
isomer and for complex 6b, the synthesis must be performed at -
30°C. Besides, for the same phosphonium moiety, complexes
bearing ADIP isomerize faster than those bearing ADPP.
These isomerization processes have been also detected for
rhodium and iridium complexes [MCl(η5-C5Me5){ĸ2(P,C)-
iPr2PCH2CH(PPh3)CH2}][BPh4].18
The mechanism proposed for these rhodium and iridium
complexes starts with a β-H elimination to give a metal hydride
which would insert into the alkene to give the thermodynamic
product. Even when this mechanism can be proposed for our
complexes (Scheme 6, pathway A), we cannot rule out the
opening of the ruthenaphosphacycle (Scheme 6, pathway B).
In order to get insight into the mechanism of these isomerization
processes, a sample of complex 6b in CD2Cl2 was prepared at
233 K and monitorized by 31P{1H} NMR spectroscopy (Figure 7).
As the temperature was raising up, the isomerization from the
kinetic product 6b to the thermodynamic product 6b´ was
observed and the formation of transient species is assessed by
the 31P{1H} NMR spectra, which show peaks corresponding to
complex [RuCl(η6-C10H14){κ3P,C,C-Ph2PCH2CH=CH2}][BPh4] (2)
together with small peaks which can be assigned to complex 7.
Figure 6. Molecular structure and atom-labeling scheme for the cation of
complex [RuCl(ƞ6-C10H14){ĸ2(P,C)-Ph2PCH2CH(Ph2PCH2CH=CH2)CH2}][BPh4]
(6c’). Hydrogen atoms (except for the ruthenaphosphacycle) have been
omitted for clarity. Non-hydrogen atoms are represented by their 20%
probability ellipsoids. C* = centroid of the η6-p-cymene ligand. Selected bond
lengths (Å): Ru(1)−Cl(1) = 2.412(1), Ru(1)−P(1) = 2.285(1), Ru(1)−C(13) =
2.153(2), Ru(1)-C* = 1.725(1), P(1)−C(11) = 1.842(3), C(11)−C(12) = 1.527(3),
C(12)−C(13) = 1.531(3), C(12)-P(2) = 1.799(2). Selected bond angles (deg):
Cl(1)−Ru(1)−P(1) = 93.18(2), Cl(1)-Ru(1)-C(13) = 82.99(7), P(1)-Ru(1)-C(13) =
79.84(7), C*−Ru(1)−Cl(1)
=
123.77(2), C*−Ru(1)−P(1)
131.32(6), Ru(1)−C(13)−C(12)
114.70(17), C(11)−C(12)−C(13) = 108.40(20), P(2)-
=
130.31(2),
111.10(16),
C*−Ru(1)−C(13)
=
=
=
P(2)−C(12)−C(13)
C(12)-C(11) = 114.47(17).
On the basis of this finding, the behavior towards phosphanes of
the previously reported complex [RuCl(η6-C10H14){κ3P,C,C-
After
4 h at rt, the isomerization is complete and the
iPr2PCH2CH=CH2}][BPh4]9
bearing
ADIP
ligand
was
thermodynamic complex 6b’ appears together with a small
amount of ADPP-oxide. On the bases of this finding, the
decoordination of the olefin from the metal centre is proposed for
the observed isomerization. Furthermore, no hydride signal was
observed in the 1H NMR spectra at any time and allowing
discarding pathway A.
reinvestigated through 31P{1H} NMR. Thus, the reaction of this
complex with phosphanes (PPh3 (2 min at -30°C), ADPP or
ADIP (2 min at rt)) led to the kinetically stable diastereoisomers
RRuSC/SRuRC,
[RuCl(η6-C10H14){κ2P,C-
iPr2PCH2CH(PR3)CH2}][BPh4]17 but they evolve in solution to the
thermodynamically stable diastereoisomers RRuRC/SRuSC. The
diasteroisomer RRuSC/SRuRC was found to be stable for complex
[RuCl(η6-C10H14){κ2P,C-iPr2PCH2CH(PMe3)CH2}][BPh4], at room
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10.1002/ejic.201800895
European Journal of Inorganic Chemistry
FULL PAPER
frequencies. The calculations were carried out with the program
Gaussian09.19
According to the calculations, the isomerization reactions are
spontaneous in the two cases considered. Thus, in the case of
[RuCl(η6-C10H14){κ2P,C-iPr2PCH2CH(iPr2PCH2CH=CH2)CH2}]+
complex, the diastereoisomer (RRuSC), which is formed initially,
is predicted to be 5.2 kcal mol-1 less stable than the (RRuRC)
Scheme 6. Plausible pathways for isomerization of complexes 6b and 6c.
isomer, this compound being the product of thermodynamic
control of the reaction (see Figure 8).
Figure 8. Calculations for the cation complex [RuCl(η6-C10H14){κ2P,C-
iPr2PCH2CH(iPr2PCH2CH=CH2)CH2}]+
On the other hand, in the case of the complex with the
trimethylphosphonium group, which do not experience
isomerization, the difference in stability of the two
diastereoisomers (RRuSC) and (RRuRC) results to be 2.9 kcal mol-
1, lower than in the case of the complex previously studied (see
Figure 9).
The two isomerization reactions considered are, thus, predicted
to be exothermic, but the change in the Gibbs free-energy is
higher in the first case. Using the Hammond postulate20 it can be
proposed that the reaction with a lower change in the Gibbs
free-energy, could have a higher value of the activation energy.
In the present case, this implies that the activation barrier for the
isomerization of the (RRuSC), diastereoisomer of the first complex
[RuCl(η6-C10H14){κ2P,C-iPr2PCH2CH(iPr2PCH2CH=CH2)CH2}]+ is
lower than in the case of the (RRuSC) diastereoisomer of the
[RuCl(η6-C10H14){κ2P,C-iPr2PCH2CH(PMe3)CH2}]+ complex. This
could explain that, the isomerization reaction leading to the
corresponding product of thermodynamic control of complex
[RuCl(η6-C10H14){κ2P,C-iPr2PCH2CH(PMe3)CH2}]+, under the
current reaction conditions, does not take place.
Figure 7. Monitorization of the isomerization process for complex 6b through
31P{1H} NMR spectroscopy
In order to understand the thermodynamics of this
transformation, the structure of the two diastereoisomers of the
complex
iPr2PCH2CH(PMe3)CH2}]+
iPr2PCH2CH(iPr2PCH2CH=CH2)CH2}]+
cations
[RuCl(η6-C10H14){κ2P,C-
[RuCl(η6-C10H14){κ2P,C-
and
were
investigated
theoretically with the Density-functional Theory (DFT) method.
