Regioselective synthesis of η4-dienylphosphane ruthenium complexes by oxidative coupling reactions

Article abstract of DOI:10.1021/om700476f

Complexes [Ru(η⁵-C₅H₅{κ ³(P,C,C)-Ph₂P(CH₂)_nCH=CH ₂}MeCN)][PF₆] (n = 1 (1), 2 (2)) react with C≡C bonds of propargylic alcohols to yield regioselectively the

Full text of DOI:10.1021/om700476f

Organometallics 2007, 26, 5315-5322
5315
Regioselective Synthesis of η4-Dienylphosphane Ruthenium
Complexes by Oxidative Coupling Reactions
J. D´ıez,† M. P. Gamasa,*,† E. Lastra,*,† A. Villar,† and E. Pe´rez-Carren˜o‡
Departamento de Qu´ımica Orga´nica e Inorga´nica, Instituto de Qu´ımica Organometa´lica “Enrique Moles”
(Unidad Asociada al CSIC), UniVersidad de OViedo, OViedo, Principado de Asturias, Spain, and
Departamento de Qu´ımica F´ısica y Anal´ıtica, UniVersidad de OViedo, OViedo,
Principado de Asturias, Spain
ReceiVed May 14, 2007
Complexes [Ru(η5-C5H5){κ3(P,C,C)-Ph2P(CH2)nCHdCH2}(MeCN)][PF6] (n ) 1 (1), 2 (2)) react with
CtC bonds of propargylic alcohols to yield regioselectively the complexes [Ru(η5-C5H5){κ(P),η4-Ph2P-
(CH2)nCHdCHC(R)dCH2}][PF6] (n ) 1, R ) CPh2OH (3), C(C12H8)OH (4), C(C4H8)OH (5), CMePhOH
(6a, 6b); n ) 2, R ) CPh2OH (7), C(C4H8)OH (8), CMePhOH (9a, 9b), CHPhOH (10a, 10b)). The
reaction of complex 1 with terminal alkynes also leads regioselectively to the complexes [Ru(η5-C5H5)-
{κ(P),η4-(2Z,4E)-Ph2PCH2CHdCHCHdCH(R)}][PF6] (R ) Ph (11), p-MeC6H4 (12)). Single-crystal X-ray
diffraction analyses for complexes 9a, 9b, 10b, and 12 have been carried out and allow the unambiguous
assignment of the stereochemistry of the complexes. DFT calculations regarding the thermodynamic
stability of the obtained products have also been performed.
Chart 1
Introduction
We have previously reported that ruthenium(II) complexes
[Ru(η5-CnHm)(PPh3){κ3(P,C,C)-Ph2PCH2CHdCH2}][PF6] (CnHm
) C9H7, C5H5)1 react with alkynes and propargylic alcohols to
give ruthenaphosphabicycloheptene complexes under mild
thermal conditions (Chart 1). These reactions take place through
the formation of vinylidene or allenylidene derivatives, which
undergo an unusual diastereoselective [2+2] intramolecular
cycloaddition with allyl CdC double bonds to generate the
cyclobutylidene ring.2 The progress of the reaction reflects the
hemilabile character of the allyldiphenylphosphane ligand, a fact
that has been corroborated by kinetic studies.3
On the other hand, intermolecular reactions between alkenes
and alkynes (ene-type reactions or [2+2] coupling reactions)
promoted by transition metal complexes are among the most
efficient and selective methods for C-C bond formation.4 In
spite of the great development in this area, few examples of
the reaction between alkynes and double bonds linked to the
metal atom have been reported. Thus, the reactions between
alkenylphosphane complexes of group 8 metals and terminal
alkynes have been described in recent papers. Cyclopentadi-
enylosmium(II) complexes promote the transformation of vinyl
phosphane in dienylphosphaneosmium(II) derivatives [Os(η5-
C5H5)Cl{κ3(P,C,C)-iPr2PC(dCH2)CH2CHdCH(Ph)}] through
an ene-type reaction.5 An intramolecular version of this reaction
has also been described.6 Kirchner et al. have reported the
coupling of alkynes with coordinated alkenyl phosphanes in the
complex [Ru(η5-C5H5){κ3(P,C,C)-Ph2PCH2CH2CHdCH2}-
(MeCN)][PF6], leading to a mixture of dienylphosphane com-
plexes.7 Also, an alkyne-alkene coupling involving the complex
[Ru(Tp){κ3(P,C,C)-Ph2PCHdCHC(Ph)dCH2}Cl] has also been
reported.8
In this context, we report here the synthesis of novel
cyclopentadienyl ruthenium(II) complexes containing the allyl-
diphenylphosphane ligand Ph2PCH2CHdCH2 as well as their
coupling reaction with the CtC bonds of terminal alkynes and
propargylic alcohols. The coupling reaction of the analogous
complex containing the homoallyldiphenylphosphane ligand7
[Ru(η5-C5H5){κ3(P,C,C)-Ph2PCH2CH2CHdCH2}(MeCN)]-
[PF6] and propargylic alcohols is also reported.
* Corresponding author. E-mail: pgb@uniovi.es (M.P.G.) and elb@
uniovi.es (E.L.).
† Departamento de Qu´ımica Orga´nica e Inorga´nica, Instituto de Qu´ımica
Organometa´lica “Enrique Moles”.
‡ Departamento de Qu´ımica F´ısica y Anal´ıtica.
(1) (a) Alvarez, P.; Lastra, E.; Gimeno, J.; Bran˜a, P.; Sordo, J. A.; Go´mez,
J.; Falvello, L. R.; Bassetti, M. Organometallics 2004, 23, 2956-2966. (b)
D´ıez, J.; Gamasa M. P.; Gimeno, J.; Lastra, E.; Villar, A. Eur. J. Inorg.
Chem. 2006, 78-87.
(2) (a) AÄ lvarez, P.; Lastra, E.; Gimeno, J.; Bassetti, M.; Falvello, L. R.
J. Am. Chem. Soc. 2003, 125, 2386. (b) D´ıez, J.; Gamasa, M. P.; Gimeno,
J.; Lastra, E.; Villar, A. Organometallics 2005, 24, 1410-1418.
(3) Bassetti, M.; AÄ lvarez, P.; Gimeno, J.; Lastra, E. Organometallics
2004, 23, 5127-5134.
(4) (a) Trost, B. M.; Toste, F. D.; Pinkerton, A. B. Chem. ReV. 2001,
101, 2067-2096. (b) Naota, T.; Takaya, H.; Murahashi, S.-I. Chem. ReV.
1998, 98, 2599-2660.
(5) Baya, M.; Buil, M. L.; Esteruelas, M. A.; On˜ate, E. Organometallics
2005, 24, 2030-2038.
(6) Baya, M.; Buil, M. L.; Esteruelas, M. A.; On˜ate, E. Organometallics
2005, 24, 5180-5183.
(7) Slugovc, C.; Mereiter, K.; Schmid, R.; Kirchner, K. Organometallics
1999, 18, 1011-1017.
(8) Slugovc, C.; Mereiter, K.; Schmid, R.; Kirchner, K. Eur. J. Inorg.
Chem. 1999, 1141-1149.
10.1021/om700476f CCC: $37.00 © 2007 American Chemical Society
Publication on Web 09/19/2007

5316 Organometallics, Vol. 26, No. 22, 2007
D´ıez et al.
CMePhOH (6)) and [Ru(η5-C5H5){κ(P),η4-(3Z)-Ph2P(CH2)2-
CHdCHC(R)dCH2}][PF6] (R ) CPh2OH (7), C(C4H8)OH (8),
CMePhOH (9), CHPhOH (10)), which are isolated as pink or
white solids (Scheme 1). Complexes 6, 9, and 10 have been
isolated as a mixture of two diastereoisomers as a consequence
of the presence of a ruthenium and a carbon stereogenic center.
