Synthesis of new half-sandwich ruthenium(II) complexes bearing alkenyl- and alkynylphosphane ligands

Article abstract of DOI:10.1002/ejic.200500569

Carbonyl substitution of the complex [RuI(η⁵-C ₉H₇)(CO)₂] with the activated phosphanes Ph₂PR (R = CH₂CH=CH₂, CH₂CH ₂CH=CH₂, and C≡CPh) affords the complexes [RuI(η⁵-C₉H₇)(CO)(Ph₂PR- κP)] [R = CH₂CH=CH₂ (1a), CH₂CH ₂CH=CH₂ (1b), C≡CPh (1c)]. The reaction of the complex [RuCl(η⁵-C₉H₇)(PPh ₃)₂] with the corresponding phosphanes, in refluxing THF, gives the complexes [RuCl(η⁵-C₉H₇)(PPh ₃)(Ph₂PR-κP)] [R = CH₂CH ₂CH=CH₂ (2b), C≡CPh (2c)] by substitution of PPh₃. The cationic derivatives [Ru(η⁵-C ₉H₇)(L)(Ph₂PR-κ³P,C,C)][X] [L = CO, X = SbF₆, R = CH₂CH=CH₂ (3a), CH ₂CH₂CH=CH₂ (3b); L = PPh₃, X = PF₆, R = CH₂CH₂CH=CH₂ (4b)] have been prepared by treatment of the complexes 1a,b and 2b with a halide abstractor such as AgSbF₆ or NaPF₆, respectively. Deprotonation reactions of the complexes 3b and 4b with cesium carbonate have been carried out, giving rise to the neutral complexes [Ru(η⁵-C ₉H₇)-(L)(Ph₂PCH₂CH=CHCH ₂-κ²P,C)] [L = CO (5a), PPh₃ (5b)]. The reaction of complex 3a with MeCN generates the complex [Ru(η⁵- C₉H₇)(MeCN)(CO)(Ph₂PCH₂CH=CH ₂-κP)][SbF₆] (6). The vinylidene [Ru(η⁵-C₉H₇)(PPh₃)(Ph ₂PC≡CPh-κP)-{C=C(Ph)H}][PF₆] (7) and allenylidene [Ru(η⁵-C₉H₇)(PPh ₃)-(Ph₂PC=CPh-κP)(C=C=CPh₂)][PF ₆] (8) derivatives have been synthesized by reaction of complex 2c with phenylacetylene or 1,1-diphenylprop-2-yn-1-ol, respectively. The structures of the derivatives 1c, 3a, and 4b have been determined by single-crystal X-ray diffraction analysis. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Full text of DOI:10.1002/ejic.200500569

FULL PAPER
DOI: 10.1002/ejic.200500569
Synthesis of New Half-Sandwich Ruthenium(II) Complexes Bearing Alkenyl-
and Alkynylphosphane Ligands
Josefina Díez,[a] M. Pilar Gamasa,*[a] José Gimeno,[a] Elena Lastra,*[a] and Amparo Villar[a]
Keywords: Indenyl complexes / Phosphane ligands / Ruthenium / Sandwich complexes
Carbonyl substitution of the complex [RuI(η5-C9H7)(CO)2]
with the activated phosphanes Ph2PR (R = CH2CH=CH2,
CH2CH2CH=CH2, and CϵCPh) affords the complexes
the complexes 3b and 4b with cesium carbonate have been
carried out, giving rise to the neutral complexes [Ru(η5-C9H7)-
(L)(Ph2PCH2CH=CHCH2-κ2P,C)] [L = CO (5a), PPh3 (5b)].
The reaction of complex 3a with MeCN generates the com-
plex [Ru(η5-C9H7)(MeCN)(CO)(Ph2PCH2CH=CH2-κP)][SbF6]
(6). The vinylidene [Ru(η5-C9H7)(PPh3)(Ph2PCϵCPh-κP)-
{C=C(Ph)H}][PF6] (7) and allenylidene [Ru(η5-C9H7)(PPh3)-
(Ph2PCϵCPh-κP)(C=C=CPh2)][PF6] (8) derivatives have been
synthesized by reaction of complex 2c with phenylacetylene
or 1,1-diphenylprop-2-yn-1-ol, respectively. The structures of
the derivatives 1c, 3a, and 4b have been determined by
single-crystal X-ray diffraction analysis.
[RuI(η5-C9H7)(CO)(Ph2PR-κP)] [R
=
CH2CH=CH2 (1a),
CH2CH2CH=CH2 (1b), CϵCPh (1c)]. The reaction of the
complex [RuCl(η5-C9H7)(PPh3)2] with the corresponding
phosphanes, in refluxing THF, gives the complexes [RuCl(η5-
C9H7)(PPh3)(Ph2PR-κP)] [R = CH2CH2CH=CH2 (2b), CϵCPh
(2c)] by substitution of PPh3. The cationic derivatives [Ru(η5-
C9H7)(L)(Ph2PR-κ3P,C,C)][X] [L
= CO, X = SbF6, R =
CH2CH=CH2 (3a), CH2CH2CH=CH2 (3b); L = PPh3, X = PF6,
R = CH2CH2CH=CH2 (4b)] have been prepared by treatment
of the complexes 1a,b and 2b with a halide abstractor such
as AgSbF6 or NaPF6, respectively. Deprotonation reactions of
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
Introduction
[PF6], which give rise to interesting coupling products.[6] On
the other hand, examples of complexes of ruthenium()
with alkynylphosphanes[7] are also scarce, even though alky-
nylphosphanes have been extensively used in the synthesis
of polynuclear complexes[2f,8] and have been reported to
participate in interesting rearrangement processes, some of
them involving phosphorus–carbon bond cleavage[9] or car-
bon–carbon bond formation.[10]
We have previously reported the synthesis and charac-
terization of the ruthenium() complexes [Ru(η5-
C9H7)(PPh3)(Ph2PCH2C(R)=CH2-κ3P,C,C)][PF6] (R = H,
Me), which feature a κ3P,C,C coordination mode of the
allyldiphenylphosphane as well as a diastereofacial coordi-
nation of the olefin at the ruthenium center.[11] Moreover,
these complexes have been demonstrated to be useful for
further transformations, particularly as substrates in stereo-
selective nucleophilic addition[11] and intramolecular cyclo-
addition reactions,[12,13] which lead to interesting ruthena-
phosphacyclopentane and ruthenaphosphabicycloheptene
complexes, respectively. The progress of the latter reaction
confirms the hemilabile character of the allyldiphenylphos-
phane ligand, a fact that has been corroborated by kinetic
studies.[14] Continuing with these studies, we report here the
synthesis of new half-sandwich indenyl complexes of ruthe-
nium() containing alkenyl and alkynylphosphanes as well
as some preliminary results on their reactivity.
Functionalized phosphanes bearing a multiple carbon–
carbon bond display a versatile behavior as ligands in coor-
dination chemistry and have been reasonably well explored
to date. Thus, alkenylphosphanes,[1] R2P(CH2)nCH=CH2 (n
= 0–2), and alkynylphosphanes,[2] R2PCϵCRЈ, have been
used in coordination chemistry with a wide range of transi-
tion metals. Moreover, a number of ruthenium() com-
plexes bearing different alkenylphosphanes, such as dicyclo-
hexylvinylphosphane (DCVP),[3] vinyldiphenylphosphane
(DPVP),[4] and allyldiphenylphosphane (ADPP)[5] have also
been described and their ligand hemilabile properties have
been repeatedly shown. However, the coordination proper-
ties and the hemilabile character of homoallylphosphanes
have been much less exploited in the area of ruthenium
chemistry. Recently, Kirchner and co-workers have studied
the reactions of olefins and acetylenes with the complex
[Ru(η5-C5H5)(MeCN)(Ph2PCH2CH2CH=CH2-κ3P,C,C)]-
[a] Departamento de Química Orgánica e Inorgánica, Instituto de
Química Organometálica “Enrique Moles” (Unidad Asociada
al C.S.I.C.), Universidad de Oviedo,
Oviedo, Spain
Fax: +34-985-103-446
E-mail: pgb@uniovi.es
elb@uniovi.es
78
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 78–87

Half-Sandwich Ruthenium() Complexes
FULL PAPER
Results and Discussion
Complexes with Alkenyl and Alkynylphosphanes (Ph2PR)
Acting as κP Monodentate Ligands
Synthesis of [RuI(η5-C9H7)(CO)(Ph2PR-κP)] [R =
CH2CH=CH2 (1a), CH2CH2CH=CH2 (1b), CϵCPh
(1c)]
The addition of the corresponding phosphane to a
dichloromethane solution of the complex [RuI(η5-
C9H7)(CO)(NMe3)] (prepared in situ by reaction of the
complex [RuI(η5-C9H7)(CO)2] with freshly sublimed tri-
methylamine oxide) generates the complexes [RuI(η5-
C9H7)(Ph2PR-κP)(PPh3)] [R
=
CH2CH=CH2 (1a),
CH2CH2CH=CH2 (1b), CϵCPh (1c)], which were isolated
as air-stable red solids (78–97% yield) (Scheme 1).
Figure 1. Molecular structure and atom-labelling scheme for com-
plex 1c. Non-hydrogen atoms are represented by their 10% prob-
ability ellipsoids. Hydrogen atoms and phenyl rings have been omit-
ted for clarity. Selected bond lengths [Å]: Ru(1)–I(1) = 2.7224(4),
Ru(1)–P(1) = 2.3087(9), Ru(1)–C(10) = 1.840(4), Ru(1)–C* =
1.9170, C(10)–O(1) = 1.132(5), P(1)–C(11) = 1.755(4), C(11)–C(12)
= 1.210(6). Selected bond angles [°]: P(1)–Ru(1)–I(1) = 90.17(3),
P(1)–Ru(1)–C(10) = 87.53(12), I(1)–Ru(1)–C(10) = 92.42(13), C*–
Ru(1)–I(1) = 121.81, C*–Ru(1)–P(1) = 129.53, C*–Ru(1)–C(10) =
Scheme 1.