The geometry of the two complexes was fully optimized with the
B3LYP functional, using the 6-31G* basis set for C, H, P and Cl,
and LANL2DZ for Ru. The stationary points located were
characterized as minima by calculating the vibrational
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10.1002/ejic.201800895
European Journal of Inorganic Chemistry
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operating at 600.1 (1H) MHz and 150.9
(
13C) MHz. DEPT and
bidimensional COSY HH, HSQC and HMBC experiments were carried
out for all the compounds. Chemical shifts are reported in parts per
million and referenced to TMS or 85% H3PO4 as standards. Coupling
constants J are given in hertzs. Abbreviations used: s, singlet; d, doublet;
dd, double doublet; t, triplet; q, quartet; sept, septuplet; m, multiplet; br,
broad.
Synthesis of complex [RuCl2(η6-C10H14){κ1P-Ph2PCH2CH=CH2}] (1).
To a solution of the complex [RuCl(μ-Cl)(η6-C10H14)]2 (0.5 g, 0.81 mmol)
in dichloromethane (15 mL), allyldiphenylphosphane (1.62 mmol, 370 μL)
were added. The resulting dark red mixture was stirred at room
temperature for 10 minutes. The solution was then evaporated and the
orange residue was washed with diethyl ether (3 x 10 mL) and dried
under reduced pressure. Yield: 0.82
g (95%). Anal. Calcd for
C25H29Cl2PRu: C, 56.4; H, 5.5. Found: C, 56.6; H, 5.7. IR (KBr) νmax/cm-1
1629 (C=C). 31P{1H} NMR (121.5 MHz, CDCl3, 20°C):  24.6 (s). 1H NMR
3
(400.1 MHz, CDCl3, 20°C):  0.82 (6H, d, JHH = 7.0 Hz, CHMe2), 1.88
3
2
(3H, s, Me), 2.50 (1H, sept, JHH = 7.0 Hz, CHMe2), 3.37 (2H, dd, JHP
=
3
3JHH = 8.8 Hz, PCH2), 4.61 (1H, d, JHH = 16.8 Hz, =CH2), 4.78 (1H, d,
3JHH = 9.6 Hz, =CH2), 5.13, 5.30 (2 x 2H, 2d, JHH = 5.6 Hz, p-cym), 5.37
3
(1H, m, =CH), 7.47 (6H, m, Ph), 7.86 (4H, t, JHH = 8.0 Hz, Ph). 13C{1H}
3
NMR (100.6 MHz, CDCl3, 20°C):  17.3 (s, Me), 21.3 (s, CHMe2), 28.5 (d,
Figure 9. Calculations for the cation complex [RuCl(η6-C10H14){κ2P,C-
iPr2PCH2CH(PMe3)CH2}]+
2
1JCP = 26.7 Hz, PCH2), 30.0 (s, CHMe2), 85.5 (d, JCP = 5.8 Hz, p-cym),
2
3
90.4 (d, JCP = 4.2 Hz, p-cym), 94.0, 108.0 (2s, p-cym), 119.9 (d, JCP
=
2
2
9.3 Hz, =CH2), 128.1 (d, JCP = 9.5 Hz, PPh2), 129.5 (d, JCP = 12.8 Hz,
=CH), 130.6 (d, 4JCP = 1.8 Hz, Ph), 132.1 (d, 1JCP = 42.7 Hz, PPh2), 133.6
(d, 3JCP = 8.4 Hz, PPh2). MS-ESI (m/z): 497 (M - Cl, 100%).
Conclusions
Synthesis
Ph2PCH2CH=CH2}][BPh4] (2).
of
complex
[RuCl(η6-C10H14){κ3P,C,C-
In summary, the nucleophilic attack to the coordinated ADPP
ligand in complex [RuCl(η6-C10H14){κ3P,C,C-Ph2PCH2CH=CH2}]
(2), allows the diastereoselective synthesis of complexes with
bidentate κ2P,C- ligands. The complexes are isolated as the
kinetically stable diastereoisomers (RRuSC/SRuRC) which can
undergo an isomerization to give the thermodynamically stable
diastereoisomers RRuRC/SRuSC. NMR studies in CD2Cl2 allow to
propose the decoordination of the olefin of the ADPP ligand as
the most plausible mechanism for the isomerization processes
and DFT calculations shed light on the thermodynamics of this
transformation and agree with the experimental results.
A
suspension of complex [RuCl2(η6-
C10H14){κ1P-Ph2PCH2CH=CH2}] (1) (1 mmol, 547 mg) and NaBPh4 (3
mmol, 1.03 g) in MeOH (20 mL), was stirred at room temperature for 12
h. Solvents were then decanted, the solid residue was extracted with
dichloromethane and the resultant solution was filtered through
kieselguhr and collected in hexane. Solvents were evaporated and the
yellow solid was dried under reduced pressure. Yield: 596 mg (73%).
Conductivity (acetone, 20°C): Λ = 109 S cm2 mol-1. Anal. Calcd for
C49H49BClPRu: C, 72.10; H, 6.05. Found: C, 71.9; H, 6.1%. IR (KBr)
νmax/cm-1 1478 (C=C), 737, 707 (BPh4). 31P{1H} NMR (162.1 MHz,
CD2Cl2, 20°C):  -63.4 (s). 1H NMR (400.1 MHz, CD2Cl2, 20°C):  1.24
3
3
(6H, d, JHH = 6.8 Hz, CHMe2), 1.37 (3H, s, Me), 2.39 (1H, sept, JHH
=
The nucleophilic addition to the κ3P,C,C-alkenylphosphane
ligand is competitive with the coordination of the nucleophile to
the ruthenium and substitution of the coordinated π-olefin group
as observed for N-donor and phosphite ligands.
3
6.8 Hz, CHMe2), 3.05, 3.98 (2 x 1H, 2m, PCH2), 4.24 (1H, d, JHH = 13.6
Hz, =CH2), 4.50 (1H, m, =CH), 4.68 (1H, dd, 2JHH = 3JHH = 6.0 Hz, =CH2),
4.97, 5.76 (2 x 1H, 2d, 3JHH = 5.2 Hz, p-cym), 5.52, 5.84 (2 x 1H, 2d, 3JHH
= 6.0 Hz, p-cym), 6.91 (4H, t, 3JHH = 7.2 Hz, BPh4), 7.05 (8H, t, 3JHH = 7.2
Hz, BPh4), 7.32 (8H, br s, BPh4), 7.49 – 7.66 (10H, m, PPh2). MS-ESI
(m/z) 497 (M+, 100%), 461 (M - Cl, 10).
Experimental Section
Synthesis
of
complex
[RuCl(η6-C10H14)(MeCN){κ1P-
Ph2PCH2CH=CH2}][BPh4] (3). Complex [RuCl(η6-C10H14){κ3P,C,)-
Ph2PCH2CH=CH2}][BPh4] (2) (0.25 mmol, 200 mg) was dissolved in the
minimum volume of acetonitrile. The addition of diethyl ether (2mL) and
hexane (15mL) afforded a yellow precipitate. Solvents were decanted
and the solid residue dried under reduced pressure. Yield: 157 mg (75%).