Scheme 1
Complexes 3-10 are soluble in dichloromethane and in-
soluble in diethyl ether and n-hexane. All of them have been
analytically and spectroscopically characterized (IR and 1H, 31P-
{1H}, and 13C{1H} NMR; see the Experimental Section for
details). The most significant spectroscopic features are as
follows: (i) The phosphorus signal for complexes 3-6 appears
as a singlet between δ ) -59.2 and -61.9 ppm, while that of
derivatives 7-10 is observed at δ ) 95.1 and 92.4 ppm. The
formation of five- (3-6) and six-membered (7-10) ruth-
enaphosphacycles may account for the observed shift differ-
Results and Discussion
1
ences.9 (ii) The H NMR spectra show a doublet in the range
Synthesis of [Ru(η5-C5H5){κ3(P,C,C)-Ph2PCH2CHdCH2}-
(MeCN)][PF6] (1). The air-stable cationic complex [Ru(η5-
C5H5){κ3(P,C,C)-Ph2PCH2CHdCH2}(MeCN)][PF6] (1) has been
prepared in 77% yield by the reaction of [Ru(η5-C5H5)(MeCN)3]-
[PF6] with allylphosphane in CH2Cl2 at 0 °C.
4.04-2.94 ppm (JHH ) 5.2-3.5 Hz) as well as a doublet of
doublets in the range 1.42-0.70 ppm (JHP ) 20.4-16.1 and
JHH ) 5.2-3.5 Hz), which are assigned to the geminal protons
of the olefin group. (iii) The internal olefinic protons appear as
multiplets at δ 6.49-4.72 ppm. The observed J values of ca. 8
Hz for complexes 7-10 are in agreement with the Z stereo-
chemistry around the double bond. (iv) The signal for the
terminal olefinic carbon in the 13C{1H} NMR spectra appears
as a doublet at 44.4-38.9 ppm (JCP ) 6.0-4.9 Hz).
Complex 1 is soluble in CH2Cl2 and THF and insoluble in
diethyl ether and n-hexane. Analytical and spectroscopic data
(IR and 1H, 13C{1H}, and 31P{1H} NMR) support the proposed
formulation (see Experimental Section for details). The 31P-
{1H} NMR spectrum shows a singlet resonance at δ ) -53.3
ppm, in accordance with the values obtained for analogous κ3-
(P,C,C)-allylphosphane complexes [Ru(η5-C5H5){κ3(P,C,C)-Ph2-
PCH2CHdCH2}(PPh3)][PF6] (δ ) -69.8 ppm).1b Although the
two olefin faces are diastereotopic, the coordination to the metal
A plausible reaction mechanism that would rationalize the
observed regio- and stereochemistry is shown in Scheme 2.
The generation of one coordination vacancy by MeCN dis-
sociation followed by metal-alkyne π-coordination is assumed
to be the first step. Once the alkyne is coordinated, an oxidative
coupling with the double bond of the alkenyl ligand would lead
to the ruthenacyclopentene intermediate (A), which gives the
final complex via a â-elimination/reductive elimination se-
quence. Alternatively, the formation of the metal-alkyne com-
plex might also occur by dissociation of the alkenylphosphane
ligand. Thus, κ-P intermediates have been observed for the
allylphosphane complexes 3, 4, 5, and 6, while no such species
have been detected in the case of the complexes 7, 8, and 9
bearing the homoallylphosphane ligand. This fact is in agreement
with the different hemilabile properties described for these
ligands.1-3
X-ray Crystal Structure of the Complexes 9a‚1/2OEt2, 9b,
and 10b‚1/2OEt2. Although complexes 6, 9, and 10 were
obtained as a mixture of diastereoisomers, both diastereoisomers
of complexes 9 and 10 were separated by recrystallization from
dichloromethane/diethyl ether. In order to determine their
stereochemistry, X-ray diffraction analyses of the diastereoiso-
mers 9a, 9b, and 10b have been carried out. Slow diffusion of
diethyl ether into a solution of the complexes in dichloromethane
center is completely selective since the 31P{1H} and H NMR
1
spectra of complex 1 indicate the presence of a sole stereoiso-
mer. This behavior has also been found for the complexes [Ru-
(η5-C9H7){κ3(P,C,C)-Ph2PCH2CHdCH2}(PPh3)][PF6]1a and [Ru-
(η5-C5H5){κ3(P,C,C)-Ph2PCH2CHdCH2}(PPh3)][PF6].1b
Complexes [Ru(η5-C5H5){κ3(P,C,C)-Ph2PCH2CHdCH2}-
(MeCN)][PF6] (1) and [Ru(η5-C5H5){κ3(P,C,C)-Ph2PCH2CH2-
CHdCH2}(MeCN)][PF6] (2) have been used as substrates in
the reaction with propargylic alcohols. The synthesis of complex
2 has been previously reported.7
Regioselective Synthesis of [Ru(η5-C5H5){κ(P),η4-Ph2P-
(CH2)nCHdCHC(R)dCH2}][PF6] (n ) 1; R ) CPh2OH (3),
C(C12H8)OH (4), C(C4H8)OH (5), CMePhOH (6); n ) 2; R
) CPh2OH (7), C(C4H8)OH (8), CMePhOH (9), CHPhOH
(10)). The reaction of complexes [Ru(η5-C5H5){κ3(P,C,C)-Ph2-
PCH2CHdCH2}(MeCN)][PF6] (1) and [Ru(η5-C5H5){κ3(P,C,C)-
Ph2PCH2CH2CHdCH2}(MeCN)][PF6] (2) with propargyl al-
cohols in refluxing THF leads to the formation of the complexes
[Ru(η5-C5H5){κ(P),η4-(2Z)-Ph2PCH2CHdCHC(R)dCH2}]-
[PF6] (R ) CPh2OH (3), C(C12H8)OH (4), C(C4H8)OH (5),
Scheme 2

RegioselectiVe Synthesis of η4-Dienylphosphane Ru Complexes
Organometallics, Vol. 26, No. 22, 2007 5317
Figure 1. Molecular structure and atom-labeling scheme for
complex 9a‚1/2OEt2. Non hydrogen atoms are represented by their
20% probability ellipsoids. [PF6] ion, most hydrogen atoms, phenyl
rings, and solvent molecule have been omitted for clarity.
Figure 3. Molecular structure and atom-labeling scheme for
complex 10b‚1/2OEt2. Non hydrogen atoms are represented by their
20% probability ellipsoids. [PF6] ion, most hydrogen atoms, phenyl
rings, and solvent molecule have been omitted for clarity.
Table 1. Selected Bond Distances (Å) and Bond Angles (deg)
a
for 9a‚1/2OEt2, 9b, and 10b‚1/2OEt2
9a·1/2OEt2
9b
10b·1/2OEt2
Bond Distances
Ru(1)-C*
Ru(1)-P(1)
Ru(1)-C(1)
Ru(1)-C(2)
Ru(1)-C(3)
Ru(1)-C(4)
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
1.8788(4)
2.3040(13)
2.208(5)
2.190(5)
2.150(5)
2.253(5)
1.419(7)
1.429(8)
1.395(8)
1.881(16)
2.3223(19)
2.185(6)
2.187(6)
2.164(7)
2.241(7)
1.408(10)
1.418(10)
1.427(11)
1.8635(3)
2.3159(11)
2.197(4)
2.181(4)
2.172(4)
2.234(4)
1.421(6)
1.443(6)
1.415(5)
Bond Angles
C*-Ru(1)-C(1)
C*-Ru(1)-C(2)
C*-Ru(1)-C(3)
C*-Ru(1)-C(4)
C*-Ru(1)-P(1)
C(1)-C(2)-C(3)
C(2)-C(3)-C(4)
138.54(14)
128.65(13)
128.08(14)
137.32(11)
117.14(4)
119.3(5)
136.1(4)
125.9(4)
126.7(6)
137.5(5)
118.2(4)
119.8(7)
123.1(7)
134.81(12)
125.36(12)
126.50(12)
138.03(12)
117.90(3)
121.0(4)
Figure 2. Molecular structure and atom-labeling scheme for
complex 9b. Non hydrogen atoms are represented by their 20%
probability ellipsoids. [PF6] ion, most hydrogen atoms, and phenyl
rings have been omitted for clarity.
