Selective synthesis of indenylruthenium(II) vinylvinylidene complexes via unstable allenylidene intermediates:Unexpected formation of alkenyl-phosphonio complexes(E)-[Ru{C(H)=C(PPh3)R}(η5-C9H7) (PPh3)2][PF6](R=1-cyclohexenyl,1-cycloheptenyl)through nucleophilic addition

Article abstract of DOI:10.1021/om970146f

The vinylvinylidene complexes [Ru{=C=C(H)C=CRCH₂(CH₂)nCH₂}(η ⁵-C₉H₇)L₂][PF₆] (L = PPh₃, L₂ = 1,2-bis(diphenylphosphino)ethane (dppe); n = 1 (2a,b), 2 (3a,b), 3 (4a,b)) have been prepared by reaction of [RuCl(η⁵-C₉H₇)L₂] with 1-ethynyl-1-cycloalkanols and NaPF₆ in refluxing methanol. Deprotonation of the vinylidene derivatives with Al₂O₃ yields the neutral enynyl complexes [Ru{C≡CC=CHCH₂(CH₂)_nCH ₂}(η⁵-C₉H₇)L₂] (5a,b, 6a,b, and 7a,b). The reaction of the enynyl complex [Ru(C≡CR)(η⁵-C₉H₇)(PPh ₃)₂] (R = 1-cyclohexenyl; 6a) with MeOSO₂CF₃ produces the disubstituted vinylvinylidene derivative [Ru{=C=C(Me)R}-(η⁵-C₉H₇)(PPh ₃)₂][CF₃SO₃] (R = 1-cyclohexenyl; 8a). The crystal structure of 8a was determined by X-ray diffraction methods. In the structure the Ru=C=C chain is nearly linear (Ru-C(1)-C(2) = 176.2(4)°) with an Ru-C(1) distance of 1.838(5) A?. The indenyl ligand is η⁵-bonded to the metal with the benzo ring orientated trans with respect to the vinylidene group. When the reaction of [RuCl(η⁵-C₉H₇)(PPh₃) ₂] with 1-ethynylcyclohexanol or 1-ethynylcyclopentanol and NaPF₆ takes place in the presence of PPh₃, the alkynyl-phosphonio complexes [Ru{C≡CC(PPh₃)CH₂CH₂(CH ₂)nCH₂}(η⁵-C₉H ₇)(PPh₃)₂][PF₆] (n = 1 (11a), 2 (12a)) were obtained via nucleophilic attack of the PPh₃ on Cγ of the unstable allenylidene complexes [Ru{=C=C=CCH₂CH₂(CH₂)_nCH ₂}(η⁵-C₉H₇)(PPh ₃)₂][PF₆] (n = 1 (9a), 2 (10a)). The vinylvinylidene complexes 3a (n = 2) and 4a (n = 3) also react with PPh₃, giving the alkenyl-phosphonio complexes (E)-[Ru{C(H)=C(PPh₃)C=CHCH₂(CH₂) _nCH₂}(η⁵-C₉H ₇)(PPh₃)₂][PF₆] (n = 2 (13a), 3 (14a)). The structure of 13a was confirmed by X-ray diffraction methods. A possible mechanism for the formation of 13a and 14a is proposed.

Full text of DOI:10.1021/om970146f

3178
Organometallics 1997, 16, 3178-3187
Selective Syn th esis of In d en ylr u th en iu m (II)
Vin ylvin ylid en e Com p lexes via Un sta ble Allen ylid en e
In ter m ed ia tes: Un exp ected F or m a tion of
Alk en yl-P h osp h on io Com p lexes
(E)-[Ru {C(H)dC(P P h 3)R}(η5-C9H7)(P P h 3)2][P F 6] (R )
1-Cycloh exen yl, 1-Cycloh ep ten yl) th r ou gh Nu cleop h ilic
Ad d ition of Tr ip h en ylp h osp h in e on Vin ylvin ylid en e
Der iva tives
Victorio Cadierno,† M. Pilar Gamasa,† J ose´ Gimeno,*,† J avier Borge,‡ and
Santiago Garc´ıa-Granda‡
Departamento de Quı´mica Orga´nica e Inorga´nica and Departamento de Quı´mica Fı´sica y
Analı´tica, Instituto de Quı´mica Organometa´lica “Enrique Moles” (Unidad Asociada al CSIC),
Facultad de Qu´ımica, Universidad de Oviedo, 33071 Oviedo, Spain
Received February 26, 1997X
The vinylvinylidene complexes [Ru{dCdC(H)CdCHCH2(CH2)nCH2}(η5-C9H7)L2][PF6] (L
) PPh3, L2 ) 1,2-bis(diphenylphosphino)ethane (dppe); n ) 1 (2a ,b), 2 (3a ,b), 3 (4a ,b)) have
been prepared by reaction of [RuCl(η5-C9H7)L2] with 1-ethynyl-1-cycloalkanols and NaPF6
in refluxing methanol. Deprotonation of the vinylidene derivatives with Al2O3 yields the
neutral enynyl complexes [Ru{CtCCdCHCH2(CH2)nCH2}(η5-C9H7)L2] (5a ,b, 6a ,b, and 7a ,b).
The reaction of the enynyl complex [Ru(CtCR)(η5-C9H7)(PPh3)2] (R ) 1-cyclohexenyl; 6a )
with MeOSO2CF3 produces the disubstituted vinylvinylidene derivative [Ru{dCdC(Me)R}-
(η5-C9H7)(PPh3)2][CF3SO3] (R ) 1-cyclohexenyl; 8a ). The crystal structure of 8a was
determined by X-ray diffraction methods. In the structure the RudCdC chain is nearly
linear (Ru-C(1)-C(2) ) 176.2(4)°) with an Ru-C(1) distance of 1.838(5) Å. The indenyl
ligand is η5-bonded to the metal with the benzo ring orientated “trans” with respect to the
vinylidene group. When the reaction of [RuCl(η5-C9H7)(PPh3)2] with 1-ethynylcyclohexanol
or 1-ethynylcyclopentanol and NaPF6 takes place in the presence of PPh3, the alkynyl-
phosphonio complexes [Ru{CtCC(PPh3)CH2CH2(CH2)nCH2}(η5-C9H7)(PPh3)2][PF6] (n ) 1
(11a ), 2 (12a )) were obtained via nucleophilic attack of the PPh3 on Cγ of the unstable
allenylidene complexes [Ru{dCdCdCCH2CH2(CH2)nCH2}(η5-C9H7)(PPh3)2][PF6] (n ) 1 (9a ),
2 (10a )). The vinylvinylidene complexes 3a (n ) 2) and 4a (n ) 3) also react with PPh3,
giving the alkenyl-phosphonio complexes (E)-[Ru{C(H)dC(PPh3)CdCHCH2(CH2)nCH2}(η5-
C9H7)(PPh3)2][PF6] (n ) 2 (13a ), 3 (14a )). The structure of 13a was confirmed by X-ray
diffraction methods. A possible mechanism for the formation of 13a and 14a is proposed.