Anal. Calcd for C51H52BClNPRu: C, 71.45; H, 6.1; N, 1.6. Found: C, 71.6;
H, 6.2; N, 1.55%. Conductivity (acetone, 20°C): Λ = 106 S cm2 mol-1. IR
(KBr) νmax/cm-1 2362 (C≡N), 1579 (C=C), 737, 707 (BPh4). 31P{1H} NMR
(121.5 MHz, CD3CN, 20°C):  27.6 (s). 1H NMR (600.1 MHz, CD3CN,
20°C):  0.92 (6H, d, 3JHH = 6.6 Hz, CHMe2), 1.88 (3H, s, Me), 2.14 (3H, s,
All manipulations were performed under an atmosphere of dry nitrogen
using vacuum-line and standard Schlenk techniques. All reagents were
obtained from commercial suppliers and used without further purification.
Solvents were dried by standard methods and distilled under nitrogen
before use. Complexes [RuCl(µ-Cl)(η6-C10H14)]2,21 and the phosphane
Ph2PCH2CHCH2 (ADPP)22 were prepared by previously reported
procedures. Infrared spectra were recorded on a Perkin-Elmer 1720-XFT
spectrometer. The C, H and N analyses were carried out with a Perkin-
Elmer 240-B and a LECO CHNS-TruSpec microanalyzers. Mass spectra
(ESI) were determined with
a Bruker Esquire 6000 spectrometer,
3
CH3CN), 2.30 (1H, sept, JHH = 6.6 Hz, CHMe2), 3.17, 3.36 (2 x 1H, 2m,
operating in positive mode and using dichloromethane and methanol
solutions. NMR spectra were recorded on Bruker spectrometers AV400
operating at 400.1 (1H), 100.6 (13C) and 162.1 (31P) MHz, AV300
operating at 300.1 (1H), 75.5 (13C) and 121.5 (31P) MHz, and AV600
2
PCH2), 4.79 (1H, dd, JHH = 1.8 Hz, 3JHH = 16.8 Hz, =CH2), 4.91 (1H, dd,
2JHH = 1.8 Hz, 3JHH = 10.2 Hz, =CH2), 5.35 (1H, d, 3JHH = 6.0 Hz, p-cym),
5.42 (1H, m, =CH), 5.51 (1H, d, 3JHH = 6.0 Hz, p-cym), 5.54 (2H, d, 3JHH
=
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10.1002/ejic.201800895
European Journal of Inorganic Chemistry
FULL PAPER
3
3
2
6.0 Hz, p-cym), 6.83 (4H, t, JHH = 7.2 Hz, BPh4), 6.98 (8H, t, JHH = 7.8
Hz, BPh4), 7.27 (8H, m, BPh4), 7.54 (4H, m, PPh2), 7.59, 7.69, 7.75 (3 x
2H, 3m, PPh2). 13C{1H} NMR (150.9 MHz, CD3CN, 20°C):  1.4 (s,
CH3CN), 18.0 (s, Me), 21.7, 21.8 (s, CHMe2), 31.4 (s, C-CHMe2), 32.0 (d,
1JCP = 27.3 Hz, PCH2), 89.5 (d, 2JCP = 4.7 Hz, p-cym), 90.1 (d, 2JCP = 4.2
Hz, p-cym), 91.3, 95.2, 100.4, 111.6 (4s, p-cym), 121.0 (d, 3JCP = 10.0 Hz,
=CH2), 122.7, 126.6 (2s, BPh4), 129.3 (s, CH3CN), 129.6 (d, 2JCP = 10.3
p-cym), 129.0 (d, JCP = 11.8 Hz, =CH), 128.3 – 134.0 (PPh2), 135.9, (s,
BPh4), 164.1 (q, JC11B = 50.3 Hz, BPh4).. MS-ESI (m/z): 621 (M - P(OMe)3,
100%).
R = Et (5b): Yield: 33 mg (66%). Anal. Calcd for
C55H64BClO3P2Ru: C, 67.2; H, 6.6. Found: C, 67.3; H, 6.55%.
Conductivity (acetone, 20°C): Λ= 138 S cm2 mol-1. IR (KBr) νmax/cm-1
1580 (C=C), 733, 704 (BPh4). 31P{1H} NMR (121.5 MHz, CDCl3, 20°C): 
30.6 (d, JPP = 80.2 Hz, ADPP), 115.6 (d, JPP = 80.2 Hz, P(OEt)3). 1H
2
2
2
2
Hz, PPh2), 129.7 (d, JCP = 10.2 Hz, PPh2), 130.0 (d, JCP = 11.0 Hz,
=CH), 130.4 (d, JCP = 48.6 Hz, PPh2), 131.7 (d, JCP = 45.9 Hz, PPh2),
132.4 (s, PPh2), 134.1 (d, JCP = 8.7 Hz, PPh2), 134.3 (d, JCP = 9.2 Hz,
PPh2), 136.7 (s, BPh4), 164.8 (q, JC11B = 45.3 Hz, BPh4). MS-ESI (m/z):
497 (M - MeCN, 32%), 463 (M - MeCN - Cl, 100).
NMR (400.1 MHz, CDCl3, 20°C):  0.78, 1.08 (2 x 3H, 2d, 3JHH = 6.8 Hz,
1
1
3
CHMe2), 1.30 (9H, t, JHH = 7.2 Hz, CH2CH3), 1.49 (3H, s, C-Me), 2.44
3
3
3
(1H, sept, JHH = 6.8 Hz, CHMe2), 2.86, 3.64 (2 x 1H, 2m, PCH2), 4.14
(6H, m, CH2CH3), 4.50 (1H, d, 3JHH = 6.0 Hz, p-cym), 4.71 (1H, dd, 2JHH
=
3
2.8 Hz, JHH = 17.2 Hz, =CH2), 4.96 (2H, m, =CH2, p-cym), 5.29 (1H, d,
3JHH = 6.0 Hz, p-cym), 5.40 (1H, m, =CH), 5.60 (1H, m, p-cym), 6.85 (4H,
3
3
[RuCl(η6-C10H14)(py){κ1P-
t, JHH = 7.2 Hz, BPh4), 6.97 (8H, t, JHH = 7.2 Hz, BPh4), 7.34 (8H, m,
Synthesis
of
complex
BPh4), 7.35 - 7.63 (10H, m, PPh2). 13C{1H} NMR (100.6 MHz, CDCl3,
Ph2PCH2CH=CH2}][BPh4] (4). To a solution of the complex [RuCl(η6-
C10H14){κ3P,C,C-Ph2PCH2CH=CH2}][BPh4] (2) (0.1 mmol, 81.6 mg) in
THF (10 mL), 1 equivalent of pyridine (0.1 mmol, 8 µl) was added and
the mixture was stirred for 5 minutes at reflux temperature. The addition
of hexane (50 mL) affords a yellow precipitate which was washed with
hexane (3 x 10 mL) and dried under reduced pressure. Yield: 64 mg
(72%). Anal. Calcd for C54H54BClNPRu: C, 72.4; H, 6.1; N, 1.6. Found: C,
72.5; H, 6.1; N, 1.5%. Conductivity (acetone, 20°C): Λ = 143 S cm2 mol-1.