123.1(5)
121.9(4)
allowed us to collect suitable crystals for X-ray diffraction
studies. An ORTEP-type representation of the cation of the
complexes is shown in Figures 1-3. Selected bonding data are
collected in Table 1.
The crystals belong to P21/c (9a), Cc (9b), and P21/n (10b)
space groups, indicating the presence of the racemic mixture.
For complex 9b the asymmetric unit consists of two conformers
that present identical stereochemistry with relative configuration
RRuRC. The relevant structural parameters are similar in both
molecules, and the data corresponding to only one of them will
be discussed.
All complexes exhibit a three-legged piano stool geometry,
and the bond distances around the ruthenium atom are in
accordance with previously reported structures (Å):1b Ru(1)-
C* 1.8788(4) (9a), 1.881(16) (9b), 1.8635(3) (10b); Ru(1)-
P(1) 2.304(1) (9a), 2.322(2) (9b), and 2.316(1) (10b). The
C(3)-C(4) olefin atoms of the three structures adopt a Z
configuration. The C(1)-C(2)-C(3)-C(4) atoms constitute a
butadiene fragment in an s-cis conformation. The Ru-C(1),
Ru-C(2), Ru-C(3), and Ru-C(4) bond distances reflect the
coordination of the two olefins of this butadiene fragment to
the metal center with distances in the range 2.253-2.150 Å.
a C* ) centroid of C(7), C(8), C(9), C(10), C(11).
The olefinic bond distances C(1)-C(2) and C(3)-C(4) are
longer than that expected for a CdC, and the single C(sp2)-
C(sp2) bond distance C(2)-C(3) is shorter than that of a single
C-C bond, indicating some delocalization along the chain.
X-ray studies allow the unambiguous assignment of 9a as
the RRuSC diastereoisomer and of 9b and 10b as the RRuRC
diastereoisomer. It is worth noting that a different diasteroisomer
[9b (RRuRC) and 10a (RRuSC)] crystallizes from the solutions of
complexes 9 and 10. Therefore, the X-ray diffraction studies
were crucial to elucidate the structures of all of the resulting
complexes.
Regioselective Synthesis of [Ru(η5-C5H5){κ(P),η4-(2Z,4E)-
Ph2PCH2CHdCHCHdCH(R)}][PF6] (R ) Ph (11), p-MeC6H4
(12)). The reaction of complex [Ru(η5-C5H5){κ3(P,C,C)-Ph2-
PCH2CHdCH2}(MeCN)][PF6] (1) with RCtCH (R ) Ph,
p-MeC6H4) in refluxing THF for 50 min yields regioselectively
the complexes [Ru(η5-C5H5){κ(P),η4-(2Z,4E)-Ph2PCH2CHd
CHCHdCH(R)}][PF6] (R ) Ph (11), p-MeC6H4 (12)) (Scheme
3).
Complexes 11 and 12 are obtained as pale yellow solids in
(9) Garrou, P. Chem. ReV. 1981, 81, 229-266.
77% and 69% yield, respectively. Both complexes have been

5318 Organometallics, Vol. 26, No. 22, 2007
D´ıez et al.
Scheme 3
Chart 2
The crystals belong to a centrosymmetric space group, P21/
c. Complex 12 exhibits a three-legged piano stool geometry with
the ruthenium atom bonded η5 to the cyclopentadienyl ring and
to the phosphorus atom and η2 to the two olefin groups of the
dienylphosphane ligand. The bond distances around the ruthe-
nium atom are in accord with previous structures.1b Like in
complexes 9a, 9b, and 10b, the butadiene fragment C(1)-C(2)-
C(3)-C(4) of 12 presents an s-cis conformation and the Ru-
C(1), Ru-C(2), Ru-C(3), and Ru-C(4) bond distances (2.279-
2.165 Å) reflect the coordination of the two olefins to the metal
center and are longer than those found for complexes 9a, 9b,
and 10b. The bond distances C(1)-C(2) (1.410(4) Å), C(2)-
C(3) (1.437(4) Å), and C(3)-C(4) (1.415(5) Å) are relatively
uniform, in accordance with electronic delocalization along the
chain. For this complex, the C(1)-C(23) bond distance (1.486-
(4) Å) indicates that delocalization can also occur through the
aromatic ring (see Chart 2). The torsion angles C(3)-C(2)-
C(1)-C(23) and C(4)-C(3)-C(2)-C(1) (8.1(2)° and 4.9(4)°)
agree with the planarity of the chain. The stereochemistry around
the C(1)-C(2) and C(3)-C(4) double bonds are E and Z,
respectively.
Theoretical Calculations. As shown before, the reaction of
complexes 1 and 2 with propargylic alcohols leads to complexes
that contain a branched butadiene fragment, while the reaction
of 1 with RCtCH (R ) Ph, p-MeC6H4) yields complexes 11
and 12, containing a linear butadiene fragment.
In order to understand the regiochemistry of these reactions,
minimum-energy structure calculations were carried out by DFT
methods. Calculations were performed on selected molecules
isolated in the present work and on hypothetical ones.
No simplified model compounds were used for the calcula-
tions. Calculated structures are assigned Roman numbers. The
isomers that present a branched dienylphosphane ligand are
named as “a”, and the complexes with a linear one are named
as “b”. Computer-generated images of all these structures are
given as Supporting Information.
fully characterized by spectroscopic methods. Thus, the IR
spectra show the characteristic ν(PF6) band at 838 (11) and 839
cm-1 (12). The 1H NMR spectra of both complexes show
characteristic signals for the internal olefinic protons of the η4-
butadiene fragment in the range 6.97-4.95 ppm. The dCHR
proton appears at lower fields (2.90 (11) and 2.91 (12) ppm) as
a doublet of doublets (JHP 15.5-15.4, JHH 9.7-9.5 Hz). The
31P{1H} NMR spectra show the characteristic high-field signals
for the ligand at -64.60 and -64.26 ppm for 11 and 12,
respectively. Other analytical and spectroscopic data are in
agreement with the proposed formulations.
The most interesting feature in the reactions of complex 1
with terminal alkynes RCtCH (R ) Ph, p-MeC6H4) is the high
regioselectivity observed, unlike the reaction between 2 and
alkynes reported by Kichner, where the linear dienyl regioisomer
is formed along with the branched dienyl regioisomer.7
On the other hand, it is interesting to note that a reversed
regioselectivity is observed in the reaction of complex 1 with
alkynes and propargylic alcohols. Thus, complexes 11 and 12
result from alkynes (see Scheme 3), while complexes 3-6,
having a branched butadiene unit, are formed from propargylic
alcohols (see Scheme 1).
X-ray Crystal Structure of the Complex [Ru(η5-C5H5)-
{κ(P),η4-(2Z,4E)-Ph2PCH2CHdCHCHdCH(p-MeC6H4)}]-
[PF6] (12). Slow diffusion of n-hexane into a solution of the
complex 12 in dichloromethane allowed us to collect suitable
crystals for X-ray diffraction studies. An ORTEP-type repre-
sentation of the cation is shown in Figure 4, and selected
bonding data are collected in the caption.
Table 2 shows the relative energies of optimized structures.
The calculated more stable isomers are in accord with the
experimental results, even when the energy differences are only
0.3 to 2.7 kcal mol-1. Thus, complexes 6 (IIa), 9 (VIa), and 10
(VIIa), containing a branched dienylphosphane ligand, are more
stable than the corresponding “b” isomers (IIb, VIb, and VIIb),
having a linear dienylphosphane ligand. In order to know the
influence of the OH group in the regiochemistry of the reaction,
calculations for a hypothetical complex where the OH group is
replaced by an H atom (V and X) were carried out. For both
complexes the type “a” isomer with the linear dienylphosphane
ligand is still the thermodynamically more stable isomer,
pointing out that the OH group is not responsible for the
observed regiochemistry. The same results were found for R )
Me (complexes IV and IX). On the other hand, for complex 12
the regioisomer displaying the linear dienylphosphane ligand
(IIIb) is 2.1 kcal mol-1 more stable than the IIIa isomer. The
formation of complexes IIIb and VIIIb as the more stable iso-
mers agrees with the stabilization due to the linear conjugation
with the aromatic ring, which cannot occur with any other
substituent.