In tr od u ction
plexes was that reported for the first time by Selegue.4
The process is based on the direct activation of propargyl
alcohols with ruthenium(II) chloride complexes (Scheme
1), and involves the formation of hydroxyvinylidene A,5
through an initial chloride elimination, followed by the
During the last decade, the chemistry of ruthenium-
(II) vinylidene complexes [Ru]+dCdCR2 has experi-
enced important developments due to the discovery of
general synthetic methodologies1 and their involvement
in selective catalytic transformations of terminal al-
kynes.2 In contrast, the chemistry of allenylidene ana-
logs [Ru]+dCdCdCR2 has been less developed1 and the
potential utility of such types of derivatives in chemical
transformations has not yet been exploited.3 So far, the
most general route to ruthenium(II) allenylidene com-
(2) (a) Trost, B. M. Chem. Ber. 1996, 129, 1313 and references cited
therein. (b) Ho¨fer, J .; Doucet, H.; Bruneau, C; Dixneuf, P. H. Tetra-
hedron Lett. 1991, 32, 7409. (c) Doucet, H.; Ho¨fer, J .; Bruneau, C.;
Dixneuf, P. H. J . Chem. Soc., Chem. Commun. 1993, 850. (d) Rappert,
T.; Yamamoto, A. Organometallics 1994, 13, 4984. (e) Bianchini, C.;
Frediani, P.; Masi, D.; Peruzzini, M.; Zanobini, F. Organometallics
1994, 13, 4616. (f) Doucet, H.; Mart´ın-Vaca, B. M.; Bruneau, C.;
Dixneuf, P. H. J . Org. Chem. 1995, 60, 7247. (g) Yi, C. S.; Liu, N.
Organometallics 1996, 15, 3968. (h) Slugovc, C.; Mereiter, K.; Zobetz,
E.; Schmid, R.; Kirchner, K. Organometallics 1996, 15, 5275.
(3) The first example of the involvement of ruthenium allenylidene
species in catalysis have been reported for coupling of 2-propyn-1-ol
derivatives with allylic alcohols in the presence of the [RuCl(η5-C5H5)-
(PPh3)2] catalyst: Trost, B. M.; Flygare, J . A. J . Am. Chem. Soc. 1992,
114, 5476.
† Departamento de Qu´ımica Orga´nica e Inorga´nica.
‡ Departamento de Qu´ımica F´ısica y Anal´ıtica.
X Abstract published in Advance ACS Abstracts, J une 15, 1997.
(1) (a) Bruce, M. I.; Swincer, A. G. Adv. Organomet. Chem. 1983,
22, 59. (b) Bruce, M. I. Chem. Rev. 1991, 91, 197. (c) Antonova, A. B.;
J ohansson, A. A. Russ. Chem. Rev. (Engl. Transl.) 1989, 58, 693.
(4) Selegue, J . P. Organometallics 1982, 1, 217.
S0276-7333(97)00146-5 CCC: $14.00 © 1997 American Chemical Society

Indenylruthenium(II) Vinylvinylidene Complexes
Organometallics, Vol. 16, No. 14, 1997 3179
Sch em e 1
Resu lts a n d Discu ssion
Syn th esis of Vin ylvin ylid en e Com p lexes. The
reaction of complexes [RuCl(η5-C9H7)L2] (L2 ) 2PPh3
(1a ), dppe (1b)) with 1-ethynyl-1-cycloalkanols in re-
fluxing methanol and in the presence of NaPF6 and
MgSO4 results in the formation of vinylvinylidene
complexes 2a ,b, 3a ,b, and 4a ,b, which have been
isolated as brown air-stable hexafluorophosphate salts
(56-89% yield) (Scheme 2). No isomeric allenylidene
species are detected even when the reactions are carried
out at room temperature.6c
All the complexes 2-4 are soluble in chlorinated
solvents and tetrahydrofuran. They have been charac-
terized by microanalysis, conductance measurements,
and IR and NMR (1H, 31P{1H}, and 13C{1H}) spectros-
copy (details are given in the Experimental Section and
Tables 1 and 2). Conductivity data (in acetone) show
that the complexes are 1:1 electrolytes, and the IR
spectra (KBr) exhibit the expected absorption for the
hexafluorophosphate anion [PF6]- (see Experimental
Section). Absorption bands which appear in the range
1600-1700 cm-1 could be tentatively assigned to ν-
(CdC) of the vinylidene group, but they are in general
overlapped by those of the phosphines, and conse-
quently, the assignment is uncertain.
spontaneous dehydration of the acidic vinylidene proton
to give the allenylidene complexes B.
However, the dehydration of hydroxyvinylidene spe-
cies A, containing hydrogen atoms adjacent to the
hydroxy group, can occur in a different way to give
vinylvinylidene derivatives C.6a,b The fate of the dehy-
dration reaction clearly depends on the electronic
properties of the metal auxiliary and the nature of the
propargyl alcohol substituents. This alternative process
shows the synthetic limitations of this well-established
methodology.