IR (KBr) νmax/cm-1 1602 (C=C), 733, 703 (BPh4). 31P{1H} NMR (162.1
MHz, CD2Cl2, 20°C):  25.7 (s). 1H NMR (400.1 MHz, CD2Cl2, 20°C): 
1.04, 1.11 (2 x 3H, 2d, 3JHH = 6.8 Hz, CHMe2), 1.60 (3H, s, Me), 2.28 (1H,
sept, 3JHH = 6.8 Hz, CHMe2), 2.92, 3.18 (2 x 1H, 2m, PCH2), 4.80 (d, 3JHH
3
20°C):  16.1 (d, JCP = 6.2 Hz, CH2CH3), 17.4 (s, Me), 19.6, 22.6 (2s,
CHMe2), 30.7 (d, 1JCP = 30.5 Hz, PCH2), 30.9 (s, CHMe2), 64.7 (d, 2JCP
=
9.5 Hz, CH2CH3), 87.8, 94.7, 94.9, 99.1, 100.1 (5s, p-cym), 121.0 (d, 3JCP
= 10.4 Hz, =CH2), 121.7, 125.5 (2s, BPh4), 128.9 (d, 2JCP = 9.9 Hz, =CH),
129.5 (s, p-cym), 128.0 – 134.6 (PPh2), 136.3 (s, BPh4), 164.1 (q, JC11B
50.3 Hz, BPh4). MS-ESI (m/z): 663 (M+, 100%), 360 (M – P(OEt)3 – p-
cym, 55). Ph (5c): Yield: 38 mg (68%). Anal. Calcd for
=
R
=
C67H64BClO3P2Ru: C, 71.4; H, 5.7. Found: C, 70.9; H, 5.3%. Conductivity
(acetone, 20°C): Λ= 134 S cm2 mol-1. IR (KBr) νmax/cm-1 1587 (C=C), 734,
705 (BPh4). 31P{1H} NMR (121.5 MHz, CDCl3, 20°C):  29.6 (d, JPP
=
2
80.2 Hz, ADPP), 114.9 (d, 2JPP = 80.2 Hz, P(OPh)3). 1H NMR (400.1 MHz,
CDCl3, 20°C):  0.85, 0.95 (2 x 3H, 2d, 3JHH = 6.8 Hz, CHMe2), 1.42 (3H,
3
= 16.8 Hz, 1H, =CH2), 4.90 (1H, d, JHH = 10.0 Hz, =CH2), 5.16 (1H, d,
3
3JHH = 6.0 Hz, p-cym), 5.24 – 5.36 (4H, m, =CH, p-cym), 6.89 (4H, t, 3JHH
= 7.2 Hz, BPh4), 7.03 (8H, t, 3JHH = 7.2 Hz, BPh4), 7.25 (2H, t, 3JHH = 6.8
Hz, py), 7.33 – 7.80 (19H, m, PPh2, BPh4, py), 8.64 (2H, d, 3JHH = 5.6 Hz,
py). 13C{1H} NMR (100.6 MHz, CD2Cl2, 20°C):  17.2 (s, Me), 21.4, 21.8
s, Me), 2.23 (1H, sept, JHH = 6.8 Hz, CHMe2), 2.87, 3.74 (2 x 1H, 2m,
PCH2), 3.97 (1H, d, JHH = 6.0 Hz, p-cym), 4.35, 5.04, 5.80 (3 x 1H, 3s,
3
br, p-cym), 4.55 (1H, d, 3JHH = 15.2 Hz, =CH2), 4.85 (1H, d, 3JHH = 8.8 Hz,
=CH2), 5.29 (1H, m, =CH), 6.81 (4H, t, 3JHH = 7.2 Hz, BPh4), 7.90 (8H, t,
3JHH = 7.2 Hz, BPh4), 7.04 – 7-.74 (33H, m, BPh4, PPh2, P(OPh)3).
13C{1H} NMR (100.6 MHz, CDCl3, 20°C):  17.4 (s, Me), 19.9, 21.8 (2s,
1
(2s, CHMe2), 30.6 (s, C-CHMe2), 30.9 (d, JCP = 27.2 Hz, PCH2), 86.3,
88.3, 90.4, 91.1, 99.9, 113.0 (6s, p-cym), 120.8 (d, 3JCP = 9.9 Hz, =CH2),
CHMe2), 30.7 (d, 1JCP = 28.7 Hz, PCH2), 31.2 (s, CHMe2), 85.8 (d, 2JCP
=
2
121.7, 125.6 (2s, BPh4), 126.0 (s, py), 128.4 (d, JCP = 11.5 Hz, =CH),
2
8.6 Hz, p-cym), 93.6 (d, JCP = 14.4 Hz, p-cym), 98.3, 98.9, 99.1 (3s, p-
cym), 121.5 (d, 3JCP = 10.0 Hz, =CH2), 121.7, 125.4 (2s, BPh4), 128.4 (d,
127.0 – 132.0 (PPh2), 135.9 (s, BPh4), 139.4, 155.8 (2s, py), 164.1 (q,
JC11B = 50.3 Hz, BPh4). MS-ESI (m/z): 577 (M - py, 100%), 461 (M - py -
Cl, 20).
2JCP = 11.8 Hz, =CH), 132.7 (s, p-cym), 136.3 (s, BPh4), 121.3 – 134.4
3
(PPh2, P(OPh)3), 151.0 (d, JCP = 13.5 Hz, P(OPh)3), 164.1 (q, JC11B
50.3 Hz, BPh4). MS-ESI (m/z): 807 (M+, 100%).
=
Synthesis
of
complexes
[RuCl(η6-C10H14){κ1P-
Ph2PCH2CH=CH2}{P(OR)3}][BPh4] (R = Me (5a), Et (5b), Ph (5c)). To a
solution of complex [RuCl(η6-C10H14){κ3P,C,C-Ph2PCH2CH=CH2}][BPh4]
Synthesis of complexes (RRuSC/SRuRC)-[RuCl(η6-C10H14){ĸ2(P,C)-
Ph2PCH2CH(PR3)CH2}][BPh4] (PR3 = PMe3 (6a), PPh3 (6b), ADPP (6c),
(2) (0.05 mmol, 40.8 mg) in THF (8 mL),
1 equivalent of the
ADIP (6d)).