Complexes 1a–c are soluble in CH2Cl2, THF, and diethyl
ether and slightly soluble in hexane. Analytical and spectro-
scopic data (IR and 1H, 13C{1H}, and 31P{1H} NMR spec-
troscopy) support the proposed formulation (see Experi-
mental Section for details). In particular, the IR spectra
show the strong characteristic ν(CO) absorption at 1940 (1a
and 1c) and 1930 cm–1 (1b) as well as the ν(CϵC) absorp-
tion at 2176 cm–1 (1c), a singlet resonance is observed at δ
= 45.0 (1a), 44.0 (1b) and 22.5 ppm (1c) for the phosphanes
in the 31P{1H} NMR spectra, and a low-field doublet signal
is observed in the 13C{1H} NMR spectra due to the car-
bonyl group at δ = 203.0 (1a), 203.5 (1b) and 202.4 ppm
(1c) [2JC,P Ϸ 20.7–21.3 Hz]. The 13C{1H} NMR spectrum
of 1c also shows two doublet signals for the alkynyl carbon
124.44, P(1)–C(11)–C(12)
= 172.0(4), C(11)–C(12)–C(18) =
176.9(4). C* represents the centroid of atoms C(1), C(2), C(3), C(4),
and C(5).
and [Ru(η5-1,2,3-Me3C9H4)(CO)(PPh3)(C=C=CPh2)][BF4]
[1.83(1) and 1.15(1) Å].[17]
The alkynyl carbon–carbon bond length C(11)–C(12)
[1.210(6) Å] is in the typical range for a carbon–carbon tri-
ple bond (1.205 Å in the free acetylene) and slightly longer
than in other alkynylphosphaneruthenium complexes[7a]
such as [RuCl2(η6-p-cymene)(Ph2PCϵCC6H4-4-CH3-κP)]
[1.198(3) Å] or [RuCl(η6-p-cymene)(Ph2PCϵCtBu-κP)]-
[OTf] [1.196(6) Å]. The alkynyl fragment of the phosphane
displays a nearly linear geometry [C(11)–C(12)–C(18) =
176.9(4)°].
nuclei at δ = 84.1 (JC,P = 93.6 Hz) and 108.9 ppm (2JC,P
14.4 Hz).
=
Slow diffusion of hexane into a solution of 1c in diethyl
ether allowed the isolation of crystals suitable for X-ray dif-
fraction studies. An ORTEP-type representation of the
molecule is shown in Figure 1. Selected bonding data are
collected in the caption.
Both enantiomers are present in equal numbers in the
crystal, as the crystal belongs to the centric space group P1.
The (R) enantiomer is shown in Figure 1.
¯
Synthesis of [RuCl(η5-C9H7)(Ph2PR-κP)(PPh3)] [R =
CH2CH2CH=CH2 (2b), CϵCPh (2c)]
The molecule exhibits a pseudooctahedral three-legged
piano-stool geometry. The η5-indenyl ligand displays the
The reaction of the complex [RuCl(η5-C9H7)(PPh3)2]
usual allylene coordination mode with the benzo ring ori- with the corresponding phosphane in refluxing THF results
ented trans to the carbonyl group, as shown by the dihedral in the formation of the complexes [RuCl(η5-C9H7)(Ph2PR-
angle (1.14°) between the planes C*–C**–Ru and C*–Ru– κP)(PPh3)] [R = CH2CH2CH=CH2 (2b), CϵCPh (2c)],
C(10).[15]
which were isolated as air-stable, red solids in 60% yield
The Ru–C(10) [1.840(4) Å] and C(10)–O(1) [1.132(5) Å] (Scheme 2). Complexes 2b,c are soluble in dichloromethane
bond lengths are comparable to those found in other in- and diethyl ether and insoluble in hexane, and were charac-
denyl carbonyl ruthenium() complexes such as [RuI- terized by analytical and spectroscopic techniques (See Ex-
(η5-C9H7)(CO)(PCy3)] [1.817(13) and 1.142(15) Å][16] perimental Section for details).
Eur. J. Inorg. Chem. 2006, 78–87
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
79

J. Díez, M. P. Gamasa, J. Gimeno, E. Lastra, A. Villar
FULL PAPER
Complexes 3a,b and 4b were isolated as air-stable, yellow
solids that are soluble in dichloromethane and insoluble in
diethyl ether and hexane. They were characterized analyti-
cally and spectroscopically (IR and 1H, 31P{1H}, and
13C{1H} NMR spectroscopy; see Experimental Section for
details).
The 31P{1H} NMR spectra show a singlet resonance for
the complexes 3a (δ = –56.4 ppm) and 3b (δ = 74.6 ppm),
while two doublet signals at δ = 69.3 [Ph2P(CH2)2CH=CH2]
and 47.3 ppm (PPh3; 2JP,P = 29.5 Hz) are found for complex
4b. The phosphorus resonance of the allyldiphenylphos-
phane is clearly shifted upfield in the complex 3a (δ =
74.6 ppm) in comparison with its precursor 1a (δ =
45.0 ppm) wherein the allylphosphane acts as a mono-
dentate ligand. However, the phosphorus resonances of the
homoallyldiphenylphosphane in complexes 3b and 4b are
shifted downfield with respect to those of the corresponding
monodentate phosphanes in the complexes 1b (δ =
44.0 ppm) and 2b (δ = 45.6 ppm). The formation of five-
(3a) and six-membered (3b, 4a) ruthenaphosphacycles may
account for the observed shift differences.[18]
Scheme 2.
The most remarkable features of those complexes are (a)
the ν(CϵC) absorption at 2168 cm–1 in the IR spectrum for
complex 2c, (b) the expected doublets in the 31P{1H} NMR
spectra at δ = 49.0 and 45.6 ppm (2JP,P = 42.9 Hz) for 2b
and δ = 48.1 and 29.1 ppm (2JP,P = 45.0 Hz) for 2c, and (c)
the 13C{1H}NMR spectrum of 2c shows two doublets at δ
= 109.1 (2JC,P = 11.5 Hz) and 87.2 ppm (2JC,P = 80.7 Hz)
for the acetylene carbons. One olefinic carbon appears at δ
= 113.8 ppm in the 13C{1H}NMR spectrum of 2b, while
the other one is overlapped by aromatic carbons.
Although the two olefin faces are diastereotopic when
the alkenylphosphane ligands are bound in a didentate
manner, the coordination to the metal is found to be com-
pletely selective, affording a sole diastereoisomer, as re-
vealed by the analysis of the 31P{1H} NMR spectra of com-
plexes 3a,b and 4b. Such a selectivity has also been reported
previously for the complexes [Ru(η5-C9H7)(PPh3)-
(Ph2PCH2CH=CH2-κ3P,C,C)][PF6][11] and [Ru(η5-C5H5)-
(PPh3)(Ph2PCH2CH=CH2-κ3P,C,C)][PF6].[13] In addition,
the 31P{1H} NMR spectra remain unchanged over a wide
temperature range, thus ruling out a dynamic process be-
tween the two diastereoisomers on the NMR time scale.
Contrary to these results, the analogous derivative
[Ru(η5-C5Me5)(Ph2PCH2CH=CH2-κP)(Ph2PCH2CH=
CH2-κ3P,C,C)][PF6] was found to be fluxional, giving rise
to a rapid equilibrium between the two diastereomeric con-
formations present in solution.[5c]
Complexes with Alkenylphosphanes Ph2P(CH2)nCH=CH2
(n = 1, 2) Acting as κ3P,C,C Chelate Ligands: Synthesis of
the Complexes [Ru(η5-C9H7)(L)(Ph2PR-κ3P,C,C)][X] [L =
CO, X = SbF6, R = CH2CH=CH2 (3a), CH2CH2CH=CH2
(3b); L = PPh3, X = PF6, R = CH2CH2CH=CH2 (4b)]
Due to the interest of the reactions carried out with the
complex [Ru(η5-C9H7)(PPh3)(Ph2PCH2CH=CH2-κ3P,C,C)]-
[PF6],[11–13] our interest focused on the synthesis of novel
complexes with allyl- and homoallylphosphanes coordi-
nated in a κ3P,C,C mode, which can be formed from com-
plexes 1a,b and 2b by halide abstraction and subsequent
olefin coordination to the metal. Thus, the treatment of
complexes 1a,b with AgSbF6 in dichloromethane leads al-
most
quantitatively
to
the
complexes
[Ru(η5-
C9H7)(CO)(Ph2PR-κ3P,C,C)][SbF6] [R
=
CH2CH=CH2
(3a), CH2CH2CH=CH2 (3b)]. Similarly, the reaction of the
complex 2b with NaPF6 in refluxing ethanol affords the
1
The relatively large difference of the H NMR chemical
shifts for the CH2 geminal protons of the olefin in com-
plexes 3a,b and 4 points to a parallel orientation of the
complex
[Ru(η5-C9H7)(PPh3)(Ph2PCH2CH2CH=CH2-
κ3P,C,C)][PF6] (4b) in 67% yield (Scheme 3).
Scheme 3.