We have recently reported the synthesis of novel ru-
thenium(II) allenylidene complexes via the activation
of aromatic propargyl alcohols with the indenyl deriva-
tives [RuCl(η5-C9H7)L2] (L2 ) 2PPh3, 1,2-bis(diphenyl-
phosphino)ethane (dppe), bis(diphenylphosphino)methane
(dppm)).5d Furthermore, we have also reported that the
allenylidene complexes [Ru(dCdCdCRR′)(η5-C9H7)-
(PPh3)2][PF6] (R ) Ph, R′ ) Ph, H; R ) R′ ) H)
are excellent building blocks for the preparation of
organometallic derivatives containing polyunsaturated
chains.7
Continuing with these studies, we report herein the
synthesis of stable indenylruthenium(II) vinylvinylidene
complexes by activation of 1-ethynyl-1-cycloalkanols
with [RuCl(η5-C9H7)L2] (L2 ) 2PPh3, dppe). It is also
shown that the formation of these vinylidene derivatives
involves the initial formation of unstable allenylidene
species which rapidly undergo a tautomerization to the
most thermodynamically stable vinylvinylidene com-
plexes. Part of this work has been previously com-
municated.8
The 31P{1H} NMR spectra of all the vinylvinylidene
complexes show, at room temperature, a single reso-
nance (Table 1). The chemical equivalence of the
phosphorus atoms is consistent with a rapid rotation of
the vinylidene group around the RudC bond on the
NMR time scale, which is in agreement with the data
reported for other indenylruthenium(II) vinylidene com-
plexes.9 Proton and 13C{1H} NMR spectra exhibit
resonances for aromatic, indenyl, methylene ((CH2)2P2),
and cyclopentenyl (2a ,b), cyclohexenyl (3a ,b), or cyclo-
heptenyl (4a ,b) moieties (Tables 1 and 2), in accordance
with the proposed structures. The resonance of the
vinylidene hydrogen appears as a singlet in the range
δ 4.03-5.31 ppm. The 13C{1H} NMR spectra show a
low-field triplet signal for the carbenic CR atom, due to
the coupling with the two equivalent phosphorus atoms
2
(δ 337.88-358.33 ppm, J CP ) 14.4-17.4 Hz). This
typical low-field resonance has been explained as a
consequence of a paramagnetic σP term rather than of
an electron deficiency.10 The Câ atom appears as a
singlet at δ 112.81-123.63.
Indenyl carbon resonances (Table 2) have also been
assigned, and they are in accordance with the proposed
η5 coordination.11 As has been proven previously, the
parameter ∆δ(C-3a,7a) ) δ(C-3a,7a(η-indenyl complex))
- δ(C-3a,7a(sodium indenyl)) can be used as an indica-
tion of the indenyl distortion.12 The calculated values
(5) Ruthenium hydroxyvinylidene derivatives have been isolated:
(a) Touchard, D.; Haquette, P.; Pirio, N.; Toupet, L.; Dixneuf, P. H.
Organometallics 1993, 12, 3132. (b) Le Lagadec, R.; Roman, E.; Toupet,
L.; Mu¨ller, U.; Dixneuf, P. H. Organometallics 1994, 13, 5030. (c)
Braun, T.; Steinert, P.; Werner, H. J . Organomet. Chem. 1995, 488,
169. (d) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Gonza´lez-Cueva, M.;
Lastra, E.; Borge, J .; Garc´ıa-Granda, S.; Pe´rez-Carren˜o, E. Organo-
metallics 1996, 15, 2137.
(6) (a) Selegue, J . P.; Young, B. A.; Logan, S. L. Organometallics
1991, 10, 1972. (b) Touchard, D.; Pirio, N.; Dixneuf, P. H. Organome-
tallics 1995, 14, 4920. (c) We have recently reported similar results
using indenylosmium and tricarbonyltungsten derivatives: Gamasa,
M. P.; Gimeno, J .; Gonza´lez-Cueva, M.; Lastra, E. J . Chem. Soc., Dalton
Trans. 1996, 2547. Zhang, L.; Gamasa, M. P.; Gimeno, J .; Carbajo, R.
J .; Lo´pez-Ortiz, F.; Lanfranchi, M.; Tiripicchio, A. Organometallics
1996, 15, 4274.
(8) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Lastra, E.; Borge, J .;
Garc´ıa-Granda, S. Organometallics 1994, 13, 745.
(9) Gamasa, M. P.; Gimeno, J .; Mart´ın-Vaca, B. M.; Borge, J .; Garc´ıa-
Granda, S.; Pe´rez-Carren˜o, E. Organometallics 1994, 13, 4045.
(10) Czech, P. T.; Ye, X. G.; Fenske, R. F. Organometallics 1990, 9,
2016.
(11) (a) Zhou, Z.; J ablonski, C.; Bridson, J . J . Organomet. Chem.
1993, 461, 215 and references therein. (b) Ceccon, A.; Elsevier, C. J .;
Ernsting, J . M.; Gambaro, A.; Santi, S.; Venzo, A. Inorg. Chim. Acta
1993, 204, 15.
(12) (a) Baker, R. T.; Tulip, T. H. Organometallics 1986, 5, 839. (b)
Kohler, F. G. Chem. Ber. 1974, 107, 570.
(7) (a) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Lastra, E. J .
Organomet. Chem. 1994, 474, C27. (b) Cadierno, V.; Gamasa, M. P.;
Gimeno, J .; Borge, J .; Garc´ıa-Granda, S. J . Chem. Soc., Chem.
Commun. 1994, 2495. (c) Houbrechts, S.; Clays, K.; Persoons, A.;
Cadierno, V.; Gamasa, M. P.; Gimeno, J . Organometallics 1996, 15,
5266.
(13) Selegue, J . P.; Lomprey, J . R. J . Am. Chem. Soc. 1992, 114,
5518.
(14) Bruce, M. I.; Wong, F. S.; Shelton, B. W.; White, A. H. J . Chem.
Soc., Dalton Trans. 1982, 2203.
(15) Bruce, M. I.; Humphrey, M. G.; Snow, M. R.; Tiekink, E. R. T.
J . Organomet. Chem. 1986, 314, 213.

3180 Organometallics, Vol. 16, No. 14, 1997
Cadierno et al.