To a
solution of complex [RuCl(η6-C10H14){κ3P,C,C-
correspondent phosphite P(OR)3 was added and the mixture was stirred
at room temperature for 2 minutes. The solution was then concentrated
under vacuum to a volume of approx. 1 mL. Addition of hexane (20 mL)
afforded a yellow precipitate. Solvents were decanted and the solid was
washed with hexane (2 x 10 mL) and dried under reduced pressure. The
complexes can be recrystallized from dichloromethane/ diethyl ether if
Ph2PCH2CH=CH2}][BPh4] (2) (0.05 mmol, 40.8 mg) in THF (8 mL), 1
equivalent of the correspondent PR3 was added (0.05 mmol, 4.5 µl,
PMe3; 13.1 mg, PPh3, 11 µl , ADPP; 8 μl, ADIP) and the mixture is stirred
for 2 minutes at room temperature (PMe3, ADPP and ADIP) or -30°C
(PPh3). The solution was then concentrated under vacuum to a volume of
approx. 1 mL. Addition of diethyl ether (6a, 6b) or hexane (6c, 6d) (20
mL) afforded a yellow precipitate. Solvents were decanted and the solid
was washed with diethyl ether (6a, 6b) or hexane (6c, 6d) (2 x 10 mL)
and dried under reduced pressure. PR3 = PMe3 (6a): Yield:31 mg (69%).
Anal. Calcd for C52H58BClP2Ru: C, 70.00; H, 6.55. Found: C, 69.9; H,
6.6%. Conductivity (acetone, 20°C): Λ = 142 S cm2 mol-1. IR (KBr)
νmax/cm-1 732, 704 (BPh4). 31P{1H} NMR (121.5 MHz, CD2Cl2, 20°C): 
required.
R = Me (5a): Yield: 28 mg (60%). Anal. Calcd for
C52H58BClO3P2Ru: C, 66.4; H, 6.2. Found: C, 66.7; H, 6.3%. Conductivity
(acetone, 20°C): Λ= 126 S cm2 mol-1. IR (KBr) νmax/cm-1 1578 (C=C), 733,
2
702 (BPh4). 31P{1H} NMR (121.5 MHz, CD2Cl2, 20°C):  30.4 (d, JPP
=
81.4 Hz, ADPP), 119.8 (d, JPP = 81.4 Hz, P(OMe)3). 1H NMR (400.1
MHz, CD2Cl2, 20°C):  0.90, 1.09 (2 x 3H, 2d, JHH = 6.8 Hz, CHMe2),
1.78 (3H, s, Me), 2.53 (1H, sept, JHH = 6.8 Hz, CHMe2), 3.00, 3.66 (2 x
1H, 2m, PCH2), 3.86 (9H, d, 3JHP = 11.2 Hz, P(OMe)3), 4.80 (1H, d, 3JHH
2
3
3
3
3
71.7 (d, JPP = 71.3 Hz, Ru-PPh2), 26.6 (d, JPP = 71.3 Hz, PMe3). 1H
=
3
NMR (400.1 MHz, CD2Cl2, 20°C):  0.99, 1.16 (2 x 3H, 2d, JHH = 6.8 Hz,
16.8 Hz, =CH2), 4.98 (2H, m, =CH2 p-cym), 5.27 (1H, m, p-cym), 5.42
CHMe2), 1.34 (9H, d, 2JHP = 13.2 Hz, PMe3), 1.98 (3H, s, Me), 2.19 - 2.40
(4H, m, Ru-PCH2, Ru-CH2, CHP), 2.51 (1H, sept, 3JHH = 6.8 Hz, CHMe2),
3
(1H, m, =CH), 5.50, 5.89 (2 x 1H, 2d, JHH = 6.0 Hz, p-cym), 6.90 (4H, t,
3
3JHH = 7.2 Hz, BPh4), 7.05 (8H, t, JHH = 7.2 Hz, BPh4), 7.34 (8H, m,
3
BPh4), 7.55 –7.77 (10H, m, PPh2). 13C{1H} NMR (100.6 MHz, CDCl3,
20°C):  17.5 (s, Me), 20.0, 22.0 (2s, CHMe2), 30.9 (s, CHMe2), 31.3 (d,
3.03 (1H, m, Ru-CH2), 4.91, 5.02, 5.31, 5.51 (4 x 1H, 4d, JHH = 6.0 Hz,
p-cym) 6.90 (4H, t, 3JHH = 7.2 Hz, BPh4), 7.06 (8H, t, 3JHH = 7.6 Hz, BPh4)
7.18 - 7.78 (18H, m, PPh2, BPh4). 13C{1H} NMR (100.6 MHz, CD2Cl2,
2
2
1JCP = 28.4 Hz, PCH2), 55.5 (d, JCP = 9.5 Hz, P(OMe)3), 88.4 (d, JCP
=
1
8.2 Hz, p-cym), 95.1 (d, 2JCP = 11.8 Hz, p-cym), 95.4, 100.1, 101.5 (3s, p-
cym) 120.9 (d, JCP = 10.7 Hz, =CH2), 121.7, 125.6 (2s, BPh4), 125.6 (s,
20°C):  7.1 (d, JCP = 55.0 Hz, PMe3), 15.4 (m, Ru-CH2), 17.9 (s, Me),
22.1, 22.2 (2s, CHMe2), 30.7 (s, CHMe2), 33.4 (d, JCP = 28.8 Hz, Ru-
1
3
This article is protected by copyright. All rights reserved.

10.1002/ejic.201800895
European Journal of Inorganic Chemistry
FULL PAPER
PCH2), 34.9 (m, CHP), 87.0, 87.3, 88.9, 89.3, 100.2, 110.6 (6s, p-cym),
121.8, 125.7 (2s, BPh4), 128.2 – 134.0 (PPh2), 136.0 (s, BPh4), 164.1 (q,
JC11B = 60.4 Hz, BPh4). MS-ESI (m/z): 573 (M+, 100%). PR3 = PPh3 (6b):
Yield: 29 mg (53%). Anal. Calcd for C67H64BClP2Ru: C, 74.6; H, 6.0.
Found: C, 74.5; H, 6.0%. Conductivity (acetone, 20°C): Λ = 132 S cm2
mol-1. IR (KBr) νmax/cm-1 732, 704 (BPh4). 31P{1H} NMR (121.5 MHz,
completed. After this time period, the solution was evaporated and the
yellow residue was washed with diethyl ether (3 x 20 mL) and dried
under reduced pressure. Spectroscopic data for complex [RuCl(η6-
C10H14){κ2P,C-Ph2PCH2CH(Ph2PCH2CH=CH2)CH2}][Cl] are the same
than for complex 6c except for those signals due to the BPh4 anion. Anal.