Figure 4. Molecular structure and atom-labeling scheme for
complex 12. Non hydrogen atoms are represented by their 20%
probability ellipsoids. [PF6] ion, most hydrogen atoms, and phenyl
rings have been omitted for clarity. Selected bond lengths (Å): Ru-
(1)-C* ) 1.86226(19), Ru(1)-P(1) ) 2.2938(7), Ru(1)-C(1) )
2.279(3), Ru(1)-C(2) ) 2.165(3), Ru(1)-C(3) ) 2.181(3), Ru-
(1)-C(4) ) 2.277(3), C(1)-C(2) ) 1.410(4), C(2)-C(3)) 1.437-
(4), C(3)-C(4) ) 1.415(5). Selected bond angles (deg): C*-
Ru(1)-C(1) ) 135.71(7), C*-Ru(1)-C(2) ) 128.62(8), C*-
Ru(1)-C(3) ) 131.14(8), C*-Ru(1)-C(4) ) 138.33(8), C*-
Ru(1)-P(1) ) 125.827(19), C(1)-C(2)-C(3) ) 122.6(3), C(2)-
C(3)-C(4) ) 125.5(3), C(3)-C(4)-C(5) ) 127.8(3), C* )
centroid of C(6), C(7), C(8), C(9), C(10).

RegioselectiVe Synthesis of η4-Dienylphosphane Ru Complexes
Organometallics, Vol. 26, No. 22, 2007 5319
Table 2. Relative Energies (kcal mol-1) of DFT-Optimized Structures (0.0 kcal mol-1 is the energy assigned to the most stable
isomer)
HMBC) were performed in selected complexes. Coupling constants
J are given in hertz. Abbreviations used: Ar, aromatic; s, singlet;
d, doublet; dd, doublet of doublets; t, triplet; m, multiplet; br, broad.
The 31P NMR spectra of the complexes show the corresponding
PF6 septuplet signal. The following atom labels have been use for
For complexes 9a, 10a, and 12, the distances found for DFT-
optimized structures are in agreement with the distances found
by the X-ray analysis. So, DFT calculations can also be used
to analyze structural aspects of the hypothetical complexes.
Thus, according to the statement that the delocalization through
the aromatic ring is an important factor for the higher stability
of IIIb and VIIIb, the calculated distances C(2)-Cipso for the
type “a” isomers (1.4915 Å for IIIa and 1.4905 Å for VIIIa)
are longer than those calculated for the isomers of type “b”
(1.4725 Å for IIIb and 1.4745 Å for VIIIb), in agreement with
linear conjugation in type “b” isomers versus cross-conjugation
in type “a” isomers.
1
the H and 13C{1H} NMR spectroscopic data:
Synthesis of [Ru(η5-C5H5){κ3(P,C,C)-Ph2PCH2CHdCH2}-
(MeCN)][PF6] (1). A solution of [Ru(η5-C5H5)(MeCN)3][PF6] (200
mg, 0.35 mmol) and allyldiphenylphosphane (82 µL, 0.38 mmol)
in CH2Cl2 (35 mL) was stirred at 0 °C for 1.5 h. The solution was
then evaporated to dryness, the crude product extracted with
dichloromethane (2 × 10 mL), and the extract filtered. Concentra-
tion of the resulting solution to ca. 3 mL followed by the addition
of 30 mL of diethyl ether precipitated a pale yellow solid, which
was washed with diethyl ether (2 × 5 mL) and vacuum-dried.
Yield: 156 mg, 77%. IR (Nujol, ν(PF6), ν(CN), cm-1): 839, 2968.
Molar conductivity (acetone, Ω-1 cm2 mol-1): 106. 1H NMR (300.1
MHz, CD2Cl2,18 °C): δ 2.01 (s, 3H, CH3), 3.14 (m, 2H, P-CH2,
dCH2), 3.95 (m, 1H, dCH2), 4.43 (m, 2H, P-CH2, dCH), 4.87
(s, 5H, C5H5), 7.40-7.65 (m, 10H, Ph). 13C{1H} NMR (100.6 MHz,
acetone-d6,18 °C): δ 2.9 (s, CH3), 32.5 (d, JCP ) 34.2 Hz, P-CH2),
45.9 (d, JCP ) 21.9 Hz, dCH), 52.8 (d, JCP ) 6.1 Hz, dCH2),
82.8 (s, C5H5), 127.5-135.0 (CN, Ph). 31P{1H} NMR (121.5 MHz,
CD2Cl2, 18 °C): δ -53.3 (s). C22H23F6NP2Ru (578.43 g/mol). MS
(FAB+): m/z 393 [Ru(C5H5)(Ph2PCH2CHdCH2)]+.
Conclusions
In summarizing, the present work describes the synthesis of
a series of complexes bearing η4-dienylphosphane ligands via
the C-C coupling of CtC bonds with alkenylphosphanes. The
X-ray structure of representative derivatives of these complexes
allows the comparison between different alkenylphosphanes and
alkynes showing different regioselectivity depending on the
alkyne. Theoretical calculations have been carried out to explain
the high regioselectivity of the process. Even when the differ-
ences in energy are low, it was found that regioselectivity agrees
in all cases with the experimentally obtained complex.
Experimental Section
General Procedures. All manipulations were performed under
an atmosphere of dry nitrogen using vacuum-line and standard
Schlenk techniques. Solvents were dried by standard methods and
distilled under nitrogen before use. The complexes [Ru(η5-C5H5)-
(MeCN)3][PF6]10 and [Ru(η5-C5H5){κ3(P,C,C)-Ph2PCH2CH2CHd
CH2}(MeCN)][PF6]7 were prepared by previously reported methods.
Other reagents were obtained from commercial suppliers and used
without further purification. 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 microanalyzer. Mass
spectra (FAB) were recorded using a VG-Autospec spectrometer,
operating in the positive mode; 3-nitrobenzyl alcohol (NBA) was
used as the matrix. Mass spectra (MALDI-TOF) were determined
with a Microflex Bruker spectrometer, operating in the positive
mode; dihydroxyanthranol was used as the matrix. NMR spectra
were recorded on Bruker AC 300 and 300 DPX instruments at 300.1
MHz (1H), 121.5 MHz (31P), or 75.4 MHz (13C) and a Bruker AC
400 instrument at 400.1 MHz (1H), 162.0 MHz (31P), or 100.6 MHz
(13C) using SiMe4 or 85% H3PO4 as standard. DEPT experiments
were carried out for all the compounds reported. 2D-NMR (HSQC,
Synthesis of [Ru(η5-C5H5){κ(P),η4-(2Z)-Ph2PCH2CHdCHC-
(R)dCH2}][PF6] (R ) CPh2OH (3), C(C12H8)OH (4), C(C4H8)-
OH (5), CMePhOH (6)). A solution of [Ru(η5-C5H5){κ3(P,C,C)-
Ph2PCH2CHdCH2}(MeCN)][PF6] (58 mg, 0.1 mmol) and the
corresponding propargyl alcohol (0.3 mmol) in THF (10 mL) was
refluxed for 50 min. The solution was then evaporated to dryness,
the crude product extracted with dichloromethane (2 × 10 mL),
and the extract filtered. Concentration of the resulting solution to
ca. 3 mL followed by the addition of 30 mL of diethyl ether afforded
complexes 3-6 as pink solids, which were washed with diethyl
ether (2 × 5 mL) and vacuum-dried. Yield of 3: 59 mg, 79%. IR
(KBr, ν(PF6), cm-1): 840. Molar conductivity (acetone, Ω-1 cm2
1
mol-1): 107. H NMR (300.1 MHz, acetone-d6, 18 °C): δ 1.42
(dd, JHP ) 20.4 Hz, JHH ) 5.2 Hz, 1H, H-5), 3.39 (m, 1H, H-1),
3.54 (d, JHH ) 5.2 Hz, 1H, H-5), 4.05 (m, 1H, H-1), 4.84 (m, 1H,
(10) Trost, B. M.; Older, C. M. Organometallics 2002, 21, 2544-2546.