Sch em e 2
Ta ble 1. 31P {1H} a n d 1H NMR Da ta for th e Vin ylvin ylid en e Com p lexesa
1H
η5-C9H7
f
complex 31P{1H} H-1,3
H-2
J HH H-4,7, H-5,6 RudCdCH
dCH
J HH
others
2a b
3a c
4a c
2bb
3bc
37.80 s 5.55 d 5.85 t 2.6
37.55 s 5.50 d 5.79 t 2.7
37.67 s 5.53 d 5.74 t 2.6
73.53 s 5.83 d 5.94 t 2.7
78.78 s 5.79 d 5.88 t 2.7
5.91 md
5.85 md
5.99 md
d
5.31 s
4.81 s
4.90 s
4.42 s
4.03 s
5.08 bs
1.73 (m, CH2); 1.94 (m, CH2); 2.44 (m, CH2);
6.86-7.49 (m, PPh3)
5.37 bs
5.49 t
1.41 (m, 2 CH2); 1.64 (m, CH2); 2.14 (m, CH2);
6.78-7.52 (m, PPh3)
6.7 1.29 (m, CH2); 1.42 (m, CH2); 1.63 (m, CH2); 1.93
(m, CH2); 2.21 (m, CH2); 6.81-7.50 (m, PPh3)
1.57 (m, CH2); 1.91 (m, CH2); 2.23 (m, CH2); 2.33
and 2.73 (m, P(CH2)2P); 6.70-7.58 (m, PPh2)
0.81 (m, CH2); 1.12 (m, CH2); 1.25 (m, CH2); 1.89
(m, CH2); 2.32 and 2.69 (m, P(CH2)2P);
4.97 bs
4.90 bs
d
6.65-7.53 (m, PPh2)
4bc
73.41 s
e
e
e
6.30 md
4.10 s
5.01 t
5.9 0.99 (m, CH2); 1.15 (m, CH2); 1.28 (m, CH2); 1.51
(m, CH2); 1.90 (m, CH2); 2.39 and 2.69 (m,
P(CH2)2P); 6.73-7.53 (m, PPh2)
a
b
δ in ppm and J in Hz. Abbreviations: s, singlet; bs, broad singlet; d, doublet; t, triplet; m, multiplet. Spectra recorded in CD2Cl2.
c Spectra recorded in CDCl3. Overlapped by PPh3 or PPh2 protons. e 5.84 ppm (m, H-1,3 and H-2). f Legend for indenyl skeleton:
d
for the vinylvinylidene complexes, which are in the
range ca. -13 to -18 ppm, can be compared to that of
[Ru(dCdCR2)(η5-C9H7)L2]+ 9 and are indicative of a
moderate distortion of the η5-indenyl coordination.
Syn th esis of En yn yl Com p lexes. The efficient
access to the cationic vinylvinylidene derivatives al-
lowed the synthesis of enynylruthenium derivatives
through deprotonation reactions to be explored. Thus,
complexes 2-4 are readily deprotonated by treatment
with an excess of Al2O3 in dichloromethane at room
temperature, to give the orange enynyl complexes 5a ,b,
6a ,b, and 7a ,b (84-97% yield) (Scheme 2). These
deprotonations are reversible, since the addition of 1
equiv of HBF4‚Et2O in diethyl ether at room tempera-
ture to the enynyl complexes give selectively the parent
vinylvinylidene derivatives. Complexes 5-7 were ana-
lytically and spectroscopically characterized (see Tables
3 and 4 and Experimental Section). In particular, IR
spectra exhibit the expected ν(CtC) absorption band in
the range 2051-2069 cm-1 and 13C{1H} NMR spectra
display characteristic triplet resonances at δ 104.47-
113.98 ppm (2J CP ) 24.5-25.8 Hz) for the RusCt
carbon nucleus. The Câ resonance appears as a singlet
in the range δ 109.77-118.20 ppm. Indenyl carbon
resonances (Table 4) have also been assigned, and the
calculated values for the parameter ∆δ(C-3a,7a), which
are in the range ca. -20 to -25 ppm, are indicative of
a nondistorted η5-indenyl coordination.12
Syn th esis a n d Molecu la r Str u ctu r e of th e Com -
p lex [Ru {dCdC(Me)R}(η5-C9H7)(P P h 3)2][CF 3SO3]
(R ) Cycloh exen yl; 8a ). Alkynyl complexes can be
used as suitable precursors of methyl-substituted vinyli-
dene complexes through electrophilic additions of meth-
yl groups.1 Thus, the reaction of 6a with MeOSO2CF3
in Et2O leads to the formation of the disubstituted vinyl-
(16) Borge, J .; Garc´ıa-Granda, S. Unpublished results.

Indenylruthenium(II) Vinylvinylidene Complexes
Organometallics, Vol. 16, No. 14, 1997 3181
Ta ble 2. 13C{1H} NMR Da ta for th e Vin ylvin ylid en e Com p lexesa
η5-C9H7
complex C-1,3 C-2 C-3a,7a ∆δ(C-3a,7a)b C-4,7, C-5,6
RudCR J CP
Câ
dCH
dC
others
2
2a
83.26 99.28 116.33
-14.37
123.65, 130.52 355.65 t 16.4 115.28 126.67 127.90 24.27, 32.41, and 35.57 (s, CH2);
128.80-134.37 (m, PPh3)
355.36 t 16.5 121.58 124.14 124.84 22.56, 23.39, 26.38, and
3a
83.19 99.74 116.80
-13.90
124.01c
30.49 (s, CH2); 129.15-134.45
(m, PPh3)
4a
2b
3b
4b
83.29 99.45 116.23
78.76 98.61 113.40
78.59 98.46 113.25
79.29 98.45 113.26
-14.47
-17.30
-17.45
-17.44
123.74, 130.70 340.26 t 15.1 123.63 128.17
c
c
26.92, 27.75, 28.97, 32.52, and
34.59 (s, CH2); 129.06-134.06
(m, PPh3)
23.70, 32.48, and 33.89 (s, CH2);
26.33 (m, P(CH2)2P);
123.67, 125.89 358.33 t 16.5 112.81
c
128.99-134.32 (m, PPh2)
122.53c
123.77c
358.21 t 14.4 119.07 121.81 123.33 21.90, 22.85, 25.77, and 28.09
(s, CH2); 26.20 (m, P(CH2)2P);
127.20-134.75 (m, PPh2)
337.88 t 17.4 121.30 126.50
c
26.81, 27.51, 28.57, 32.41, and
32.53 (s, CH2); 26.40 (m,
P(CH2)2P); 129.53-134.21
(m, PPh2)
a
b
Spectra recorded in CD2Cl2; δ in ppm and J in Hz. Abbreviations: s, singlet; t, triplet; m, multiplet. ∆δ(C-3a,7a) ) δ(C-3a,7a(η-
indenyl complex)) - δ(C-3a,7a(sodium indenyl)), δ(C-3a,7a) for sodium indenyl 130.70 ppm. c Overlapped by PPh3 or PPh2 carbons.