80
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 78–87

Half-Sandwich Ruthenium() Complexes
FULL PAPER
olefin with respect to the indenyl ring. Similar data have
been reported in other cyclopentadienyl and indenyl π-ole-
fin complexes.[19]
In order to compare the structure of the derivatives 3a
and 4b with that of the complex [Ru(η5-C9H7)-
(PPh3)(Ph2PCH2CH=CH2-κ3P,C,C)][PF6],[11] and to find
out which of the two olefin faces in the Ph2P(CH2)n-
CH=CH2-κP ligand is most favored for coordination, an
X-ray diffraction study was carried out. Single crystals suit-
able for X-ray diffraction analysis were obtained by slow
diffusion of diethyl ether into a solution of complexes 3a
and 4b in dichloromethane. The crystals belong to the cen-
¯
trosymmetric space groups P1 (3a) and P21/c (4b), thereby
indicating the presence of a racemic mixture.
In both cases, the asymmetric unit consists of two mole-
cules. For complex 4b, the two molecules are conformers
with identical stereochemistry, the relative configuration at
the ruthenium center being RRu and the olefin being coordi-
nated through the re face (RRure). However, in the case of
complex 3a the two molecules in the asymmetric unit are a
pair of diastereoisomers with relative configuration (RRusi)
and (SRure) (Figure 2). For both 3a and 4b the more rel-
evant structural parameters are similar in both mole-
cules,[20] and thus only the data corresponding to one mole-
cule will be discussed.
Figure 3. Molecular structure and atom-labelling scheme for the
cation of complex 3a. Non-hydrogen atoms are represented by their
10% probability ellipsoids. Hydrogen atoms and phenyl rings have
been omitted for clarity.
Figure 4. Molecular structure and atom-labelling scheme for the
cation of complex 4b. Non-hydrogen atoms are represented by their
10% probability ellipsoids. Hydrogen atoms and phenyl rings have
been omitted for clarity.
Both structures exhibit a three-legged piano-stool geom-
etry with the η5-indenyl ligand displaying the usual allylene
coordination mode. The Ru(1)–C(10) and Ru(1)–C(11)
bond lengths reflect the coordination of the olefin to the
metal center[20] [2.276(11) and 2.230(11) (3a) and 2.228(7)
and 2.245(9) (4b)]. The C(10)–C(11) bond length is
1.389(17) Å in 3a and 1.363(11) Å in 4b, similar to that
Figure 2. The two diastereoisomers found in the asymmetric unit
for the cation of complex 3a with configurations RRusi and SRure.
Non-hydrogen atoms are represented by their 20% probability el-
lipsoids. Hydrogen atoms and phenyl rings have been omitted for
clarity.
found
in
the
complex
[Ru(η5-C9H7)(PPh3)(Ph2-
PCH2CH=CH2-κ3P,C,C)][PF6].[11] It is also interesting to
note that the benzo ring of the indenyl ligand is oriented
ORTEP-type representations of the cations of one of the almost trans to the CO group for complex 3a and trans to
molecules for complexes 3a and 4b are shown in Figures 3 the PPh3 ligand for complex 4b, as is shown by the dihedral
and 4, respectively. Selected bonding data are collected in angle between the planes C**–C*–Ru(1) and C*–Ru(1)–
Table 1.
C(25) of 12.45° (3a) and C**–C*–Ru(1) and C*–Ru(1)–P(2)
Eur. J. Inorg. Chem. 2006, 78–87
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
81

J. Díez, M. P. Gamasa, J. Gimeno, E. Lastra, A. Villar
FULL PAPER
Table 1. Selected bond lengths [Å] and bond angles [°] for 3a and –0.7 ppm for 5b) and two signals for the olefinic carbons of
4b.[a]
2
5a (δ = 116.4 and 146.0 ppm; JC,P = 14.4 Hz) and 5b
2
(δ = 115.3 and 147.0 ppm; JC,P = 13.6 Hz). Moreover, the
analogous complexes [Ru(η5-C9H7)(L)(Ph2PCH2CH=CH2-
κ3P,C,C)][X] [L = CO, X = SbF6 (3a); L = PPh3, X =
PF6[11]] do not suffer deprotonation and are recovered un-
altered after treatment with KOtBu or Cs2CO3 under sim-
ilar reaction conditions.
3a
4b
Ru(1)–C(10)
Ru(1)–C(11)
C(10)–C(11)
Ru(1)–C*
Ru(1)–P(1)
Ru(1)–C(25)
C(25)–O(1)
C(25)–Ru(1)–P(1)
C(25)–Ru(1)–C(10) 94.62(2)
C(25)–Ru(1)–C(11) 103.8(5)
P(1)–Ru(1)–C(10)
P(1)–Ru(1)–C(11)
C(25)–Ru(1)–C*
P(1)–Ru(1)–C*
C(10)–Ru(1)–C*
C(11)–Ru(1)–C*
2.276(11)
2.230(11)
1.389(17)
1.9117
2.322(3)
1.860(14)
1.148(15)
90.1(3)
Ru(1)–C(10)
Ru(1)–C(11)
C(10)–C(11)
Ru(1)–C*
Ru(1)–P(1)
Ru(1)–P(2)
2.228(7)
2.245(9)
1.363(11)
1.9298
2.344(2)
2.301(2)
π-Olefin Exchange Reactions: Synthesis of the Complex
[Ru(η5-C9H7)(CO)(MeCN)(Ph2PCH2CH=CH2-κP)]-
[SbF6] (6)
P(1)–Ru(1)–P(2)
102.45(8)
P(2)–Ru(1)–C(10) 88.2(2)
P(2)–Ru(1)–C(11) 96.5(3)
P(1)–Ru(1)–C(10) 107.0(2)
P(1)–Ru(1)–C(11) 71.5(3)
P(2)–Ru(1)–C*
P(1)–Ru(1)–C*
C(10)–Ru(1)–C*
C(11)–Ru(1)–C*
94.0(3)
65.5(3)
124.65
129.62
122.73
125.76
The complex 3a reacts with acetonitrile to generate the
complex [Ru(η5-C9H7)(CO)(MeCN)(Ph2PCH2CH=CH2-
κP)][SbF6] (6), which was isolated as a yellow solid in 91%
yield (Scheme 5).
121.41
119.18
113.8
133.40
[a] C* = centroid of C(1), C(2), C(3), C(4), and C(5).
11.94° (4b).[15] The Ru(1)–C(25) [1.860(14) Å] and C(25)–
O(1) [1.148(15) Å] bond lengths for complex 3a are similar
to those found in complex 1c.
Reactivity of the Complexes [Ru(η5-C9H7)(L)(Ph2PR-
κ3P,C,C)][X]
Scheme 5.
Complex 6 was characterized analytically and spectro-
scopically (see Experimental Section for details). In particu-
lar, its IR spectrum shows a strong ν(CO) absorption at
1977 cm–1, a broad singlet resonance is observed at δ =
2.2 ppm for the methyl group of the acetonitrile ligand in
the 1H NMR spectrum, a singlet signal appears in the
31P{1H} NMR spectrum at δ = 46.9 ppm, which is in the
typical range for monodentate coordination of the phos-
phane and in agreement with the value found for complex
1a (δ = 45.0 ppm), and the 13C{1H} NMR spectrum shows
a singlet signal at δ = 3.7 ppm for the methyl group of the
acetonitrile and a low-field doublet signal at δ = 200.2 ppm
(2JC,P = 18.9 Hz) for the CO ligand.
Deprotonation Reactions: Synthesis of [Ru(η5-C9H7)(L)-
(Ph2PCH2CH=CHCH2-κ2P,C)] [L = CO (5a), PPh3
(5b)]
The complexes [RuCl(η5-C9H7)(L)(Ph2PCH2CH2CH=
CH2-κ3P,C,C)][X] [X = SbF6, L = CO (3b); X = PF6, L =
PPh3 (4b)] undergo deprotonation reactions in the presence
of base. Thus, the treatment of 3b and 4b with KOtBu or
Cs2CO3 in CH2Cl2 gives the neutral allylruthenium com-
plexes [Ru(η5-C9H7)(L)(Ph2PCH2CH=CHCH2-κ2P,C)] [L
= CO (5a), PPh3 (5b)], which were isolated as yellow solids
in 80–86% yield (Scheme 4).
This result agrees with that reported recently for the de-
rivative [Ru(η5-C9H7)(PPh3)(Ph2PCH2CH=CH2-κ3P,C,C)]-
[PF6], which reacts with acetonitrile to generate
a
Ph2CH2CH=CH2-κP complex, thus emphasizing the hemi-
labile character of the allylphosphane.[11,14] However, all
attempts to open the Ph2PCH2CH2CH=CH2-κ3P,C,C che-
late ring of derivatives 3b and 4b by treatment with acetoni-
trile were unsuccessful, probably due to the higher stability
of the six-membered ring.
Scheme 4.
Reaction of [RuCl(η5-C9H7)(PPh3)(Ph2PCϵCPh-κP)]
(2c) with Alkynes: Synthesis of Vinylidene [Ru(η5-C9H7)-
(PPh3)(Ph2PCϵCPh-κP){C=C(Ph)H}][PF6] (7) and
Allenylidene [Ru(η5-C9H7)(PPh3)(Ph2PCϵCPh-κP)-
(C=C=CPh2)][PF6] (8) Derivatives
Their analytical and spectroscopic data support the pro-
posed formulations (see Experimental Section for de-
tails).[21] The most significant spectroscopic features are (a)
the IR spectrum of 5a shows the ν(CO) absorption at
1920 cm–1, (b) the 31P{1H} spectra of 5a and 5b show the
resonance of the chelate-ring phosphorus atom at δ = 101.3
Complex 2c reacts with terminal alkynes to give cumu-
2
(singlet) and 91.8 ppm (doublet, JP,P = 33.7 Hz), respec- lenylidene complexes. Thus, the reaction of 2c with
tively, and (c) the 13C{1H} NMR spectra show a high-field PhCϵCH or Ph2C(OH)CϵCH in the presence of NaPF6
signal for the Ru–CH2 carbon (δ = –4.1 ppm for 5a; δ = in refluxing ethanol leads to the expected vinylidene [Ru(η5-
82
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 78–87

Half-Sandwich Ruthenium() Complexes
FULL PAPER
Scheme 6.