Calcd for C40H44Cl2P2Ru: C, 63.3; H, 5.85. Found: C, 63.25; H, 5.8.
3
3
CD2Cl2, 20°C):  72.7 (d, JPP = 81.4 Hz, Ru-PPh2), 26.0 (d, JPP = 81.4
Hz, PPh3). 1H NMR (400.1 MHz, CD2Cl2, 20°C):  1.11, 1.17 (2 x 3H, 2d,
3JHH = 6.8 Hz, CHMe2) 1.85 (3H, s, Me), 1.97 (2H, m, Ru-PCH2, Ru-CH2),
2.48 (1H, sept, 3JHH = 6.8 Hz, CHMe2), 2.88 (1H, m, Ru-PCH2), 3.55 (1H,
m, Ru-CH2), 4.44 (1H, m, CHP), 4.53, 4.68, 4.92, 5.26 (4 x 1H, 4d, 3JHH
= 6.0 Hz, p-cym), 6.89 (4H, t, 3JHH = 7.2 Hz, BPh4), 7.04 (8H, t, 3JHH = 7.6
Hz, BPh4) 6.64 - 7.90 (33H, m, PPh, BPh4). 13C{1H} NMR (100.6 MHz,
CD2Cl2, 20°C):  16.8 (m, Ru-CH2), 17.6 (s, Me), 21.7, 22.9 (2s, CHMe2),
30.6(s, CHMe2), 32.1 (d, 1JCP = 33.0 Hz, Ru-PCH2), 32.5 (m, CHP), 86.7,
87.6, 88.5, 88.7, 100.8, 111.4 (6s, p-cym), 121.7, 125.6 (2s, BPh4), 128.6
– 135.2 (PPh), 135.9 (s, BPh4), 164.3 (q, JC11B = 49.5 Hz, BPh4). 163.3,
163.8, 164.2, 164.8 MS-ESI (m/z): 759 (M+, 100%), 497 (M - PPh3+, 82).
PR3 = ADPP (6c): Yield: 42 mg (81%). Anal. Calcd for C64H64BClP2Ru: C,
73.7; H, 6.2. Found: C, 73.9; H, 6.1%. Conductivity (acetone, 20°C): Λ =
136 S cm2 mol-1. IR (KBr) νmax/cm-1 1579 (C=C), 733, 704 (BPh4). 31P{1H}
Synthesis
of
complex
[RuCl(η6-C10H14){κ1P-
Ph2PCH2CH=CH2}(PPh3)][BPh4] (7). Method A: To a solution of the
complex [RuCl(η6-C10H14){κ3P,C,C-Ph2PCH2CH=CH2}][BPh4] (2) (100 mg,
0.12 mmol) in THF (15 mL) 1 equivalent of PPh3 (32 mg, 0.12 mmol) was
added and the mixture was heated at reflux temperature for 30 minutes.
The solution was then concentrated under vacuum to a volume of approx.
1 mL. Addition of hexane (30 mL) afforded a yellow precipitate. Solvents
were decanted and the solid was washed with hexane (2 x 10 mL) and
dried under reduced pressure. Yield: 78 mg, 60%. Method B: Complex
[RuCl(η6-C10H14){ĸ2(P,C)-Ph2PCH2CH(PPh3)CH2}][BPh4] (6b) (130 mg,
0.12 mmol) was refluxed in THF for 30 minutes. The solution was then
concentrated to a volume of approx. 1 mL. and hexane (15 mL) was
added. The yellow solid was washed with hexane (2 x 10 mL) and dried
under reduced pressure. Yield: 69 mg, 53%. Anal. Calcd for
C67H64BClP2Ru: C, 74.6; H, 6.0. Found: C, 74.5; H, 6.1%. Conductivity
(acetone, 20°C): Λ = 135 S cm2 mol-1. IR (KBr) νmax/cm-1 1579 (C=C),
733, 702 (BPh4). 31P{1H} NMR (121.5 MHz, CDCl3, 20°C):  19.5 (d, 2JPP
3
NMR (162.1 MHz, CDCl3, 20°C):  72.5 (d, JPP = 85.2 Hz, Ru-PPh2),
25.9 (d, 3JPP = 85.2 Hz, CH-PPh2). 1H NMR (400.1 MHz, CD2Cl2, 20°C): 
3
1.15, 1.23 (2 x 3H, 2d, JHH = 6.8 Hz, CHMe2), 1.90 – 2.08 (2H, m, Ru-
= 52.2 Hz, PPh3), 23.6 (d, JPP = 52.2 Hz, ADPP). 1H NMR (400.1 MHz,
CDCl3, 20°C):  0.38 (3H, s, C-Me), 1.26 (6H, m, CHMe2), 1.28 (1H, m,
2
PCH2, Ru-CH2), 2.12 (3H, s, Me), 2.79 (2H, m, CHMe2, Ru-PCH2), 3.60
(1H, m, Ru-CH2), 4.43 (1H, m, PCH2-CH=), 4.57 (1H, m, CHP), 4.86 (1H,
m, PCH2-CH=), 4.93, 5.01 (2 x 1H, 2d, 3JHH = 5.6 Hz, p-cym), 5.07 (1H, d,
3JHH = 6.0 Hz, p-cym), 5.26 (1H, dd, 2JHH = 3.2 Hz, 3JHH = 9.6 Hz, =CH2),
3
PCH2), 2.74 (1H, sept, JHH = 6.8 Hz, CHMe2), 3.15 (1H, m, PCH2), 4.36
3
3
(1H, d, JHH = 16.8 Hz, =CH2), 4.63 (1H, d, JHH = 10.4 Hz, =CH2), 4.71
(1H, m, =CH), 4.83, 5.32 (2 x 2H, 2m, p-cym), 6.81 (4H, t, 3JHH = 7.2 Hz,
BPh4), 6.92 (8H, t, 3JHH = 7.2 Hz, BPh4), 7.18 – 7.86 (45H, m, PPh3, PPh2,
BPh4). 13C{1H} NMR (100.6 MHz, CDCl3, 20°C):  14.9 (s, Me), 21.1, 21.6
5.43 (2H, m, =CH2, p-cym), 5.59 (1H, m, =CH), 6.92 (4H, t, 3JHH = 7.2 Hz,
3
BPh4), 7.06 (8H, t, JHH = 7.6 Hz, BPh4) , 7.36 – 7.72 (28H, m, PPh2
,
BPh4). 13C{1H} NMR (100.6 MHz, CD2Cl2, 20°C):  18.4 (s, Me), 20.1 (dd,
2JCP
=
3JCP = 11.4 Hz, Ru-CH2), 21.9, 23.1 (2s, CHMe2), 27.9 (d, JCP
=
1
1
(2s, CHMe2), 26.7 (d, JCP = 26.3 Hz, PCH2), 31.7 (s, CHMe2), 87.1 (d,
46.6 Hz, PCH2-CH=), 30.8 (s, CHMe2), 33.9 (d, 1JCP = 25.3 Hz, Ru-PCH2),
2JCP = 11.4 Hz, p-cym), 88.7 (d, JCP = 9.9 Hz, p-cym), 95.2, 99.2, 98.1,
2
2
3
39.0 (m, CHP), 85.4, 87.7 (2s, p-cym), 88.1 (d, JCP = 3.8 Hz, p-cym),
115.2 (4s, p-cym), 120.5 (d, JCP = 9.9 Hz, =CH2), 121.6, 125.4 (2s,
88.3 (d, 2JCP = 5.2 Hz, p-cym), 103.4, 113.9 (2s, p-cym), 121.7 (s, BPh4),
123.8 (d, 3JCP = 12.5 Hz, =CH2), 125.1 (d, 2JCP = 10.0 Hz, =CH), 125.6 (s,
BPh4), 128.6 (d, 2JCP = 11.5 Hz, =CH), 129.0 – 134.5 (PPh3, PPh2), 136.2
(s, BPh4), 164.1 (q, JC11B = 50.3 Hz, BPh4). MS-ESI (m/z): 759 (M+,
100%), 497 (M – PPh3, 23).