Ta ble 3. 31P {1H} a n d 1H NMR Da ta for th e En yn yl Com p lexesa
1H
η5-C9H7
complex
31P{1H}
H-1,3
H-2
J HH
H-4,7, H-5,6
dCH
J HH
others
5a
6a
51.98 s
52.35 s
4.71 d
4.95 d
5.83 t
5.83 t
2.2
2.1
6.30 m, 6.66 m
6.58 m, 6.92 m
5.64 t
6.25 bs
2.5
1.92 (m, CH2); 2.57 (m, 2 CH2); 6.90-7.52 (m, PPh3)
1.90 (m, 2 CH2); 2.49 (m, CH2); 2.64 (m, CH2);
7.18-7.74 (m, PPh3)
7a
5b
6b
7b
52.33 s
87.67 s
87.98 s
87.60 s
4.69 d
5.27 d
5.27 d
5.28 d
5.58 t
5.42 t
5.41 t
5.42 t
2.2
2.5
2.7
2.5
6.36 m, 6.66 m
7.10 mb
6.20 t
5.51 bs
5.65 t
5.84 t
6.8
1.60 (m, 2 CH2); 1.75 (m, CH2); 2.29 (m, CH2);
2.54 (m, CH2); 6.91-7.49 (m, PPh3)
1.92 (m, CH2); 2.34 (m, CH2); 2.54 (m, CH2);
2.10 and 2.69 (m, P(CH2)2P); 7.25-7.89 (m, PPh2)
1.67 (m, 2 CH2); 2.08 (m, CH2); 2.23 (m, CH2);
2.70 (m, P(CH2)2P); 7.26-7.90 (m, PPh2)
1.63 (m, 2 CH2); 1.83 (m, CH2); 2.27 (m, 2 CH2);
2.09 and 2.70 (m, P(CH2)2P); 7.26-7.89 (m, PPh2)
7.13 mb
1.7
6.8
7.11 mb
a
Spectra recorded in C6D6; δ in ppm and J in Hz. Abbreviations: s, singlet; bs, broad singlet; d, doublet; t, triplet; m, multiplet.
b
Overlapped by PPh3 or PPh2 protons.
Ta ble 4. 13C{1H} NMR Da ta for th e En yn yl Com p lexesa
η5-C9H7
complex C-1,3 C-2 C-3a,7a ∆δ(C-3a,7a)b C-4,7, C-5,6
Ru-CR J CP
Câ
dCH
dC
others
2
5a
74.89c 95.70 109.37
-21.33
123.09, 125.87 110.41 t 24.9 111.63 125.36 131.33 24.00, 33.03, and 38.29 (s, CH2);
127.29-139.18 (m, PPh3)
6a
75.54 96.29 109.94
-20.76
123.41, 126.22 104.47 t 24.5 117.22 124.39
d
23.42, 23.68, 26.88, and 32.61
(s, CH2); 126.87-139.55
(m, PPh3)
7a
5b
6b
7b
74.85 95.55 109.27
70.75 93.27 108.62
68.64 91.17 106.59
68.63 91.15 106.52
-21.43
-22.08
-24.11
-24.18
123.09, 125.82 104.86 t 25.1 118.20
d
133.66 27.54, 28.55, 29.32, 33.55, and
36.69 (s, CH2); 127.34-139.27
(m, PPh3)
124.48, 124.95 113.98 t 25.0 109.77 125.83 131.91 24.41, 33.41, and 38.55 (s, CH2);
28.85 (m, P(CH2)2P);
128.21-142.89 (m, PPh2)
122.37, 122.93 105.25 t 25.8 112.82 122.14 125.05 21.38, 22.10, 24.55, and 30.05
(s, CH2); 26.84 (m, P(CH2)2P);
126.87-139.55 (m, PPh2)
122.34, 122.88 106.00 t 25.5 114.58
d
131.92 25.86, 26.69, 27.68, 31.88, and
34.91 (s, CH2); 26.71 (m,
P(CH2)2P); 126.31-140.76
(m, PPh2)
a
b
Spectra recorded in C6D6; δ in ppm and J in Hz. Abbreviations: s, singlet; t, triplet; m, multiplet. ∆δ(C-3a,7a) ) δ(C-3a,7a(η-
indenyl complex)) - δ(C-3a,7a(sodium indenyl)), δ(C-3a,7a) for sodium indenyl 130.70 ppm. c t, 2J CP ) 3.4. Overlapped by PPh3 or PPh2
carbons.
d
vinylidene complex 8a , which has been isolated as an
insoluble solid from the reaction mixture (Scheme 2).
The spectroscopic properties of 8a are similar to those
of the monosubstituted vinylvinylidene complex 3a .
Significantly, NMR spectra show the expected proton
and carbon resonances of the methyl group at δ 1.50
(1H NMR) and δ 10.38 (13C{1H} NMR), respectively. The
13C{1H} NMR spectra also show the carbenic CR reso-
nance at δ 352.77 (t, J CP ) 17.7 Hz). It is noteworthy
that the Câ resonance appears at a field lower than that
of the monosubstituted species, a shift which is also
observed in the spectra of similar derivatives.9
We have previously reported that the orientation of
the benzo ring of the indenyl ligand in indenylruthe-
2

3182 Organometallics, Vol. 16, No. 14, 1997
Cadierno et al.
the legs show values typical of a pseudooctahedron. The
vinylidene ligand is bound to Ru with an Ru-C(1)
distance of 1.838(5) Å, a C(1)-C(2) distance of 1.299(6)
Å, and a Ru-C(1)-C(2) angle of 176.2(4)°. These
bonding parameters can be compared to those reported
for other ruthenium vinylidene complexes (Table 6). The
dihedral angle DA between the pseudo mirror plane of
the metallic moiety (containing the Ru atom, the C(1)
atom, and the centroid C* of the five-carbon ring of the
indenyl ligand) and the mean vinylidene plane (contain-
ing the C(1), C(2), C(3), and C(4) atoms) is 118.1(5)°,
showing a deviation from the orthogonal relationship
calculated by theoretical studies.17 Typical deviations
of this relationship are also observed in other vinylidene
complexes. The C(4)-C(9) bond length (1.316(7) Å)
shows a value typical of a CdC bond.