C9H7)(PPh3)(Ph2PCϵCPh-κP){C=C(Ph)H}] (7; 82% yield)
The reactivity of the alkenylphosphane ligand is highly
and allenylidene complexes [Ru(η5-C9H7)(PPh3)(Ph2P- dependent on the size of the chelate ring. Thus, the com-
CϵCPh-κP)(C=C=CPh2)] (8; 76% yield) as orange and plex 3a, which contains the allylphosphane ligand
purple solids, respectively (Scheme 6).
Ph2PCH2CHCH2-κ3P,C,C, undergo ring opening upon re-
Complexes 7 and 8 are soluble in CH2Cl2 and THF and action with two-electron ligands, thus emphasizing the
insoluble in diethyl ether and hexane. Both complexes were hemilabile character of the ligand, while complexes 3b and
characterized analytically and spectroscopically (see Experi- 4b, with the six-membered chelate ring Ph2PCH2CH2-
mental Section for details). In particular, some data should CHCH2-κ3P,C,C, undergo no transformation in acetoni-
be noted: (a) the IR spectra show the ν(CϵC) absorption trile.
at 2171 (7) and 2169 cm–1 (8) and the ν(C=C=C) absorp-
The alkynylphosphane complex 1c is able to activate ter-
tion at 1931 cm–1; (b) the 31P{1H} NMR spectra show two minal alkynes, leading to the formation of vinylidene
doublets at δ = 20.6 and 41.7 ppm (2JP,P = 27.2 Hz) for [Ru(η5-C9H7)(PPh3)(Ph2PCϵCPh-κP){C=C(Ph)H}][PF6]
complex 7 and δ = 26.0 and 48.3 ppm (2JP,P = 28.7 Hz) for (7) and allenylidene [Ru(η5-C9H7)(PPh3)(Ph2PCϵCPh-
complex 8; (c) the 13C{1H} NMR spectra show two signals κP)(C=C=CPh2)][PF6] (8) derivatives.
for the alkynyl carbons at δ = 112.9 and 81.6 (7) and 111.3
and 81.7 ppm (8). A low-field pseudotriplet signal (2JC,P
=
Experimental Section
18.5–16.4 Hz) is observed for the Cα nuclei of the cumulenic
group at δ = 355.4 (7) and 293.2 ppm (8).
General: All manipulations were performed under an atmosphere
of dry nitrogen using vacuum-line and standard Schlenk tech-
niques. All reagents were obtained from commercial suppliers and
used without further purification. Solvents were dried by standard
methods and distilled under nitrogen before use. The compounds
[RuCl(η5-C9H7)(PPh3)2],[23] [RuI(η5-C9H7)(CO)2],[24] Ph2PCH2-
CH=CH2,[25] Ph2PCH2CH2CH=CH2,[26] and Ph2PCϵCPh[27] were
prepared by previously reported methods. Infrared spectra were re-
corded with a Perkin–Elmer 1720-XFT or a Perkin–Elmer 599 IR
spectrometer. The C, H, and N analyses were carried out with a
Perkin–Elmer 240-B microanalyzer. NMR spectra were recorded
with Bruker AC 300 and 300 DPX instruments at 300 (1H), 121.5
(31P), or 75.4 MHz (13C) or a Bruker AC 400 instrument at 400.1
(1H), 161.9 (31P), or 100.6 MHz (13C) with SiMe4 or 85% H3PO4
as standards. DEPT experiments were carried out for all the com-
plexes. The following atom labels have been used for the 1H and
13C{1H} NMR spectroscopic data.
Conclusions
In summary, the present work describes the synthesis of a
series of chiral-at-ruthenium indenyl complexes containing
alkynyl- and alkenylphosphane ligands. In the case of alk-
enylphosphane complexes both κP and κ3P,C,C coordina-
tion modes have been shown to occur. In complexes with
κ3P,C,C-alkenylphosphane coordination, an effective chiral
recognition of a prochiral allyl group has been achieved, the
olefin being coordinated to the metal in a diastereoselective
way.[22]
The X-ray structure analysis of representative derivatives
showing the κ3P,C,C coordination mode has been per-
formed and their structure compared with that of the pre-
viously described allylphosphane complexes [Ru(η5-
C9H7)(PPh3){Ph2PCH2CR=CH2-κ3P,C,C}][PF6] (R = H,
Me).[11] Moreover, these complexes can be used as model
systems to study the diastereoselective coordination found
for the alkenylphosphane ligand in Ph2P(CH2)nCH=CH2-
κ3P,C,C complexes.
Eur. J. Inorg. Chem. 2006, 78–87
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
83

J. Díez, M. P. Gamasa, J. Gimeno, E. Lastra, A. Villar
FULL PAPER
Synthesis of [RuI(η5-C9H7)(CO)(Ph2PR-κP)] [R = CH2CH=CH2 H, 6-H, or 7-H, Ar) ppm. 13C{1H} NMR (75.4 MHz, CDCl3,
(1a), CH2CH2CH=CH2 (1b), CϵCPh (1c)]: Previously sublimed 18 °C): δ = 20.3 (d, JC,P = 22.9 Hz, P–CH2), 28.7 (d, 2JC,P = 8.3 Hz,
2
Me3NO (188 mg, 2.50 mmol) was added to a solution of [RuI(η5-
C9H7)(CO)2] (500 mg, 1.25 mmol) in CH2Cl2 (5 mL), and the mix-
ture was stirred for 10 min at room temperature. After this time,
the initial orange solution turned nearly black, and the complex
[Ru(η5-C9H7)(NMe3)(CO)] had formed (checked by IR spec-
troscopy in solution). The corresponding phosphane ligand was
then added (1.5 mmol) and the reaction mixture stirred for 15–
30 min. The resulting solution was evaporated to dryness and the
residue extracted with toluene (2×20 mL) and vacuum-dried. The
solid residue was then recrystallized from CH2Cl2/hexane and com-
plexes 1a–c were obtained as red solids.
CH2), 61.6 (s, C-1 or C-3), 69.4 (d, JC,P = 11.4 Hz, C-1 or C-3),
90.6 (s, C-2), 109.8, 111.3 (s, C-3a, C-7a), 113.8 (s, =CH2), 123.3–
138.2 (=CH, C-4,5,6,7, Ar) ppm. 31P{1H} NMR (121.5 MHz,
2
2
CDCl3, 18 °C): δ = 45.6 (d, JP,P = 42.9 Hz), 49.0 (d, JP,P
42.9 Hz) ppm. C43H39ClP2Ru (754.24): calcd. C 68.47, H 5.21;
found C 67.05, H 4.30.
=
Synthesis of [RuCl(η5-C9H7)(PPh3)(Ph2PCϵCPh-κP)] (2c): A solu-
tion of [RuCl(η5-C9H7)(PPh3)2] (500 mg, 0.64 mmol) and phenylal-
kynyldiphenylphosphane (161 mg, 0.77 mmol) in THF (55 mL) was
refluxed for 10 min. The solution was then evaporated to dryness
and the solid residue extracted with diethyl ether (2×20 mL). The
solution was concentrated under vacuum and the product precipi-
tated as a red solid upon addition of hexane; it was vacuum-dried.
Yield: 307 mg (60%). IR (KBr): ν(CϵC) = 2168 cm–1. 1H NMR
(300 MHz, C6D6, 18 °C): δ = 3.80, 4.29, 4.87 (s, 4 H, 1,2,3-H and
4-H, 5-H, 6-H, or 7-H), 6.84–7.87 (m, 33 H, 4-H, 5-H, 6-H, or 7-
1a: Time: 15 min. Yield: 596 mg (80%). IR (KBr): ν(CO) =
1
1940 cm–1. H NMR (300 MHz, CDCl3, 18 °C): δ = 3.33 (m, 1 H,
P–CH2), 3.51 (m, 1 H, P–CH2), 3.58 (s, 1 H, 1-H or 3-H), 4.92 (m,
2 H, =CH2), 5.28 (m, 1 H, 2-H), 5.58 (m, 2 H, =CH, 1-H or 3-H),
7.29 (m, 14 H, 4,5,6,7-H, Ar) ppm. 13C{1H} NMR (75.4 MHz,
CDCl3, 18 °C): δ = 38.1 (d, JC,P = 30.3 Hz, P–CH2), 70.4 (s, C-1
H, Ar) ppm. 13C{1H} NMR (75.4 MHz, C6D6, 18 °C): δ = 66.6 (s,
C-1 or C-3), 69.5 (d, JC,P = 9.5 Hz, C-1 or C-3), 87.2 (d, JP,C
80.7 Hz, P–CϵC), 91.8 (s, C-2), 109.1, (d, JC,P = 11.5 Hz, P–CϵC),
110.5 (s, C-3a or C-7a), 111.8 (d, JC,P = 3.8 Hz, C-3a or C-7a),
2
or C-3), 71.3 (d, JC,P = 7.1 Hz, C-1 or C-3), 89.4 (s, C-2), 110.5,
2
=
2
111.9 (s, C-3a, C-7a), 119.3 (d, JC,P = 11.1 Hz, =CH2), 123.0–
2
137.4 (=CH, C-4,5,6,7, Ar), 203.0 (d, JC,P = 21.2 Hz, CO) ppm.
2
31P{1H} NMR (121.5 MHz, CDCl3, 18 °C): δ = 45.0 ppm (s).