1
BPh4), 127.9 – 134.5 (PPh2), 135.2 (s, BPh4), 164.1 (q, JCB = 49.1 Hz,
BPh4). MS-ESI (m/z): 723 (M+, 100%). PR3 = ADIP (6d): Yield: 34 mg
(70%). Anal. Calcd for C58H68BClP2Ru: C, 71.5; H, 7.0. Found: C, 69.4; H,
6.8%. Conductivity (acetone, 20°C): Λ = 131 S cm2 mol-1. IR (KBr)
νmax/cm-1 1579 (C=C), 733, 705 (BPh4). 31P{1H} NMR (162.1 MHz,
Synthesis of complexes (RRuRC/SRuSC)-[RuCl(η6-C10H14){ĸ2(P,C)-
Ph2PCH2CH(PR3)CH2}][BPh4] (PR3
solution of the corresponding complex 6b or 6c (0.05 mmol) in THF was
stirred at room temperature for 2 h (6b) or 7 days (6c). The solution was
then concentrated under vacuum to a volume of approx. 1 mL. Addition
of hexane (30 mL) afforded complexes 6b’ and 6c’ as a yellow
precipitate. R = PPh3 (6b’): Yield: 47 mg (87%). 31P{1H} NMR (121.5 MHz,
CD2Cl2, 20°C):  66.6 (d, JPP = 74.1 Hz, Ru-PPh2), 25.6 (d, JPP = 74.1
Hz, PPh3). R = ADPP (6c’): Yield: 46 mg (89%). 31P{1H} NMR (162.1
MHz, CDCl3, 20°C):  68.0 (d, JPP = 70.5 Hz, Ru-PPh2), 27.4 (d, JPP
70.5 Hz, CH-PPh2). All the other analytical and spectroscopic data are
the same as found for 6b and 6c, respectively.
= PPh3 (6b’), ADPP (6c’)). A
3
3
CD2Cl2, 20°C):  71.8 (d, JPP = 68.1 Hz, Ru-PPh2), 37.7 (d, JPP = 68.1
Hz, CH-PiPr2). 1H NMR (400.1 MHz, CD2Cl2, -30°C):  0.87, 1.10 (2 x 3H,
2d, JHH = 6.8 Hz, CHMe2), 1.26 – 1.41 (12H, m, Me2CH-P), 2.07 (3H, s,
3
Me), 2.42 - 2.56 (4H, m, Ru-PCH2, CHP, CHMe2), 2.58 – 2.65 (3H, m,
2
3
Ru-CH2, Me2CH-P), 2.94 (2H, dd, JHH = 13.8 Hz, JHH = 7.6 Hz, PCH2-
3
3
3
CH=), 3.13 (m, 1H, Ru-CH2), 4.88 (1H, br s, p-cym), 4.97 (1H, d, JHH
=
5.9 Hz, p-cym), 5.41 – 5.47 (3H, m, =CH2, p-cym), 5.54 (1H, d, 3JHH = 5.9
Hz, p-cym), 5.73 (1H,m, =CH), 6.90 (4H, t, 3JHH = 7.2 Hz, BPh4), 7.05 (8H,
3
3
=
3
t, JHH = 7.2 Hz, BPh4), 7.32 (8H, m, BPh4), 7.12 – 7.80 (10H, m, PPh2).
13C{1H} NMR (100.6 MHz, CD2Cl2, -30°C):  16.4 (m, Ru-CH2), 17.0, 17.2
(2s, br, Me2CH-P), 18.4 (s, Me), 21.1 (d, JCP = 15.6 Hz, Me2CH-P), 21.5
1
X-Ray Crystal Structure Determination of Complexes 1, 3, 5a,
6a·CH3OH, 6c’ and 7. The most relevant crystal and refinement data are
collected in Table S2 in the Supporting Information.
1
1
(d, JCP = 14.4 Hz, Me2CH-P), 21.9 (s, CHMe2), 22.5 (d, JCP = 42.9 Hz,
PCH2-CH=), 22.6 (s, CHMe2), 30.8 (s, CHMe2), 32.3 (m, CHP), 33.4 (d,
1JCP = 31.7 Hz, Ru-PCH2), 86.7, 87.2, 88.9, 89.3, 101.4, 109.8 (6s, p-
cym) 121.9 (s, BPh4), 124.2 (d, 2JCP = 8.0 Hz, =CH), 124.7 (d, 3JCP = 11.1
Hz, =CH2), 125.8 (s, BPh4), 128.3 – 133.7 (PPh2), 135.8, (s, BPh4),
164.0 (q, JC11B = 50.3 Hz, BPh4).
X-ray crystallographic data for 1, 3, 5a, 6a ·MeOH, 7 and 6c’ in CIF
format (CCDC 1459032-1459037).
(RRuSC/SRuRC)-[RuCl(η6-C10H14){κ2P,C-
In all cases, diffraction data were recorded on an Oxford Diffraction
Xcalibur Nova (Agilent) single crystal diffractometer, using Cu-Kα
radiation (λ= 1.5418 Å). Images were collected at a 63 mm fixed crystal-
detector distance, using the oscillation method, with 1° oscillation and
variable exposure time per image. Data collection strategy was
calculated with the program CrysAlis Pro CCD.23 Data reduction and cell
Synthesis
of
complex
Ph2PCH2CH(Ph2PCH2CH=CH2)CH2}][Cl]. To a solution of the complex
[RuCl(μ-Cl)(η6-C10H14)]2 (0.1 g, 0.16 mmol) in methanol (10 mL), 5
equivalents of ADPP (0.8 mmol, 183 μL) were added. The resulting
suspension was stirred for 2 hours at room temperature until solution is
This article is protected by copyright. All rights reserved.