5320 Organometallics, Vol. 26, No. 22, 2007
D´ıez et al.
H-2), 5.27 (s, 5H, C5H5), 5.62 (m, 1H, H-3), 6.00 (s, 1H, OH),
7.23-7.72 (m, 20H, Ph). 13C{1H} NMR (75.4 MHz, acetone-d6,
18 °C): δ 28.8 (d, JCP ) 39.6 Hz, C-1), 43.7 (d, JCP ) 5.3 Hz,
C-5), 44.9 (d, JCP ) 28.1 Hz, C-2), 82.7 (s, C-6), 87.9 (s, C5H5),
88.1 (d, JCP ) 4.7 Hz, C-3), 114.6 (s, C-4), 127.7-149.9 (Ph).
31P{1H} NMR (121.5 MHz, acetone-d6, 18 °C): δ -61.9 (s).
C35H32F6OP2Ru (745.64 g/mol). MS (MALDI): m/z 601 [Ru-
(C5H5){Ph2PCH2CHdCHC(CPh2OH)dCH2}]+. Yield of 4: 54 mg,
73%. IR (KBr, ν(PF6), cm-1): 841. Molar conductivity (acetone,
from CH2Cl2/Et2O, yielding white crystals of 9a and 10b, respec-
tively. The corresponding solutions contained the complexes 9b
and 10a, which were isolated by precipitation with n-hexane. Yield
of 7: 61 mg, 80%. IR (KBr, ν(PF6), cm-1): 841. Molar conductivity
1
(acetone, Ω-1 cm2 mol-1): 126. H NMR (400.1 MHz, acetone-
d6, 18 °C): δ 1.35 (dd, JHP ) 18.1 Hz, JHH ) 4.8 Hz, 1H, H-6),
1.41 (m, 1H, H-2), 2.52 (m, 1H, H-2), 3.00 (d, JHH ) 4.8 Hz, 1H,
H-6), 3.60 (m, 1H, H-1), 3.76 (m, 1H, H-1), 5.12 (s, 5H, C5H5),
5.51 (m, 1H, H-3), 6.06 (d, JHH ) 8.1 Hz, 1H, H-4), 6.09 (s, 1H,
OH), 7.22-7.78 (m, 20H, Ph). 13C{1H} NMR (100.6 MHz, acetone-
d6, 18 °C): δ 26.4 (d, JCP ) 7.0 Hz, C-2), 44.4 (d, JCP ) 6.0 Hz,
C-6), 47.1 (d, JCP ) 35.2 Hz, C-1), 77.7 (s, C-3), 82.2 (s, C-7),
84.4 (s, C-4), 88.5 (s, C5H5), 117.1 (s, C-5), 127.7-149.0 (Ph).
31P{1H} NMR (162.0 MHz, acetone-d6, 18 °C): δ 94.7 (s). Anal.
Calcd for C36H34F6OP2Ru (759.66 g/mol): C 56.92, H 4.51.
Found: C 57.46, H 4.99. Yield of 8: 55 mg, 83%. IR (KBr, ν-
(PF6), cm-1): 840. Molar conductivity (acetone, Ω-1 cm2 mol-1):
1
Ω-1 cm2 mol-1): 105. H NMR (300.1 MHz, acetone-d6, 18 °C):
δ 0.70 (dd, JHP ) 19.8 Hz, JHH ) 4.7 Hz, 1H, H-5), 2.90 (m, 1H,
H-1), 3.43 (d, JHH ) 4.7 Hz, 1H, H-5), 4.03 (m, 1H, H-1), 4.89
(m, 1H, H-2), 5.58 (s, 5H, C5H5), 5.74 (s, 1H, OH), 6.00 (m, 1H,
H-3), 7.36-7.86 (m, 18H, Ph). 13C{1H} NMR (75.4 MHz, acetone-
d6, 18 °C): δ 28.5 (d, JCP ) 39.2 Hz, C-1), 40.0 (d, JCP ) 4.9 Hz,
C-5), 45.4 (d, JCP ) 28.0 Hz, C-2), 84.8 (s, C-6), 85.1 (d, JCP
)
5.1 Hz, C-3), 87.9 (s, C5H5), 112.3 (s, C-4), 122.3-151.3 (Ph).
31P{1H} NMR (121.5 MHz, acetone-d6, 18 °C): δ -61.6 (s).
C35H30F6OP2Ru (743.62 g/mol). MS (MALDI): m/z 599 ([Ru-
(C5H5){Ph2PCH2CHdCHC(C(C12H8)OH)dCH2}]+. Yield of 5: 45
mg, 70%. IR (KBr, ν(PF6), cm-1): 841. Molar conductivity
135. 1H NMR (400.1 MHz, acetone-d6, 18 °C): δ 0.88 (dd, JHP
)
16.8 Hz, JHH ) 4.5 Hz, 1H, H-6), 1.07 (m, 1H, H-2), 1.75 (m, 2H,
-(CH2)4-), 2.07 (m, 6H, -(CH2)4-), 2.34 (m, 1H, H-2), 3.00 (d,
JHH ) 4.5 Hz, 1H, H-6), 3.48 (m, 1H, H-1), 3.69 (m, 1H, H-1),
4.80 (s, 1H, OH), 5.17 (s, 5H, C5H5), 5.48 (m, 1H, H-3), 6.21 (d,
JHH ) 8.2 Hz, 1H, H-4), 7.48-7.99 (m, 10H, Ph). 13C{1H} NMR
(100.6 MHz, acetone-d6, 18 °C): δ 24.9 (s, -(CH2)4-), 26.2 (d,
JCP ) 7.5 Hz, C-2), 26.7 (s, -(CH2)4-), 40.1 (s, -(CH2)4-), 44.0
(s, C-6), 47.2 (d, JCP ) 34.3 Hz, C-1), 48.8 (s, -(CH2)4-), 78.9
(d, JCP ) 3.3 Hz, C-3), 81.9 (s, C-4), 84.8 (s, C-7), 88.3 (s, C5H5),
115.8 (s, C-5), 130.7-142.8 (Ph). 31P{1H} NMR (162.0 MHz,
acetone-d6, 18 °C): δ 93.5 (s). Anal. Calcd for C28H32F6OP2Ru
(661.56 g/mol): C 50.83, H 4.88. Found: C 51.41, H 5.31. Yield
of 9a: 24 mg, 34%. IR (KBr, ν(PF6), cm-1): 840. Molar
conductivity (acetone, Ω-1 cm2 mol-1): 134. 1H NMR (300.1 MHz,
acetone-d6, 18 °C): δ 0.80 (dd, JHP ) 18.0 Hz, JHH ) 4.3 Hz, 1H,
H-6), 0.98 (m, 1H, H-2), 2.08 (s, 3H, CH3), 2.40 (m, 1H, H-2),
2.94 (d, JHH ) 4.3 Hz, 1H, H-6), 3.46 (m, 1H, H-1), 3.66 (m, 1H,
H-1), 5.17 (s, 5H, C5H5), 5.35 (s, 1H, OH), 5.55 (m, 1H, H-3),
6.34 (d, JHH ) 8.0 Hz, 1H, H-4), 7.26-7.83 (m, 15H, Ph). 13C-
{1H} NMR (75.4 MHz, acetone-d6, 18 °C): δ 26.3 (d, JCP ) 7.5
Hz, C-2), 32.3 (s, CH3), 40.8 (d, JCP ) 6.0 Hz, C-6), 47.0 (d, JCP
) 34.5 Hz, C-1), 77.2 (s, C-7), 78.2 (d, JCP ) 3.7 Hz, C-3), 83.5
(s, C-4), 88.5 (s, C5H5), 117.1 (s, C-5), 126.7-148.9 (Ph). 31P-
{1H} NMR (162.0 MHz, acetone-d6, 18 °C): δ 95.1 (s). Anal. Calcd
for C31H32F6OP2Ru‚CH2Cl2 (782.52 g/mol): C 49.12, H 4.38.