C25H22IOPRu (597.39): calcd. C 50.26, H 3.71; found C 51.38, H
3.95.
122.5–134.7 (C-4,5,6,7, Ar) ppm. 31P{1H} NMR (121.5 MHz,
C6D6, 18 °C): δ = 29.1 (d, 2JP,P = 45.0 Hz), 48.1 (d, 2JP,P = 45.0 Hz)
ppm. C47H37ClP2Ru·CH2Cl2 (800.27): calcd. C 65.13, H 4.44;
found C 66.41, H 4.04.
1b: Time: 30 min. Yield: 596 mg (78%). IR (KBr): ν(CO) =
1
1930 cm–1. H NMR (300 MHz, CDCl3, 18 °C): δ = 1.85 (m, 1 H,
Synthesis of [Ru(η5-C9H7)(CO)(Ph2PR-κ3P,C,C)][SbF6] [R
=
CH2), 2.07 (m, 1 H, CH2), 2.52 (m, 1 H, P–CH2), 2.74 (m, 1 H, P–
CH2), 4.57 (s, 1 H, 1-H, 2-H or 3-H), 4.91 (m, 2 H, =CH2), 5.28
(s, 1 H, 1-H, 2-H or 3-H), 5.60 (s, 1 H, 1-H, 2-H or 3-H), 5.69 (m,
1 H, =CH), 6.69 (d, JH,H = 8.26 Hz, 1 H, 4-H, 5-H, 6-H, or 7-H),
6.86 (t, JH,H = 7.4 Hz, 1 H, 4-H, 5-H, 6-H, or 7-H), 7.14–7.63 (m,
12 H, 4-H, 5-H, 6-H, or 7-H, Ar) ppm. 13C{1H} NMR (75.5 MHz,
CDCl3, 18 °C): δ = 28.4 (s, CH2), 32.1 (d, JC,P = 30.5 Hz, P–CH2),
CH2CH=CH2 (3a), CH2CH2CH=CH2 (3b)]: A solution of the
complex [RuCl(η5-C9H7)(Ph2PR-κ1P)(CO)] [R = CH2CH=CH2
(1a), CH2CH2CH=CH2 (1b)] (0.82 mmol) and AgSbF6 (337 mg,
0.98 mmol) in CH2Cl2 (80 mL) was stirred for 1 h at room tempera-
ture in the absence of light. A change of color from red to yellow
was observed. After this time, the suspension was exposed to light
for 1 h, then filtered through kieselguhr and the solvents evapo-
rated to dryness. The solid residue was recrystallized from CH2Cl2/
hexane (1:10), washed with hexane (2×20 mL), and vacuum-dried.
3a: Yield: 562 mg (97%). IR (KBr): ν(CO) = 2012, ν(SbF6) =
658 cm–1. Conductivity (acetone): 123 Ω–1 cm2 mol–1. 1H NMR
(400.1 MHz, CD2Cl2, 18 °C): δ = 2.36 (m, 1 H, =CH2), 2.82 (m, 1
H, P–CH2), 3.47 (m, 1 H, =CH2), 3.92 (m, 1 H, =CH), 4.43 (m, 1
H, P–CH2), 5.47 (pseudo t, JH,H = 2.5 Hz, 1 H, 2-H), 5.85, 6.05 (s,
1 H each, 1-H, 3-H), 6.78 (d, JH,H = 8.6 Hz, 1 H, 4-H, 5-H, 6-H,
or 7-H), 7.16–7.71 (m, 13 H, 4-H, 5-H, 6-H, or 7-H, Ar) ppm.
2
70.6 (s, C-1 or C-3), 72.0 (d, JC,P = 7.4 Hz, C-1 or C-3), 89.7 (s,
C-2), 111.0, 112.3 (s, C-3a, C-7a), 114.8 (s, =CH2), 123.2–137.5
(=CH, C-4,5,6,7, Ar), 203.5 (d, 2JC,P = 21.3 Hz, CO) ppm. 31P{1H}
NMR (121.5 MHz, CDCl3, 18 °C): δ = 44.0 ppm (s). C26H24IOPRu
(611.42): calcd. C 51.08, H 3.96; found C 52.47, H 4.44.
1c: Time 30 min. Yield: 797 mg (97%). IR (KBr): ν(CϵC) = 2176,
1
ν(CO) = 1940 cm–1. H NMR (300 MHz, CDCl3, 18 °C): δ = 4.82
(br. s, 1 H, 1-H or 3-H), 5.57 (pseudo t, JH,H = 2.6 Hz, 1 H, 2-H),
5.79 (br. s, 1 H, 1-H or 3-H), 6.95–7.73 (m, 19 H, 4,5,6,7-H, Ar)
ppm. 13C{1H} NMR (75.4 MHz, CDCl3, 18 °C): δ = 71.0 (s, C-1
13C{1H} NMR (100.6 MHz, CD2Cl2, 18 °C): δ = 34.0 (d, JC,P
38.2 Hz, P–CH2), 55.1 (d, JC,P = 20.1 Hz, =CH), 57.0 (d, JC,P
6.0 Hz, =CH2), 73.8, 76.3 (s, C-1, C-3), 93.9 (s, C-2), 106.9, 108.9
=
=
2
or C-3), 73.7 (d, JC,P = 9.9 Hz, C-1 or C-3), 84.1 (d, JC,P
=
93.6 Hz, P–CϵC), 90.0 (s, C-2), 108.9 (d, 2JC,P = 14.4 Hz, P–CϵC),
111.0, 111.7 (s, C-3a, C-7a), 121.2–134.1 (C-4,5,6,7, Ar), 202.4 (d,
2JC,P = 20.7 Hz, CO) ppm. 31P{1H} NMR (121.5 MHz, CDCl3,
18 °C): δ = 22.5 ppm (s). C30H22IOPRu (657.44): calcd. C 54.81, H
3.37; found C 53.26, H 2.90.
2
(s, C-3a, C-7a), 122.6–134.7 (C-4,5,6,7, Ar), 202.0 (d, JC,P
=
16.1 Hz, CO) ppm. 31P{1H} NMR (161.9 MHz, CD2Cl2, 18 °C): δ
= –56.4 ppm (s). C25H22F6OPRuSb (706.24): calcd. C 42.52, H,
3.14; found C 42.12, H 3.09.
Synthesis of [RuCl(η5-C9H7)(PPh3)(Ph2PCH2CH2CH=CH2-κP)] 3b: Yield: 561 mg (95%). IR (KBr): ν(CO) = 2001, ν(SbF6) =
(2b): A solution of [RuCl(η5-C9H7)(PPh3)2] (500 mg, 0.64 mmol) 659 cm–1. Conductivity (acetone): 144 Ω–1 cm2 mol–1. 1H NMR
and homoallyldiphenylphosphane (168 mg, 0.70 mmol) in THF
(40 mL) was refluxed for 20 min. It was then concentrated to about
10 mL and CuI (183 mg, 0.96 mmol) was added. After 30 min at
room temperature, the solution was evaporated to dryness and the
residue extracted with diethyl ether (2×20 mL), vacuum-dried, and
recrystallized from diethyl ether/hexane (1:10) to obtain complex
2b as a red solid. Yield: 290 mg (60%). 1H NMR (300 MHz,
(400.1 MHz, CD2Cl2, 18 °C): δ = 1.73 (m, 1 H, CH2), 2.11 (d, JH,H
= 8.6 Hz, 1 H, =CH2), 2.66 (m, 2 H, CH2 and P–CH2), 3.06 (m, 1
H, P–CH2), 3.13 (d, JH,H = 13.0 Hz, 1 H, =CH2), 4.48 (m, 1 H,
=CH), 5.61 (m, 1 H, 2-H), 5.87 (s, 1 H, 1-H or 3-H), 6.27 (s, 1 H,
1-H or 3-H), 6.60 (dd, JH,H = 8.6, JH,H = 1.0 Hz, 1 H, 4-H, 5-H,
6-H, or 7-H), 7.27–7.69 (m, 13 H, 4-H, 5-H, 6-H, or 7-H, Ar) ppm.
13C{1H} NMR (100.6 MHz, CD2Cl2, 18 °C): δ = 28.1 (d, JC,P
=
CDCl3, 18 °C): δ = 0.81 (m, 1 H, CH2), 0.97 (m, 1 H, CH2), 1.50 6.0 Hz, CH2), 38.8 (d, JC,P = 34.2 Hz, P–CH2), 54.9 (s, =CH2),
(m, 1 H, CH2), 2.56 (m, 1 H, CH2), 4.67 (m, 4 H, 1-H, 3-H, =CH2), 74.6, 77.8 (s, C-1, C-3), 85.2 (d, JC,P = 5.0 Hz, =CH), 94.7 (s, C-
4.84 (t, JH,H = 2.0 Hz, 2-H), 5.33 (m, 1 H, =CH), 6.30 (d, JH,H
8.2 Hz, 1 H, 4-H, 5-H, 6-H, or 7-H), 6.81–8.00 (m, 28 H, 4-H, 5-
=
2), 107.5, 110.0 (s, C-3a, C-7a), 121.7–134.7 (C-4,5,6,7, Ar), 200.2
2
(d, JC,P = 18.1 Hz, CO) ppm. 31P{1H} NMR (162.0 MHz,
84
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 78–87

Half-Sandwich Ruthenium() Complexes
CD2Cl2, 18 °C): δ = 74.6 ppm (s). C26H24F6OPRuSb·CH2Cl2 to dryness and the residue extracted with CH2Cl2 (2×20 mL). The
FULL PAPER
(720.26): calcd. C 40.28, H 3.25; found C 40.18, H 2.78.