F igu r e 1. View of the structure of the vinylvinylidene
complex [Ru{dCdC(Me)R}(η5-C9H7)(PPh3)2]+ (R ) 1-cy-
clohexenyl; 8a ). For clarity, aryl groups of the triphen-
ylphosphine ligands are omitted (C* ) centroid of the
indenyl ring).
Although the indenyl group is η5-bonded to ruthe-
nium, the structure shows moderate distortions of the
five-carbon ring from planarity, which are similar to
those shown by analogous vinylidene derivatives (see
Tables 5 and 7). The moderate distortions toward an
η3 binding mode in the solid state appear to be main-
tained in solution, according to the value ∆δ(C-3a,7a)
) -13.75 obtained from the 13C{1H} NMR spectra. As
has been also observed for the indenyl vinylidene
complexes [Ru(dCdCMe2)(η5-C9H7)(PPh3)2]+ 9 and [Ru-
{dCdC(H)Ph}(η5-C9H7)(PPh3)2]+,16 the preferred con-
formation of the indenyl ligand is such that the benzo
ring is oriented trans to the vinylidene group. However,
their C(1) and C(2) atoms are not contained in the
mirror plane of the indenyl ring (Figure 1), showing a
conformational angle (CA) (Table 5) of 160.0(3)°. The
preferred trans conformation for the vinylidene deriva-
tives can be rationalized on the basis of theoretical
calculations (EHMO), which predict that the trans
orientation (CA ) 180°) is energetically more favored
than the cis (CA ) 0°).9 It is noteworthy that the cis
orientation is preferred to the trans in indenylruthe-
nium(II) allenylidene complexes (Table 7).5d
Ta ble 5. Selected Bon d Dista n ces a n d Slip
P a r a m eter ∆a (Å) a n d Bon d An gles a n d Dih ed r a l
An gles F A,b HA,c DA,d a n d CAe (d eg) for
Com p lex 8a
Distances
Ru-C*
1.970(9)
2.373(1)
2.353(1)
2.423(5)
2.237(5)
2.216(5)
2.246(5)
2.456(5)
1.834(5)
1.834(5)
1.849(5)
1.839(5)
1.839(5)
P(2)-C(61)
Ru-C(1)
C(1)-C(2)
C(2)-C(3)
C(2)-C(4)
C(4)-C(5)
C(4)-C(9)
C(5)-C(6)
C(6)-C(7)
C(7)-C(8)
C(8)-C(9)
∆
1.830(5)
1.838(5)
1.299(6)
1.501(7)
1.513(7)
1.509(7)
1.316(7)
1.503(8)
1.475(8)
1.513(8)
1.500(8)
0.198(5)
Ru-P(1)
Ru-P(2)
Ru-C(70)
Ru-C(71)
Ru-C(72)
Ru-C(73)
Ru-C(74)
P(1)-C(11)
P(1)-C(21)
P(1)-C(31)
P(2)-C(41)
P(2)-C(51)
Angles
C*-Ru-C(1)
C*-Ru-P(1)
C*-Ru-P(2)
C(1)-Ru-P(1)
C(1)-Ru-P(2)
P(1)-Ru-P(2)
Ru-C(1)-C(2)
C(1)-C(2)-C(3)
C(1)-C(2)-C(4)
FA
121.9(2)
117.1(2)
124.9(2)
94.5(2)
C(2)-C(4)-C(9)
C(2)-C(4)-C(5)
C(4)-C(2)-C(3)
C(4)-C(9)-C(8)
C(9)-C(4)-C(5)
C(9)-C(8)-C(7)
C(8)-C(7)-C(6)
C(7)-C(6)-C(5)
C(6)-C(5)-C(4)
HA
121.6(5)
115.9(4)
118.2(4)
123.1(5)
122.5(5)
122.9(5)
111.9(5)
112.3(6)
112.1(5)
7.5(4)
87.3(1)
103.9(1)
176.2(4)
123.1(5)
118.6(5)
12.2(4)
Syn t h esis of Alk yn yl-P h osp h on io Com p lexes.
The complex [RuCl(η5-C9H7)(PPh3)2] reacts with the
propargyl alcohols 1-ethynyl-1-cyclopentanol and 1-ethy-
nyl-1-cyclohexanol to afford, in the presence of an excess
of triphenylphosphine, the alkynyl-phosphonio deriva-
tives 11a (73%) and 12a (61%) (Scheme 3). Analytical
and spectroscopic data (IR and 1H, 31P{1H}, and
13C{1H} NMR) are in accordance with the proposed
formulations. The IR spectra show the typical ν(CtC)
and ν(PF6-) absorptions (see Experimental Section for
details), and the 31P{1H} NMR spectra exhibit reso-
nances consistent with an A2M system (11a , δ 28.85 (t,
DA
118.1(5)
CA
160.0(3)
a
∆ ) d(Ru-C(74),C(70)) - d(Ru-C(71),C(73)). b FA (fold angle)
) angle between normals to least-squares planes defined by C(71),
C(72), C(73) and C(70), C(74), C(75), C(76), C(77), C(78). c HA
(hinge angle) ) angle between normals to least-squares planes
d
defined by C(71), C(72), C(73) and C(71), C(74), C(70), C(73). DA
(dihedral angle) ) angle between normals to least-squares planes
defined by C*, Ru, C(1) and C(1), C(2), C(3). e CA (conformational
angle) ) angle between normals to least-squares planes defined
by C**, C*, Ru and C*, Ru, C(1). C* ) centroid of C(70), C(71),
C(72), C(73), C(74). C** ) centroid of C(70), C(74), C(75), C(76),
C(77), C(78).