10.1002/ejic.201800895
European Journal of Inorganic Chemistry
FULL PAPER
refinement was performed with the program CrysAlis Pro RED.23 An
empirical absorption correction was applied using the SCALE3
ABSPACK algorithm as implemented in the program CrysAlis Pro RED.23
136, 7943-7953; c) C. Metallinos, L. Van Belle, J. Organomet. Chem.
2010, 696, 141-149.
[2]
[3]
a) B. Ye, N. Cramer, Acc. Chem. Res. 2015, 48, 1308-1318; b) A.
Linden, L. Llovera, J. Herrera, R. Dorta, G. Agrifoglio, R. Dorta
Organometallics 2012, 31, 6162-6171; c) Y. Hiroi, N. Komine, M.
Hirano, S. Komiya, Organometallics 2011, 30, 1307-1310; d) C.
Defieber, H. Grützmacher, E. M. Carreira, Angew. Chem. Int. Ed. 2008,
47, 4482-4502.
The software package WINGX24 was used for space group determination,
structure solution and refinement. The structures for 1 and 5a were
solved by Patterson interpretation and phase expansion using DIRDIF.25
For complexes 3, 6a, 6c’ and 7 the structures were solved by direct
methods using SIR92.26 In the crystal of 6a·CH3OH, one solvent
molecule per unit formula of the complex is present. In 7, solvent
molecules in the structure were highly disordered and were impossible to
refine using conventional discrete-atom models. To resolve these issues,
the contribution of solvent electron density was removed by the
SQUEEZE/PLATON.27
a) H. Brunner, M. Muschiol, T. Tsuno, H. Ike, T. Kurosawa, K. Koyama,
Angew. Chem. Int. Ed. 2012, 51, 1067-1070; b) H. Brunner, M.
Muschiol, T. Tsuno, H. Ike, T. Kurosawa, K. Koyama, M. Zabel,
Organometallics 2011, 30, 3666-3676; c) L. Hintermann, L. Xiao, A.
Labonne, U. Englert, Organometallics 2009, 28, 5739-5748; d) J. W.
Faller, P. P. Fontaine, Organometallics 2007, 26, 1738-1743.
a) J. L. McBee, T. D. Tilley, Organometallics 2010, 29, 184-192; b) C.
Hahn, Chem. Eur. J. 2004, 10, 5888-5899.
[4]
[5]
[6]
Isotropic least-squares refinement on F2 using SHELXL201328 was
performed. During the final stages of the refinements, all the positional
parameters and the anisotropic temperature factors of all the non-H
atoms were refined. The H atoms were geometrically placed riding on
their parent atoms with isotropic displacement parameters set to 1.2
times the Ueq of the atoms to which they are attached (1.5 for methyl
groups) (except for 1, which the H atoms were found from different
Fourier maps and included in a refinement with isotropic parameters).
a) G. Lorusso, C. R. Barone, N. G. Di Masi, C. Pacifico, L. Maresca, G.
Natile, Eur. J. Inorg. Chem. 2007, 2144-2150.
a) Z. Liu, H. Yamamichi, S. T. Madrahimov, J. F. Hartwig, J. Am. Chem.
Soc. 2011, 133, 2772-2782; b) B. M. Cochran, J. Am. Chem. Soc. 2008,
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[7]
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The function minimized was [∑w(Fo2- Fc2)/∑w(Fo2)]1/2 where w = 1/[σ2
(Fo2) + (aP)2 + bP] (a and b values are collected in Table S2) with σ(Fo2)
from counting statistics and P = (Max (Fo2, 0) + 2Fc2)/3.
Atomic scattering factors were taken from the International Tables for X-
Ray Crystallography International.29 The crystallographic plots were
made with PLATON.27
Computational Methods. The structure of the two diastereoisomers of
the complex cations [RuCl(η6-C10H14){κ2P,C-iPr2PCH2CH(PMe3)CH2}]+
and [RuCl(η6-C10H14){κ2P,C-iPr2PCH2CH(iPr2PCH2CH=CH2)CH2}]+ were
investigated theoretically with the Density-functional Theory (DFT)
method. The geometry of the two complexes was fully optimized with the
B3LYP functional, using the 6-31G* basis set for C, H, P and Cl, and
LANL2DZ for Ru. The stationary points located were characterized as
minima by calculating the vibrational frequencies. The calculations were
carried out with the program Gaussian09.19
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[9]
I. García de la Arada, J.
Díez, M. P. Gamasa, E. Lastra,
Organometallics 2013, 32, 4342-4352.
Acknowledgements
[10] 13C{1H} NMR spectrum of complex 2 could not be obtained due to the
low solubility of the product in in CD2Cl2. Solutions of the complex in
more polar solvents such as methanol or acetone led the complexes
with the ADPP coordinated κ1P.
This work was supported by the Spanish Ministerio de
Educación y Ciencia (CTQ-2010-17005 and CTQ-2011-26481 )
and Consolider Ingenio 2010 (CSD2007-00006). I. G. de la
Arada thanks the Spanish Ministerio de Educación Cultura y
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Deporte for
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Keywords: allylphosphanes • chelating phosphorus-carbon
ligands • nucleophilic additions • p-cymene complexes •
ruthenium(II) complexes
[17] Complexes
RRuSC/SRuRC-[RuCl(η6-C10H14){κ2P,C-
iPr2PCH2CH(PR3)CH2}]+ (PR3 = PPh3 or ADPP) have been synthesized
following the same procedures as for 6c and 6d, respectively.
Experimental details for their synthesis and for the isomerization
reactions can be found in the Supporting Information.
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10.1002/ejic.201800895
European Journal of Inorganic Chemistry
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10.1002/ejic.201800895
European Journal of Inorganic Chemistry
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Diasteroselective addition
I. García de la Arada, J. Díez, M. P.
Gamasa and E. Lastra*.
Page No. – Page No.
ISOMERIZATION PROCESSES ON
ORGANORUTHENIUM COMPLEXES
BEARING κ2P,C- BIDENTATE
LIGANDS GENERATED THROUGH
NUCLEOPHILIC ADDITION TO
COORDINATED ALKENYL
New ruthenium complexes containing bidentate κ2P,C-ligands [RuCl(η6-
C10H14){κ2P,C-Ph2PCH2CH(PR3)CH2}][BPh4] have been diastereoselectively
synthesized as the kinetically stable isomer (RRuSC/SRuRC). This diastereoisomer
spontaneously evolves to the thermodynamically stable diastereoisomer
(RRuRC/SRuSC). 31P{1H} NMR monitoring experiments shed light on the isomerization
processes. DFT calculations agreee with the experimental results.
PHOSPHANES
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