solvent was then concentrated to about 2 mL and hexane (20 mL)
was added. The yellow solid obtained was washed with hexane
(2×10 mL) and vacuum-dried. Yield: 530 mg (91%). IR (KBr):
ν(CO) = 1977, ν(SbF6) = 658 cm–1. Conductivity (acetone):
123 Ω–1 cm2 mol–1. 1H NMR (300 MHz, CDCl3, 18 °C): δ = 2.23
(br. s, 3 H, CH3), 3.35 (m, 2 H, P–CH2), 5.15 and 5.28 (2×m, 5
H, =CH2 and 1,2,3-H), 5.48 (m, 1 H, =CH), 7.22–7.68 (m, 14 H,
4,5,6,7-H, Ar) ppm. 13C{1H} NMR (75.5 MHz, CDCl3, 18 °C): δ
= 3.7 (s, CH3), 36.6 (d, JC,P = 30.2 Hz, P–CH2), 65.8, 67.1 (s, C-1,
Synthesis of
[Ru(η5-C9H7)(PPh3)(Ph2PCH2CH2CH=CH2-
A
κ3P,C,C)][PF6] (4b): solution of the complex [RuCl(η5-
C9H7)(PPh3)(Ph2PCH2CH2CH=CH2-κP)] (500 mg, 0.66 mmol)
and NaPF6 (222 mg, 1.32 mmol) in EtOH (30 mL) was refluxed for
5 min. After this time, the solution was evaporated to dryness and
the residue extracted with CH2Cl2 (2×20 mL). The solvent was
then concentrated to about 2 mL and diethyl ether (20 mL) was
added. The yellow solid obtained was washed with diethyl ether
(2×10 mL) and vacuum-dried. Yield: 382 mg (67%). IR (KBr):
ν(PF6) = 838 cm–1. Conductivity (acetone): 97 Ω–1 cm2 mol–1. 1H
NMR (300.1 MHz, CD2Cl2, 18 °C): δ = 1.78 (d, JH,H = 8.8 Hz, 1
H, =CH2), 2.24 (m, 2 H, CH2), 2.54 (m, 2 H, CH2), 3.57 (m, 1 H,
=CH2), 5.10 (s, 1 H, 1-H, 2-H or 3-H), 5.30 (m, 1 H, =CH), 5.37
C-3), 93.3 (s, C-2), 109.3, 112.9 (s, C-3a, C-7a), 121.4 (d, JC,P
=
=
2
12.1 Hz, =CH2), 123.5–132.3 (C-4,5,6,7, Ar), 200.2 (d, JC,P
18.9 Hz, CO) ppm. 31P{1H} NMR (121.5 MHz, CDCl3, 18 °C): δ
= 46.9 ppm (s). C27H25F6OPNRuSb (747.29): calcd. C 43.40, H
3.37, N 1.87; found C 42.48, H 3.67, N 1.90.
(s, 1 H, 1-H, 2-H or 3-H), 5.51 (s, 1 H, 1-H, 2-H or 3-H), 6.79– Synthesis of [Ru(η5-C9H7)(PPh3)(Ph2PCϵCPh-κP){=C=C(Ph)H}]-
7.69 (m, 29 H, 4,5,6,7-H, Ar) ppm. 13C{1H} NMR (75.4 MHz,
[PF6] (7): A solution of [RuCl(η5-C9H7)(PPh3)(Ph2PCϵCPh-κP)]
2
CD2Cl2, 18 °C): δ = 24.4 (d, JC,P = 6.7 Hz, P–CH2), 40.0 (d, JC,P (50 mg, 0.07 mmol), NaPF6 (23 mg, 0.14 mmol), and phenylacety-
2
= 33.5 Hz, CH2), 79.3 (s, C-1 or C-3), 82.1 (d, JC,P = 12.0 Hz, C-
lene (36 mg, 0.35 mmol) in EtOH (8 mL) was refluxed for 15 min.
1 or C-3), 87.6 (s, C-2), 97.5, 103.6 (s, C-3a, C-7a), 107.4 (d, JC,P After this time the solution was evaporated to dryness and the resi-
= 3.4 Hz, =CH2), 122.5–133.6 (=CH, C-4,5,6,7, Ar) ppm. 31P{1H}
due was extracted with CH2Cl2 (2×10 mL). The solvent was then
concentrated to about 2 mL and hexane (20 mL) was added. The
orange solid obtained was washed with hexane (2×10 mL) and
vacuum-dried. Yield: 58 mg (82%). IR (KBr): ν(CϵC) = 2171,
ν(PF6) = 838 cm–1. Conductivity (acetone): 96 Ω–1 cm2 mol–1. 1H
NMR (300 MHz, CD2Cl2, 18 °C): δ = 5.30, 5.54, 5.74 (s, 1 H each,
1,2,3-H), 5.94 (d, JH,H = 8.3 Hz, 1 H, 4-H, 5-H, 6-H, or 7-H), 6.21
(s, 1 H, =CH), 6.37 (d, JH,H = 8.3 Hz, 1 H, 4-H, 5-H, 6-H, or 7-
H), 6.78–7.58 (m, 37 H, 4-H, 5-H, 6-H, or 7-H, Ar) ppm. 13C{1H}
2
NMR (121.5 MHz, CD2Cl2, 18 °C): δ = 47.3 (d, JP,P = 29.5 Hz),
2
69.3 (d, JP,P = 29.5 Hz) ppm. MS (FAB+): m/z = 719 [M+].
Synthesis of [Ru(η5-C9H7)(L)(Ph2PCH2CH=CHCH2-κ2P,C)] [L =
CO (5a), PPh3 (5b)]:
A
solution of [Ru(η5-C9H7)(L)-
(Ph2PCH2CH2CH=CH2-κ3P,C,C)][X] [X = SbF6, L = CO (3b); X
= PF6, L = PPh3 (4b)] (0.14 mmol) and Cs2CO3 (228 mg, 0.7 mmol)
in CH2Cl2 (20 mL) was stirred for 1 h at room temperature. After
this time the solution was filtered through kieselguhr and the sol-
vents evaporated to dryness. The solid residue was extracted with
20 mL of diethyl ether and precipitated with hexane. The yellow
solid obtained was washed with hexane (2×10 mL) and vacuum-
dried.
NMR (75.5 MHz, (CD3)2CO, 18 °C): δ = 81.6 (d, JC,P = 95.0 Hz,
2
P–CϵC), 82.5 (s, C-1 and C-3), 100.6 (s, C-2), 112.9 (d, JC,P
=
12.3 Hz, P–CϵC), 115.1 (s, C-3a or C-7a), 117.2 (s, Cβ), 120.9 (d,
JC,P = 2.6 Hz, C-3a or C-7a), 123.9–135.2 (Ar), 355.4 (pseudo t,
2JC,P = 16.4, Cα) ppm. 31P{1H} NMR (121.5 MHz, CD2Cl2,
1
5a: Yield: 46 mg (86%). IR (KBr): ν(CO) = 1920 cm–1. H NMR
2
18 °C): δ = 20.6 (d, JP,P = 27.2 Hz), 41.7 (d, 2JP,P = 27.2 Hz) ppm.
(400.1 MHz, C6D6, 18 °C): δ = 2.19 (m, 1 H, Ru–CH2) 2.35 (m, 1
H, Ru–CH2), 2.69 (m, 2 H, P–CH2), 4.82 (s, 1 H, 1-H or 3-H), 5.04 Synthesis of [Ru(η5-C9H7)(PPh3)(Ph2PCϵCPh-κP)(=C=C=CPh2)]-
(s, 1 H, 2-H), 5.34 (s, 1 H, 1-H or 3-H), 5.51 (m, 1 H, =CH), 6.46
[PF6] (8):
A
solution of [RuCl(η5-C9H7)(PPh3)(Ph2PCϵ
(d, JH,H = 8.1 Hz, 1 H, 4-H, 5-H, 6-H, or 7-H), 6.78 (m, 1 H, CPh-κP)] (50 mg, 0.07 mmol), NaPF6 (23 mg, 0.14 mmol), and 1,1-
=CH), 6.97–7.27 (m, 13 H, 4-H, 5-H, 6-H, or 7-H, Ar) ppm. diphenylprop-2-yn-1-ol (72 mg, 0.35 mmol) in EtOH (8 mL) was
13C{1H} NMR (100.6 MHz, C6D6, 18 °C): δ = –4.1 (d, JC,P
8.8 Hz, Ru–CH2), 26.8 (d, JC,P = 22.4 Hz, CH2), 72.0 (d, JC,P
=
=
refluxed for 20 min. After this time the solution was evaporated to
dryness and the residue was extracted with CH2Cl2 (2×10 mL).
2
7.2 Hz, C-1 or C-3), 74.3 (s, C-1 or C-3), 98.3 (s, C-2), 108.1 (s, C- The solution was concentrated under vacuum and the product pre-
3a, C-7a), 116.4 (s, =CH), 122.5–141.6 (C-4,5,6,7, Ar), 146.0 (d,
cipitated and washed with hexane (2×10 mL). The violet solid ob-
tained was vacuum-dried. Yield: 59 mg (76%). IR (KBr): ν(CϵC)
= 2169, ν(C=C=C) = 1931, ν(PF6) = 837 cm–1. Conductivity (ace-
2
JC,P = 14.4 Hz, =CH), 205.4 (d, JC,P = 16.8 Hz, CO) ppm.
31P{1H}(162.0 MHz, C6D6, 18 °C): δ = 101.3 ppm (s). MS (FAB+):
m/z = 485 [M+ + 1].