5
5J PP ) 3.8 Hz, C-PPh3), 49.34 (d, J PP ) 3.8 Hz, Ru-
5
PPh3); 12a , δ 25.42 (t, J PP ) 3.9 Hz, C-PPh3), 49.02
5
(d, J PP ) 3.9 Hz, Ru-PPh3)), also in accordance with
nium(II) alkynyl, vinylidene and allenylidene complexes
depends on the nature of the unsaturated chain.5d,9 In
order to find out this orientation in the vinylvinylidene
complexes, the structure of complex 8a has been deter-
mined by X-ray diffraction. The molecular structure is
shown in Figure 1 and consists of [Ru{dCdC(Me)R}-
(η5-C9H7)(PPh3)2]+ (R ) 1-cyclohexenyl) cations and
triflate anions. Selected bond distances and angles are
listed in Table 5. The molecule exhibits the usual
allylene structure of the η5-indenyl ligand in the pseu-
dooctahedral three-legged piano-stool geometry. The
interligand angles P(1)-Ru-P(2), C(1)-Ru-P(1), and
C(1)-Ru-P(2) and those between the centroid C* and
the spectra shown by similar alkynyl-phosphonio com-
plexes.7 The presence of the alkynyl group is confirmed
by the 13C{1H} NMR spectra, which show multiplet
resonances at δ 112.15 (11a ) and 113.19 (12a ), assigned
to the CR nuclei. This seems to indicate an effective
coupling of these nuclei with the two equivalent phos-
phorus atoms bonded to the metal and also with that
of the alkynyl group. Câ and Cγ resonances appear as
doublets at δ 103.84-107.12 (2J CP ) 3.5-6.8 Hz) and δ
44.22-44.96 (J CP ) 45.3-49.0 Hz), respectively.
(17) (a) Schilling, B. E. R.; Hoffmann, R.; Lichtenberger, D. L. J .
Am. Chem. Soc. 1979, 101, 585. (b) Kostic, N. M.; Fenske, R. J .
Organometallics 1982, 1, 974.

Indenylruthenium(II) Vinylvinylidene Complexes
Organometallics, Vol. 16, No. 14, 1997 3183
Ta ble 6. Com p a r a tive Str u ctu r a l Da ta for [Ru ]+dCdCRR′ Com p lexes
[Ru]
R
R’
Ru-C(1) (Å)
C(1)-C(2) (Å)
Ru-C(1)-C(2) (deg)
ref
Ru(η5-C5H5)(PMe2Ph)2
Ru(η5-C5H5)(PMe3)2
Ru(η5-C5H5)(PMe3)2
Ru(η5-C5H5)(PPh3)2
Ru(η5-C5Me5)(PMe2Ph)2
Ru(η5-C5Me5)(PMe2Ph)2
Ru(η5-C9H7)(PPh3)2
Ru(η5-C9H7)(PPh3)2
Ru(η5-C9H7)(PPh3)2
RuCl(dppm)2
H
H
H
Me
H
H
Me
H
Me
H
H
C6H9
Me
Ph
1.843(1)
1.843(7)
1.845(7)
1.86(1)
1.287(1)
1.30(1)
1.313(1)
1.29(2)
1.34(2)
1.29(1)
1.30(1)
1.270(7)
1.299(6)
1.22(1)
174.1(8)
178.2
180(2)
173
174(1)
174(6)
173.7(6)
179.1(5)
176.2(4)
178.3(8)
13
6a
14
15
5b
5b
9
16
b
5a
a
Ph
1.76(1)
CHMeOMe
Me
Ph
C6H9
H
1.854(8)
1.839(7)
1.821(5)
1.838(5)
1.882(8)
a
a
b
C6H9) cyclohexenyl. This work.
Ta ble 7. Slip P a r a m eter ∆ a n d Dih ed r a l An gles F A, HA, a n d CA for In d en yl Com p lexesa
complex
M-C* (Å)
∆ (Å)
FA (deg)
HA (deg)
CA (deg)
ref
[{Ru}(dCdCMe2)]+
1.97(9)
0.197(7)
0.175(6)
0.1974(1)
0.0820(4)
0.1211(4)
0.095(4)
0.217(5)
13.1(6)
11.9(5)
12.2(4)
5.1(5)
8.1(3)
7.9(3)
8.1(6)
6.6(5)
7.5(4)
5.3(5)
6.2(4)
5.3(3)
8.4(4)
157.8(4)
164.6(3)
160.0(3)
12.2(6)
9.6(3)
9
16
c
[{Ru}(dCdC(H)Ph)]+
1.964(6)
1.970(9)
1.942(5)
1.951(5)
1.950(5)
1.981(5)
[{Ru}(dCdC(Me)(C6H9))]+ b
[{Ru}(dCdCdC(C13H20))]+
[{Ru}(dCdCdCPh2)]+
8
5d
5d
c
[{Os}(dCdCdCPh2)]+
9.4(2)
160.5(2)
(E)-[{Ru}(C(H)dC(PPh3)(C6H9))]+ b
14.8(4)
a
∆ ) d[M-C(74),C(70)] - d[M-C(71),C(73)]. FA ) C(71),C(72),C(73)/C(70),C(74),C(75),C(76),C(77),C(78). HA ) C(71),C(72),C(73)/
C(71),C(74),C(70),C(73). CA ) C**,C*,M/C*,M,C(1). {M} ) M(η5-C9H7)(PPh3)2 (M ) Ru, Os). C6H9 ) cyclohexenyl. c This work.
b
Sch em e 3
As has been mentioned above, the activation of
1-ethynyl-1-cycloalkanols to give either allenylidene or
vinylvinylidene species (see Scheme 1) leads regiose-
lectively to vinylvinylidene complexes. We have re-
ported that alkynyl-phosphonio complexes can be
readily prepared through the regioselective nucleophilic
addition of phosphines to the Cγ atom of the allenylidene
chain.7 On the basis of this synthetic approach the
formation of 11a and 12a may be understood assuming
that allenylidene intermediates 9a and 10a are formed
as transient species which undergo a rapid nucleophilic
addition of triphenylphosphine to the electrophilic Cγ
atom. This seems to indicate that the allenylidene spe-
cies are kinetically controlled products, since in the ab-
sence of PPh3 the more stable tautomeric vinylvinyl-
idene complexes 2-4 are formed. It is noteworthy to
mention that although the reaction has taken place in
methanol as a solvent no addition of methanol or water
to the CR atom of the allenylidene chain has occurred.18
This behavior is in accordance with the inertness of the
similar indenylruthenium(II) allenylidene complexes
[Ru(dCdCdCRR′)(η5-C9H7)L2][PF6] (R ) R′ ) Ph, L )
PPh3, L2 ) dppe, dppm; RR′ ) C13H20, L ) PPh3), all of
them exhibiting an efficient protection of the CR atom
due to the preferred cis orientation of the indenyl group
with respect to the allenylidene chain.5d,8
Attempts to obtain the corresponding alkynyl-phos-
phonio complex with 1-ethynyl-1-cycloheptanol as the
starting material have failed, giving instead the vinylvi-
nylidene complex 7a . The more sterically demanding
cycloheptyl group compared to the cyclopentyl or cyclo-
hexyl group seems to prevent the triphenylphosphine
addition to the corresponding allenylidene intermediate.