Found: C 49.36, H 4.28. Yield of 9b: 16 mg, 24%. IR (KBr, ν-
(PF6), cm-1): 839. Molar conductivity (acetone, Ω-1 cm2 mol-1):
1
(acetone, Ω-1 cm2 mol-1): 109. H NMR (300.1 MHz, acetone-
d6, 18 °C): δ 0.88 (dd, JHP ) 19.8 Hz, JHH ) 4.9 Hz, 1H, C-5),
1.85 (m, 6H, -(CH2)4-), 2.18 (m, 2H, -(CH2)4-), 3.02 (m, 1H,
H-1), 3.66 (d, JHH ) 4.9 Hz, 1H, H-5), 4.01 (m, 1H, H-1), 4.75
(m, 1H, H-2), 5.09 (s, 1H, OH), 5.31 (s, 5H, C5H5), 5.68 (m, 1H,
H-3), 7.46-7.77 (m, 10H, Ph). 13C{1H} NMR (75.4 MHz, acetone-
d6, 18 °C): δ 24.9 (s, 2CH2, -(CH2)4-), 27.3 (d, JCP ) 39.1 Hz,
C-1), 38.9 (d, JCP ) 5.1 Hz, C-5), 39.2 (s, -(CH2)4-), 43.9 (d, JCP
) 28.0 Hz, C-2), 45.8 (s, -(CH2)4-), 83.4 (s, C-6), 83.8 (d, JCP
)
5.2 Hz, C-3), 85.9 (s, C5H5), 111.7 (s, C-4), 125.5-150.3 (Ph).
31P{1H} NMR (121.5 MHz, acetone-d6, 18 °C): δ -59.2 (s).
C27H30F6OP2Ru (647.53 g/mol). MS (MALDI): m/z 503 [Ru-
(C5H5){Ph2PCH2CHdCHC(C(C4H8)OH)dCH2}+. Yield of 6: 48
mg, 70%. IR (KBr, ν(PF6), cm-1): 840. Molar conductivity
1
(acetone, Ω-1 cm2 mol-1): 112. H NMR (300.1 MHz, acetone-
d6, 18 °C): δ 0.75 (m, 1H, H-5 minor), 1.12 (m, 1H, H-5 major),
1.70 (s, 3H, CH3 minor), 1.86 (s, 3H, CH3 major), 2.90 (m, 3H,
H-1 major + minor), 3.62 (d, JHH ) 4.7 Hz, 1H, H-5 minor), 3.95
(m, 1H, H-1 major+ minor), 4.04 (d, JHH ) 3.8 Hz, 1H, H-5 major),
4.72 (m, 1H, H-2 major), 4.84 (m, 1H, H-2 minor), 5.22 (s, 1H,
OH major), 5.33 (s, 5H, C5H5 minor), 5.41 (s, 5H, C5H5 major),
5.47 (s, 1H, OH minor), 5.67 (m, 1H, H-3 major), 5.87 (m, 1H,
H-3 minor), 7.27-7.79 (m, 30H, Ph). 13C{1H} NMR (75.4 MHz,
acetone-d6, 18 °C): δ 27.3 (d, JCP ) 39.5 Hz, C-1 minor), 27.4 (d,
JCP ) 38.7 Hz, C-1 major), 39.1 (d, JCP ) 5.2 Hz, C-5 minor),
40.3 (d, JCP ) 5.1 Hz, C-5 major), 43.3 (d, JCP ) 28.3 Hz, C-2
minor), 43.8 (d, JCP ) 28.2 Hz, C-2 major), 75.7 (s, C-6 minor),
76.1 (s, C-6 major), 84.3 (d, JCP ) 5.2 Hz, C-3 minor), 85.4 (d,
JCP ) 5.5 Hz, C-3 major), 86.4 (s, C5H5 minor), 86.5 (s, C5H5
major), 113.5 (s, C-4 minor), 113.8 (s, C-4 major), 125.3-149.4
(Ph). 31P{1H} NMR (121.5 MHz, acetone-d6, 18 °C): δ -59.7 (s,
minor), -60.2 (s, major). C30H30F6OP2Ru (683.57 g/mol). MS
(MALDI): m/z 539 [Ru(C5H5){Ph2PCH2CHdCHC(RCMePh)d
CH2}]+.
Synthesis of [Ru(η5-C5H5){κ(P)-η4-(3Z)-Ph2PCH2CH2CHd
CHC(R)dCH2}][PF6] (R ) CPh2OH (7), C(C4H8)OH (8),
CMePhOH (9a,b), CHPhOH (10a,b)). A solution of [Ru(η5-
C5H5){κ3(P,C,C)-Ph2PCH2CH2CHdCH2}(MeCN)][PF6] (59 mg,
0.1 mmol) and the corresponding propargyl alcohol (0.4 mmol) in
THF (10 mL) was refluxed for 1.5 h. The solution was then
evaporated to dryness, the crude product extracted with dichlo-
romethane (2 × 10 mL), and the extract filtered. Concentration of
the resulting solution to ca. 3 mL followed by the addition of 30
mL of diethyl ether afford complexes 7-10 as white solids, which
were washed with diethyl ether (2 × 5 mL) and vacuum-dried.
The complexes 9a,b and 10a,b were separated by recrystallization
1
122. H NMR (300.1 MHz, acetone-d6, 18 °C): δ 0.85 (m, 1H,
H-2), 1.02 (dd, JHP ) 17.4 Hz, JHH ) 4.9 Hz, 1H, H-6), 1.83 (s,
3H, CH3), 2.25 (m, 1H, H-2), 3.36 (d, JHH ) 4.9 Hz, 1H, H-6),
3.48 (m, 1H, H-1), 3.67 (m, 1H, H-1), 5.29 (s, 5H, C5H5), 5.44 (m,
2H, H-3, OH), 6.24 (d, JHH ) 8.3 Hz, 1H, H-4), 7.23-8.02 (m,
15H, Ph). 13C{1H} NMR (75.4 MHz, acetone-d6, 18 °C): δ 26.2
(d, JCP ) 7.6 Hz, C-2), 28.7 (s, CH3), 40.9 (d, JCP ) 5.8 Hz, C-6),
47.1 (d, JCP ) 34.4 Hz, C-1), 77.5 (s, C-7), 78.5 (d, JCP ) 4.0 Hz,
C-3), 81.7 (s, C-4), 88.6 (s, C5H5), 117.2 (s, C-5), 127.1-150.7
(Ph). 31P{1H} NMR (162.0 MHz, acetone-d6, 18 °C): δ 94.2 (s).
Anal. Calcd for C31H32F6OP2Ru (697.59 g/mol): C 53.37, H 4.62.