1
tone): 133 Ω–1 cm2 mol–1. H NMR (300 MHz, CDCl3, 18 °C): δ =
5b: Yield: 80 mg (80%). 1H NMR (400.1 MHz, CD2Cl2, –50 °C): δ 5.24, 5.66, 5.72 (s, 3 H, 1,2,3-H), 6.22 (d, JH,H = 8.0 Hz, 1 H, 4-H,
= 0.79 (m, 1 H, Ru–CH2), 1.62 (m, 1 H, P–CH2), 2.43 (m, 1 H,
Ru–CH2), 3.30 (m, 1 H, P–CH2), 3.99 (s, 1 H, 1-H or 3-H), 4.19
(s, 1 H, 1-H or 3-H), 5.15 (s, 1 H, 2-H), 5.51 (m, 1 H, =CH), 6.67
5-H, 6-H, or 7-H), 6.88–7.84 (m, 43 H, 4-H, 5-H, 6-H, or 7-H, Ar)
ppm. 13C{1H} NMR (75.5 MHz, CD2Cl2, 18 °C): δ = 80.8 (d, JC,P
3
= 5.8 Hz, C-1 or C-3), 81.7 (dd, JC,P = 92.5, JC,P = 3.5 Hz, P–
(m, 1 H, =CH), 6.92–7.66 (m, 29 H, 4,5,6,7-H, Ar) ppm. 13C{1H} CϵC), 82.6 (d, JC,P = 7.0 Hz, C-1 or C-3), 98.4 (s, C-2), 111.3 (d,
2
NMR (100.6 MHz, CD2Cl2, –50 °C): δ = –0.7 (br. s, Ru–CH2), 25.8
2JC,P = 10.4 Hz, P–CϵC), 113.5 (s, C-3a or C-7a), 119.5 (d, JC,P
2
(d, JC,P = 20.4 Hz, P–CH2), 71.1 (s, C-1 or C-3), 74.0 (d, JC,P
=
= 2.3 Hz, C-3a or C-7a), 122.6–142.8 (Ar), 158.5 (s, Cγ), 204.9 (s,
2
2
5.4 Hz, C-1 or C-3), 93.5 (pseudo t, JC,P = 4.7 Hz, C-2), 103.8,
109.7 (s, C-3a, C-7a), 115.3 (s, =CH), 121.0–144.9 (C-4,5,6,7, Ar),
147.0 (d, JC,P = 13.6 Hz, =CH) ppm. 31P{1H} NMR (162.0 MHz,
Cβ), 293.2 (pseudo t, JC,P = 18.5 Hz, Cα) ppm. 31P{1H} NMR
2
(121.5 MHz, CDCl3, 18 °C): δ = 26.0 (d, JP,P = 28.7 Hz), 48.3 (d,
2JP,P = 28.7 Hz) ppm.
2
2
CD2Cl2, 18 °C): δ = 56.2 (d, JP,P = 33.7 Hz), 91.8 (d, JP,P
=
X-ray Crystal Structure Determination of Complexes 1c, 3a, and 4b:
Crystals suitable for X-ray diffraction analysis were obtained by
slow diffusion of hexane (1c) or pentane (3a and 4b) into a satu-
33.7 Hz) ppm. MS (FAB+): m/z = 719 [M+ + 1].
Synthesis of [Ru(η5-C9H7)(MeCN)(CO)(Ph2PCH2CH=CH2-κP)]-
[SbF6] (6): A solution of [Ru(η5-C9H7)(CO)(PPh2CH2CH=CH2- rated solution of the complexes in dichloromethane. The most rel-
κ3P,C,C)][SbF6] (500 mg, 0.7 mmol) in MeCN (100 mL) was stirred
evant crystal and refinement data are collected in Table 2. Diffrac-
at room temperature for 2.5 h. The solution was then evaporated
tion data for 1c were recorded with a Bruker Smart 6k CCD area-
Eur. J. Inorg. Chem. 2006, 78–87
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
85

J. Díez, M. P. Gamasa, J. Gimeno, E. Lastra, A. Villar
FULL PAPER
Table 2. Crystal data and structure refinement for 1c, 3a, and 4b.
1c
3a
4b
Chemical formula
Mol. mass
T [K]
Wavelength [Å]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C30H22IOPRu
657.42
296(2)
C25H22F6OPRuSb
706.22
293(2)
C43H39F6P3Ru
863.72
293(2)
0.71073
monoclinic
P21/c
10.8581(13)
36.732(4)
19.627(2)
90
105.209(2)
90
7553.9(14)
8
1.519
1.54184
triclinic
1.54184
triclinic
¯
¯
P1
P1
8.71010(10)
17.1308(3)
17.7376(3)
81.6670(10)
77.1680(10)
83.3500(10)
2543.69(7)
4
12.1110(9)
13.2257(8)
16.0508(10)
80.581(4)
86.865(4)
89.774(4)
2532.5(3)
4
γ [°]
V [Å3]
Z
ρcalcd. [gcm–3]
µ [mm–1]
F(000)
1.717
15.268
1288
1.852
14.442
1376
0.603
3520
Crystal size [mm]
θ range [°]
Index ranges
0.25×0.15×0.12
2.57 to 70.62
–13 Յ h Յ 12
0 Յ kϽ Յ 45
0 Յ l Յ 24
16413
8462 [R(int) = 0.0295]
86.6%
613/0
0.125×0.05×0.025
2.79 to 70.06
–14 Յ h Յ 14
–15 Յ k Յ 16
0 Յ l Յ 19
50571
9308 [R(int) = 0.066]
96.7%
616/0
0.25×0.21×0.19
1.54 to 26.12
–13 Յ h Յ 12
0 Յ k Յ 45
0 Յ l Յ 24
37632
14418 [R(int) = 0.10]
95.8%
955/0
No. of reflns. collected
No. of unique reflns.
Completeness to θmax
No. of parameters/restraints
Goodness-of-fit on F2
Weight function (a, b)
0.984
0.959
0.0546,13.5440
0.0619
0.998
0.0694, 0.1691
0.0916
[a]
R1 [I Ͼ 2ρ(I)]
0.0312
0.0772
[a]
wR2 [I Ͼ 2ρ(I)]
0.1544
0.1061
R1 (all data)
0.0360
0.0800
1.218 and-0.565
0.1074
0.1977
2.668 and –1.042
0.2105
0.1283
0.6166 and –1.115
wR2 (all data)
Largest diff peak and hole [eÅ–3]
[a] R1 = Σ(|Fo| – |Fc|)/Σ|Fo|; wR2 = {Σ[w(Fo – Fc ) ]/Σ[w(Fo2)2]}½.
2
2 2
–
detector three-circle diffractometer (Cu-Kα radiation,
λ
=
heavy atoms (Ru, I) for 1c and near to the disordered PF6 ions
for 3a.
1.5418 Å). 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 package[28] and corrected for absorp-
tion with SADABS.[29] For 3a diffraction data were recorded with
a Nonius Kappa CCD single crystal diffractometer using Cu-Kα
radiation (λ = 1.5418 Å) − the crystal-to-detector distance was
fixed at 29 mm − and using the oscillation method, with 2° oscilla-
tion and 40 s exposure time per frame. The data collection strategy
was calculated with the program Collect.[30] Data reduction and
cell refinement were performed using the programs HKL Denzo
and Scalepack[31] and absorption correction was applied by means
of SORTAV.[32] Data for 4b were collected on a Bruker Smart CCD
diffractometer using graphite-monochromated Mo-Kα radiation (λ
= 0.71073 Å). 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 package[28] and corrected for ab-
sorption with SADABS.[29]
The function minimized was [Σw(Fo – Fc )/Σw(Fo2)]1/2 where w =
1/[σ2(Fo2) + (aP)2 + bP] (a = 0.0512 and b = 0 for 1c, a = 0.0899
and b = 0 for 3a, a = 0.0228 and b = 0 for 4b) with σ(Fo2) from
2
2
counting statistics and P = [Max(Fo2,0) + 2Fc ]/3. Atomic scat-
2
tering factors were taken from the International Tables for X-ray
Crystallography.[36] Geometrical calculations were made with
PARST.[37] The crystallographic plots were made with PLATON.[38]
CCDC-276224 (1c), -276225 (3a), and -276226 (4b) contain the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgments
This work was supported by the Spanish M.C.T. (BQU2003-00255)
and the Principado de Asturias (PR-01-GE-6). A. V. thanks the
Spanish Ministerio de Educación, Cultura y Deporte for a scholar-
ship.
The software package WINGX was used for space group determi-
nation, structure solution, and refinement.[33] The structures were
solved by Patterson interpretation and phase expansion using
DIRDIF.[34] Isotropic least-squares refinement on F2 using
SHELXL97 was performed.[35] For all the complexes, during the
final stages all non-hydrogen atoms were refined with anisotropic
displacement parameters and the H atoms were geometrically lo-
cated and their coordinates were refined riding on their parent
atoms. The maximum residual electron density is located near to
[1] For representative examples of complexes with R2PCH=CH2,
see the following: [M] = [Cr] and [Mo] a) P. G. Edwards, J. S.
Fleming, S. S. Liyanage, S. J. Coles, M. B. Hursthouse, J.
Chem. Soc., Dalton Trans. 1996, 1801–1807; [Os]: b) M. Baya,
M. L. Buil, M. A. Esteruelas, E. Oñate, Organometallics 2005,
24, 2030–2038; c) M. A. Esteruelas, A. I. González, A. M.
86
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 78–87

Half-Sandwich Ruthenium() Complexes
FULL PAPER
López, E. Oñate, Organometallics 2004, 23, 4858–4869; [Rh]:
d) L. P. Barthel-Rosa, V. J. Catalano, K. Maitra, J. H. Nelson,
Organometallics 1996, 15, 3924–3934. For representative exam-
ples of complexes with R2PCH2CH=CH2, see the following:
[M] = [Cr] and [Mo], see ref.[1a]; [W]: e) X. Morise, M. L. H.