Found: C 54.12, H 4.91. Yield of 10a: 32 mg, 47%. IR (KBr,
ν(PF6), cm-1): 838. Molar conductivity (acetone, Ω-1 cm2 mol-1):
1
110. H NMR (300.1 MHz, acetone-d6, 18 °C): δ 0.74 (m, 1H,
H-2), 0.87 (m, 1H, H-6), 2.30 (m, 1H, H-2), 3.20 (d, JHH ) 4.0
Hz, 1H, H-6), 3.51 (m, 2H, H-1), 5.24 (s, 6H, OH, C5H5), 5.48 (m,
1H, H-3), 5.62 (br, 1H, H-7), 6.49 (d, JHH ) 8.1 Hz, 1H, H-4),
7.28-8.00 (m, 15H, Ph). 13C{1H} NMR (100.6 MHz, acetone-d6,
18 °C): δ 26.8 (d, JCP ) 8.4 Hz, C-2), 42.5 (d, JCP ) 5.2 Hz,
C-6), 47.2 (d, JCP ) 33.4 Hz, C-1), 78.4, 79.4, 82.3 (3 x s, C-3,4,7),
89.2 (s, C5H5), 110.7 (s, C-5), 128.5-147.5 (Ph). 31P{1H} NMR
(162.0 MHz, acetone-d6, 18 °C): δ 92.5 (s). Anal. Calcd for

RegioselectiVe Synthesis of η4-Dienylphosphane Ru Complexes
Organometallics, Vol. 26, No. 22, 2007 5321
C30H30F6OP2Ru (683.57 g/mol): C 52.71, H 4.42. Found: C 53.25,
H 4.98. Yield of 10b: 24 mg, 35%. IR (KBr, ν (PF6), cm-1): 840.
Molar conductivity (acetone, Ω-1 cm2 mol-1): 117. 1H NMR (300.1
ing the B3LYP nonlocal gradient correction.13 The LANL2DZ basis
set, with relativistic effective core potentials, was used for the Ru
atoms.14 The basis set used for the remaining atoms was the 6-31G,
with addition of (d,p)-polarization for all atoms. All optimized
structures were confirmed as minima by calculation of analytical
frequencies. For each calculation, the input model molecule was
based on one of the X-ray-determined structures reported in this
article, conveniently modified (if necessary) by changing the
appropriate R groups.
X-ray Crystal Structure Determination of Complexes 9a‚1/
2OEt2, 9b, 10b‚1/2OEt2, and 12. Crystals suitable for X-ray
diffraction analysis were obtained by slow diffusion of diethyl ether
(9a, 9b, and 10b) or n-hexane (12) into a saturated solution of the
corresponding complex in dichloromethane.
MHz, acetone-d6, 18 °C): δ 0.75 (m, 1H, H-2), 0.98 (dd, JHP
)
16.2 Hz, JHH ) 3.5 Hz, 1H, H-6), 2.25 (m, 1H, H-2), 3.50 (m, 2H,
H-1), 3.64 (m, 1H, H-6), 5.17 (s, 5H, C5H5), 5.23 (s, 1H, OH),
5.51 (m, 1H, H-3), 5.70 (br, 1H, H-7), 6.16 (d, JHH ) 7.9 Hz, 1H,
H-4), 7.30-8.03 (m, 15H, Ph). 13C{1H} NMR (100.6 MHz, acetone-
d6, 18 °C): δ 26.6 (d, JCP ) 8.0 Hz, C-2), 39.1 (d, JCP ) 5.3 Hz,
C-6), 47.3 (d, JCP ) 33.6 Hz, C-1), 78.1 (s, C-4,7), 80.2 (d, JCP
)
3.8 Hz, C-3), 86.5 (s, C-4,7), 89.2 (s, C5H5), 111.5 (s, C-5), 128.6-
146.8 (Ph). 31P{1H} NMR (162.0 MHz, acetone-d6, 18 °C): δ 92.4
(s). Anal. Calcd for C30H30F6OP2Ru (683.57 g/mol): C 52.71, H
4.42. Found: C 52.73, H 4.79.
Synthesis of [Ru(η5-C5H5){κ(P)-η4-(2Z,4E)-Ph2PCH2CHd
CHCHdCH(R)}][PF6] (R ) Ph (11), R ) p-MeC6H4 (12)). A
solution of [Ru(η5-C5H5){κ3(P,C,C)-Ph2PCH2CHdCH2}(MeCN)]-
[PF6] (58 mg, 0.1 mmol) and the corresponding alkyne (0.3 mmol)
in THF (10 mL) was refluxed for 50 min. The solution was then
evaporated to dryness, the crude product extracted with dichlo-
romethane (2 × 10 mL), and the extract filtered. Concentration of
the resulting solution to ca. 3 mL followed by the addition of 30
mL of diethyl ether afforded complexes 11 and 12 as pale yellow
solids, which were washed with diethyl ether (2 × 5 mL) and
vacuum-dried. Yield of 11: 45 mg, 77%. IR (KBr, ν(PF6), cm-1):
838. Molar conductivity (acetone, Ω-1 cm2 mol-1): 101. 1H NMR
(300.1 MHz, acetone-d6, 18 °C): δ 2.90 (dd, JHP ) 15.5 Hz, JHH
) 9.5 Hz, 1H, H-5), 3.29 (m, 1H, H-1), 4.01 (m, 1H, H-1), 4.98
(m, 1H, H-2), 5.24 (s, 5H, C5H5), 5.71 (m, 1H, H-3), 6.60 (d, JHH
) 7.3 Hz, 1H, Ph), 6.97 (dd, JHH ) 9.5 Hz, JHH ) 6.5 Hz, 1H,
H-4), 6.94-7.84 (m, 15 H, Ph). 13C{1H} NMR (100.6 MHz,
The most relevant crystal and refinement data are collected in
Table 3. Data collection were performed on a Bruker SMART 6K
CCD area-detector three-circle diffractometer (Cu KR radiation, λ
) 1.5418 Å).15 X-ray data were collected at 100(2) K, with a
combination of three runs at different æ and 2θ angles. The data
were collected using 0.3° wide ω scans with a crystal-to-detector
distance of 40 mm. The diffraction frames were integrated using
the SAINT package16 and corrected for absorption with SADABS.17
For 12 data were collected at 150(2) K on a Nonius Kappa CCD
single-crystal diffractometer using Cu KR radiation (λ ) 1.5418
Å) with a crystal-detector distance fixed at 29 mm, using the
oscillation method, with 2° oscillation. Data colletion strategy was
calculated with the program COLLECT.18 Data reduction and cell
refinement were performed with the programs HKL Denzo and
Scalepack,19 and absorption correction was applied by means of
SORTAV.20
The software package WINGX was used for space group
determination and structure solution and refinement.21 The structures
were solved by Patterson interpretation and phase expansion using
DIRDIF.22 Isotropic least-squares refinement on F2 was performed
using SHELXL97.23 For 9a and 10b, one diethyl ether molecule
of solvation for two formula units of the complex was found to be
disordered over two positions with 0.5 site occupancy factors.
During the final stages of the refinements, all the positional para-
meters and the anisotropic temperature factors of all the non-H
atoms were refined with the exception of those from the disordered
diethyl ether solvent molecule in 10b, which were isotropically
refined. The H atoms were geometrically located and their coor-
dinates were refined riding on their parent atoms, except for the H
atoms of the molecules 10b and 12 and for H1A and H1B of 9a,
where the coordinates of H atoms were found from difference
Fourier maps and included in a refinement with isotropic param-
eters. In all cases, the maximum residual electron density is located
near heavier atoms, except for 10b, in which the highest residual
peaks are close to the disordered solvent molecule. The function
acetone-d6, 18 °C): δ 28.1 (d, JCP ) 37.9 Hz, C-1), 49.8 (d, JCP
)
26.8 Hz, C-2), 66.5, 83.3 (2 × s, C-4,5), 86.4 (d, JCP ) 6.5 Hz,
C-3), 87.9 (s, C5H5), 127.4-141.6 (Ph). 31P{1H} NMR (121.5 MHz,
acetone-d6, 18 °C): δ -64.6 (s). C28H26F6P2Ru (639.51 g/mol).
MS (FAB+): m/z 495 [Ru(C5H5){Ph2PCH2CHdCHCHdCH-
(Ph)}]+. Yield of 12: 44 mg, 69%. IR (KBr, ν(PF6), cm-1): 839.
Molar conductivity (acetone, Ω-1 cm2 mol-1): 98. 1H NMR (300.1
MHz, acetone-d6, 18 °C): δ 2.23 (s, 3H, CH3), 2.91 (dd, JHP
)
15.4 Hz, JHH ) 9.7 Hz, 1H, H-5), 3.26 (m, 1H, H-1), 3.99 (m, 1H,
H-1), 4.95 (m, 1H, H-2), 5.23 (s, 5H, C5H5), 5.70 (m, 1H, H-3),
6.49 (d, JHH ) 8.2 Hz, 1H, Ph), 6.91 (m, 2H, H-4, Ph), 6.97-7.83
(m, 14H, Ph). 13C{1H} NMR (75.4 MHz, acetone-d6, 18 °C): δ
22.1 (s, CH3), 28.7 (d, JCP ) 37.9 Hz, C-1), 50.2 (d, JCP ) 27.4
Hz, C-2), 68.9, 86.6 (2 × s, C-4,5), 86.9 (d, JCP ) 7.0 Hz, C-3),
88.4 (s, C5H5), 127.6-139.2 (Ph). 31P{1H} NMR (121.5 MHz,
acetone-d6, 18 °C): δ -64.3 (s). C29H28F6P2Ru (653.54 g/mol).
MS (FAB+): m/z 509 [Ru(C5H5){Ph2PCH2CHdCHCHdCH-
(MeC6H4)}]+.
Theoretical Calculations. All the minimum-energy structures
reported herein were optimized using hybrid density functional
theory (DFT), within the Gaussian03 program,11 using Becke’s
three-parameter hybrid exchange-correlation functional12 contain-
2
2
minimized was ([∑wFo2 - Fc2)/∑w(Fo )]1/2, where w ) 1/[σ2(Fo )
(12) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
(13) Lee, C.; Yang, W.; Parr, R. G. Phys. ReV. B 1988, 37, 785-789.
(14) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299-310.
(15) SMART version 5.625, Area-Detector Software Package; Bruker
AXS; Madison, WI, 1997-2001.
(16) SAINT version 6.02; Bruker Analytical X-ray Systems: Madison,
WI, 2000.
(17) Sheldrick, G. M. SADABS empirical absorption program; University
of Gottingen, 1996.
(11) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Montgomery, J. A.; Vreven, T.; Kudin, K. N.;
Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.;
Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.;
Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;
Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li,
X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.;
Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.;
Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.;
Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels,
A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.;
Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.;
Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz,
P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.;
Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson,
B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian03;
Gaussian, Inc.: Wallingford, CT, 2004.
(18) Collect; Nonius BV: Delft, 1997-2000.
(19) Otwinowski, Z.; Minor, W. Methods Enzymol. 1997, 276, 307-
326.
(20) Blessing, R. H. Acta Crystallogr. Sect. A 1995, 51, 33-38.
(21) Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837-838.
(22) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
Garc´ıa-Granda, S.; Gould, R. O.; Smits J. M. M.; Smykalla, C. The DIRDIF
Program System; Techical Report of the Crystallographic Laboratory;
University of Nijimegen: Nijimegen, The Netherlands, 1999.
(23) Sheldrick, G. M. SHELXL-97, Program for the Refinement of Crystal
Structures; University of Go¨ttingen, 1997.

5322 Organometallics, Vol. 26, No. 22, 2007
D´ıez et al.
Table 3. Crystal Data and Structure Refinement Details for Complexes 9a‚1/2OEt2, 9b, 10b‚1/2OEt2, and 12
9a·1/2OEt2
9b
10b·1/2OEt2
12
chemical formula
2(C31H32OPRu), 2(F6P),
C4H10O
1469.27
C31H32F6OP2Ru
2(C30H30OPRu),
2(F6P), C4H10O
1441.22
C29H28F6P2Ru
fw
697.58
653.52
T (K)
100(2)
100(2)
100(2)
150(2)
wavelength (Å)
cryst syst
space group
a (Å)
b (Å)
c (Å)
1.5418
monoclinic
P21/c
13.1933(5)
11.7672(5)
21.0420(7)
105.379(2)
3149.8(2)
1.5418
monoclinic
Cc
10.6948(2)
38.0333(8)
15.2449(2)
110.0030(10)
5826.92(18)
8
1.5418
monoclinic
P21/n
16.1051(2)
11.7230(2)
17.6605(2)
106.5630(10)
3195.95(8)
2
1.5418
monoclinic
P21/c
9.41650(10)
18.1360(2)
16.3007(2)
106.8660(10)
2664.05(5)
4
â (deg)
V (Å3)
Z
2
F
calcud (g cm-3
)
1.549
5.449
1500
1.590
5.953
2832
1.498
5.457
1468
1.629
6.437
1320
µ (mm-1
F(000)
)
cryst size (mm)
θ range (deg)
index ranges
0.09 × 0.05 × 0.02
3.47-69.49
-16 e h e 14
-14 e k e 13
-25 e l e 24
18 475
5683 [R(int) ) 0.0724]
96.2%
425/0
1.012
0.0626, 1.1655
R1 ) 0.0494
wR2 ) 0.1103
R1 ) 0.0782
wR2 ) 0.1230
0.826 and -0.518
0.08 × 0.06 × 0.04
2.32-71.22
-13 e h e 12
-42 e k e 44
-18 e l e 16
21 931
8681 [R(int) ) 0.0658]
96.9%
741/0
1.021
0.15 × 0.09 × 0.06
3.28-71.23
-19 e h e 19
-14 e k e 14
-21 e l e 20
29 361
6099 [R(int) ) 0.0456]
98.4%
501/3
1.034
0.0904, 14.6994
R1 ) 0.0527
wR2 ) 0.1461
R1 ) 0.0590
wR2 ) 0.1526
3.877 and -0.668
0.5 × 0.45 × 0.45
5.48 to 70.12
-11 e h e 10
0 e k e 22
0 e l e 19
39 332
4945 [R(int) ) 0.047]
97.7%
455/0
1.098
0.0497, 4.8305
R1 ) 0.0356
wR2 ) 0.0930
R1 ) 0.0364
wR2 ) 0.0935
0.894 and -0.841
no. reflns collected
no. unique reflns
completeness to θmax
no. params/ restraints
goodness-of-fit on F2
wt function (a, b)
R1 [I > 2F(I)]
0.0594, 0
R1 ) 0.0504
wR2 ) 0.1150
R1 ) 0.0600
wR2 ) 0.1204
1.112 and -0.354
wR2 [I > 2F(I)]
R1(all data)
wR2(all data)
largest diff peak and hole (e Å3)
+ (aP)2 + bP ] (a and b values are collected in Table 3) with
The Cambridge Crystallographic Data Centre via www.ccdc.ca-
m.ac.uk/data_request/cif.
2
2
σ(Fo ) from counting statistics and P ) (Max(Fo , 0) + 2Fc2)/3.
Atomic scattering factors were taken from the International Tables
for X-ray Crystallography.24 Geometrical calculations were made
with PARST.25 The crystallographic plots were made with PLA-
TON.26
Acknowledgment. This work was supported by the Spanish
MCT (research project BQU2003-00255 and MAT2006-01997
(E.P.-C.) and Principado de Asturias (PR-01-GE-6). A.V. thanks
the Spanish Ministerio de Educacio´n, Cultura y Deporte for a
scholarship.
CCDC-646912 (9a), CCDC-646913 (9b), CCDC-646914 (10b),
and CCDC-646915 (12) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
Supporting Information Available: Computer-generated plots
and atomic coordinates for all the DFT-optimized molecular
structures and 1H, 31P{1H}, and 13C{1H} NMR spectra are available
free of charge via the Internet at http://pubs.acs.org.
(24) International Tables for X-Ray Crystallography; Kynoch Press:
Birmingham, 1974; Vol. IV (Present distrubutor: Kluwer Academic
Publishers, Dordrecht).
(25) Nardelli, M. Comput. Chem. 1983, 7, 95-98.
(26) Spek, A. L. PLATON, a multipurpose crystallographic tool; Utrecht
University: Utrecht, The Netherlands, 2006.
OM700476F