Green, P. C. McGowan, S. J. Simpson, J. Chem. Soc., Dalton
Trans. 1994, 571–578; [Pd]: f) S. J. Coles, P. Faulds, M. B.
Hursthouse, D. G. Kelly, G. C. Ranger, A. J. Toner, N. M.
Walker, J. Organomet. Chem. 1999, 586, 234–240. For examples
of complexes with R2PCH2CH2CH=CH2, see the following:
[M] = [Ni]: g) K. Issleib, M. Haftendorn, Z. Anorg. Allg. Chem.
1967, 351, 9–17; [Rh] and [Ir]: h) D. V. Krupenya, S. I. Seliv-
anov, S. P. Tunik, M. Haukka, T. A. Pakkanen, Dalton Trans.
2004, 2541–2549; i) P. W. Clark, G. E. Hartwell, J. Organomet.
Chem. 1975, 102, 387–396.
[12]
[13]
[14]
[15]
P. Álvarez, E. Lastra, J. Gimeno, M. Bassetti, L. R. Falvello,
J. Am. Chem. Soc. 2003, 125, 2386–2387.
J. Díez, M. P. Gamasa, J. Gimeno, E. Lastra, A. Villar, Organo-
metallics 2005, 24, 1410–1418.
M. Bassetti, P. Álvarez, J. Gimeno, E. Lastra, Organometallics
2004, 23, 5127–5134.
C* represents the centroid of atoms C(1), C2), C(3), C(4), and
C(5); C** represents the centroid of atoms C(4), C(5), C(6),
C(7), C(8), and C(9).
S. García-Granda, M. Pérez-Priede, J. F. Van der Maelen, per-
sonal communication.
M. P. Gamasa, J. Gimeno, C. González-Bernardo, J. Borge, S.
García-Granda, Organometallics 1997, 16, 2483–2485.
P. Garrou, Chem. Rev. 1981, 81, 229–266.
a) J. Okuda, K. H. Zimmermann, Chem. Ber. 1989, 122, 1645–
1647; b) J. W. Faller, B. V. Johnson, J. Organomet. Chem. 1975,
88, 101–113; c) J. A. Miguel-García, H. Adams, P. M. Maitlis,
J. Organomet. Chem. 1991, 413, 427–444.
Significant distance differences are only found in the cases of
the coordination of the olefin to the ruthenium center, probably
due to steric requirements. 3a: Ru–C(10) 2.276(11) and
2.289(13); Ru–C(11) 2.230(11) and 2.263(11); C(10)–C(11)
1.389(17) and 1.395(16). 4b: Ru–C(10) 2.228(7) and 2.253(8);
Ru–C(11) 2.245(9) and 2.235(8); C(10)–C(11) 1.363(11) and
1.363(10).
Complex 5b is unstable in solution at room temperature and
the NMR spectra were therefore recorded at low temperature
(–50 °C).
J. A. Gladysz, B. I. Boone, Angew. Chem. Int. Ed. Engl. 1997,
36, 550–583.
L. A. Oro, M. A. Ciriano, M. Campo, C. Foces-Foces, F. H.
Cano, J. Organomet. Chem. 1985, 289, 117–131.
M. S. Loonat, L. Carlton, J. C. A. Boeyens, N. J. Coville, J.
Chem. Soc., Dalton Trans. 1989, 2407–2414.
[16]
[17]
[18]
[19]
[2] For representative examples of alkynylphosphane complexes,
see the following: [M] = [Fe]: a) E. Louattani, J. Suades, A.
Álvarez-Larena, J. F. Piniella, G. Germain, J. Organomet.
Chem. 1996, 506, 121–127; [Mo]: b) E. Louattani, J. Suades, J.
Organomet. Chem. 2000, 604, 234–240; [Rh], [Ir], and [Pt]: c)
J. R. Berenguer, M. Bernechea, J. Forniés, A. García, E. Lal-
inde, M. T. Moreno, Inorg. Chem. 2004, 43, 8185–8198; d) J.
Forniés, A. García, B. Gil, E. Lalinde, M. T. Moreno, Dalton
Trans. 2004, 3854–3863; e) J. Forniés, A. García, J. Gómez, E.
Lalinde, M. T. Moreno, Organometallics 2002, 21, 3733–3743;
[Au]: f) M. Bardaji, A. Laguna, P. G. Jones, Organometallics
2001, 20, 3906–3912.
[3] For recent examples of ruthenium complexes with DCVP see:
a) D. Dorota, J. H. Nelson, Dalton Trans. 2005, 92–103; b)
K. Y. Ghebreyessus, J. H. Nelson, Synth. React. Inorg. Met.-
Org. Chem. 2003, 33, 1329–1349.
[4] For recent examples of ruthenium complexes with DPVP see:
a) D. C. Wilson, J. H. Nelson, J. Organomet. Chem. 2003, 682,
272–289; b) H. D. Hansen, J. H. Nelson, Inorg. Chim. Acta
2003, 352, 4–8; c) G. Kesete, J. H. Nelson, Inorg. Chem. Com-
mun. 2003, 6, 1044–1047; d) D. Dorota, J. H. Nelson, Dalton
Trans. 2003, 449–457; e) G. Kesete, J. H. Nelson, Organometal-
lics 2000, 19, 3387–3392; f) H. Heather, J. H. Nelson, Organo-
metallics 2000, 19, 4740–4755.
[20]
[21]
[22]
[23]
[24]
[25]
P. Clark, J. L. S. Curtis, P. E. Garrou, G. E. Hartwell, Can. J.
Chem. 1974, 52¸ 1714–1720.
[26] R. S. Dickson, T. De Simona, E. M. Campi, W. R. Jackson, In-
org. Chim. Acta 1994, 220, 187–192.
[5] For recent examples of ruthenium complexes with ADPP see:
a) D. Cuervo, M. P. Gamasa, J. Gimeno, Chem. Eur. J. 2004,
10, 425–432; b) K. D. Redwine, J. H. Nelson, J. Organomet.
Chem. 2000, 613, 177–199; c) L. P. Barthel-Rosa, K. Maitra, J.
Fischer, J. H. Nelson, Inorg. Chem. 1998, 37, 633–639.
[6] C. Slugovc, K. Mereiter, R. Schmid, K. Kirchner, Organometal-
lics 1999, 18, 1011–1017.
[7] a) J. R. Berenguer, M. Bernechea, J. Forniés, A. García, E. Lal-
inde, Organometallics 2004, 23, 4288–4300; b) J. R. Berenguer,
M. Bernechea, J. Forniés, J. Gómez, E. Lalinde, Organometal-
lics 2002, 21, 2314–2324; c) C. J. Adams, M. I. Bruce, B. W.
Skelton, A. H. White, Inorg. Chem. 1992, 31, 3336–3338; d) G.
Mohamed, B. Demerseman, P. H. Dixneuf, J. Organomet.
Chem. 1992, 424, 65–70.
[8] a) F. Hong, Y. Ho, Y. Chang, Y. Lai, Tetrahedron 2004, 60,
2639–2645; b) T. Baumgartner, K. Huynth, S. Schleidt, A. J.
Lough, I. Manners, Chem. Eur. J. 2002, 8, 4622–4632; c) T.
De Simone, R. S. Dickson, B. W. Skelton, A. W. White, Inorg.
Chim. Acta 1995, 240, 323–333; d) I. Moldes, J. Ros, Inorg.
Chim. Acta 1995, 232, 75–81.
[9] J. E. Davies, M. J. Mays, P. R. Raithby, K. Sarveswaran, G. A.
Solan, J. Chem. Soc., Dalton Trans. 2001, 1269–1277.
[10] I. Ara, J. Forniés, A. García, J. Gómez, E. Lalinde, M. T. Mor-
eno, Chem. Eur. J. 2002, 8, 3698–3716.
[27] E. Louattani, J. Suades, R. Mathieu, J. Organomet. Chem.
1991, 421, 335–340.
[28] SAINT version 6.02 Bruker Analytical X-ray Systems, Madi-
son, WI, 2000.
[29] G. M. Sheldrick, SADABS empirical absorption program, Uni-
versity of Göttingen, 1996.
[30] Collect, Nonius BV, Delft, The Netherlands, 1997–2000.
[31] Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307–
326.
[32] R. H. Blessing, Acta Crystallogr., Sect. A 1995, 51, 33–38.
[33] L. J. Farrugia, J. Appl. Crystallogr. 1999, 32, 837.
[34] P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, S.
García-Granda, R. O. Gould, J. M. M. Smits, C. Smykalla, The
DIRDIF Program System, Technical Report of the Crystallo-
graphic Laboratory, University of Nijmegen, Nijmegen, The
Netherlands, 1999.
[35] G. M. Sheldrick, SHELXL97: Program for the Refinement of
Crystal Structures; University of Göttingen, Göttingen, Ger-
many, 1997.
[36] Tables for X-ray Crystallography, Kynoch Press, Birminghan,
U. K., 1974, vol. IV (present distributor: Kluwer Academic
Publishers, Dordrecht, The Netherlands).
[37] M. Nardelli, Comput. Chem. 1983, 7, 95–98.
[38] A. L. Spek, PLATON: A Multipurpose Crystallographic Tool,
University of Utrecht, The Netherlands, 2005.
Received: June 27, 2005
[11] P. Álvarez, E. Lastra, J. Gimeno, P. Braña, J. A. Sordo, J.
Gómez, L. R. Falvello, M. Bassetti, Organometallics 2004, 23,
2956–2966.
Published Online: November 22, 2005
Eur. J. Inorg. Chem. 2006, 78–87
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
87