Syn t h esis of Alk en yl-P h osp h on io Com p lexes.
Since cationic vinylvinylidene complexes 2-4 are suit-
able substrates to study the nature and positions of the
electrophilic sites, we became interested in studying the
reactivity of these complexes toward phosphines. In
particular, we expected to obtain information on the
regioselectivity of the nucleophilic additions in order to
(18) Ruthenium(II) cyclohexylallenylidene complexes have been
trapped by addition of methanol or water to yield alkenyl-carbene
derivatives: (a) Pilette, D.; Ouzzine, K.; Le Bozec, H.; Dixneuf, P. H.;
Rickard, C. E. F.; Roper, W. R. Organometallics 1992, 11, 809. (b)
Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.; On˜ate, E.;
Oro, L. A. Organometallics 1996, 15, 3423.

3184 Organometallics, Vol. 16, No. 14, 1997
Cadierno et al.
Ta ble 8. Selected Bon d Dista n ces a n d Slip
Sch em e 4
P a r a m eter ∆a (Å) a n d Bon d An gles a n d Dih ed r a l
An gles F A,b HA,c DA,d a n d CAe (d eg) for Com p lex
13a
Distances
Ru-C*
1.981(5)
2.327(2)
2.349(2)
2.465(5)
2.239(5)
2.205(2)
2.240(5)
2.447(5)
1.838(6)
1.845(5)
1.852(5)
1.855(6)
1.830(5)
1.836(6)
Ru-C(1)
2.045(6)
1.371(7)
1.499(7)
1.356(8)
1.482(8)
1.483(9)
1.34(1)
Ru-P(1)
C(1)-C(2)
C(2)-C(91)
C(91)-C(96)
C(91)-C(92)
C(92)-C(93)
C(93)-C(94)
C(94)-C(95)
C(95)-C(96)
C(2)-P(3)
Ru-P(2)
Ru-C(70)
Ru-C(71)
Ru-C(72)
Ru-C(73)
Ru-C(74)
P(1)-C(11)
P(1)-C(21)
P(1)-C(31)
P(2)-C(41)
P(2)-C(51)
P(2)-C(61)
1.44(1)
1.497(8)
1.790(6)
1.808(5)
1.819(6)
1.799(6)
0.217(5)
P(3)-C(101)
P(3)-C(111)
P(3)-C(121)
∆
Angles
C*-Ru-C(1)
C*-Ru-P(1)
C*-Ru-P(2)
C(1)-Ru-P(1)
C(1)-Ru-P(2)
P(1)-Ru-P(2)
Ru-C(1)-C(2)
124.3
C(2)-P(3)-C(101)
C(2)-P(3)-C(111)
C(2)-P(3)-C(121)
C(2)-C(91)-C(96)
C(2)-C(91)-C(92)
109.9(2)
113.1(3)
112.0(2)
120.6(5)
117.9(5)
121.8(2)
123.0(2)
89.6(2)
89.2(2)
100.23(6) C(91)-C(92)-C(93) 115.2(6)
135.9(4)
C(92)-C(93)-C(94) 119.8(7)
C(93)-C(94)-C(95) 124.5(8)
C(94)-C(95)-C(96) 112.2(6)
C(95)-C(96)-C(91) 122.6(6)
HA
CA
C(1)-C(2)-C(91) 129.6(5)
C(1)-C(2)-P(3) 117.5(4)
C(91)-C(2)-P(3) 112.5(4)
FA
DA
14.8(4)
4.9(3)
8.4(4)
160.5(2)
a
∆ ) d(Ru-C(74),C(70)) - d(Ru-C(71),C(73)). b FA (fold angle)
) angle between normals to least-squares planes defined by C(71),
C(72), C(73) and C(70), C(74), C(75), C(76), C(77), C(78). c HA
(hinge angle) ) angle between normals to least-squares planes
d
defined by C(71), C(72), C(73) and C(71), C(74), C(70), C(73). DA
(dihedral angle) ) angle between normals to least-squares planes
defined by C*, Ru, C(1) and Ru, C(1), C(2), C(3). e CA (conforma-
tional angle) ) angle between normals to least-squares planes
defined by C**, C*, Ru and C*, Ru, C(1). C* ) centroid of C(70),
C(71), C(72), C(73), C(74). C** ) centroid of C(70), C(74), C(75),
C (76), C(77), C(78).
F igu r e 2. View of the structure of the alkenyl-phosphonio
complex (E)-[Ru{C(H)dC(PPh3)R}(η5-C9H7)(PPh3)2]+ (R )
1-cyclohexenyl; 13a ). For clarity, aryl groups of the triph-
enylphosphine ligands are omitted (C* ) centroid of the
indenyl ring).
with an E configuration (the ruthenium atom is trans
to the triphenylphosphine group). Its orientation with
respect to the mirror molecular plane deviates 4.9(3)°
(dihedral angle (DA) between the planes Ru-C(1)-C*
and Ru-C(1)-C(2)) from the expected 90° according to
theoretical calculations.17b The Ru-C(1) bond length
(2.045(6) Å) is similar to that shown by the analogous
alkenylruthenium complexes (E)-[Ru{C(CO2Me)d
CH(CO2Me)}(η5-C5H5)(dppe)] (2.07(1) Å)19 and (Z)-
[Ru{C(CO2Me)dCH(CO2Me)}(η5-C5H5)(CO)(PPh3)] (2.080-
(8) Å).19 The bond lengths C(1)-C(2) ) 1.371(7) Å and
C(91)-C(96) ) 1.356(8) Å show the expected values for
CdC bonds.
compare their reactivity to that of the tautomeric
allenylidene moieties. However, the reactions follow a
different path.
Thus, compounds 3a and 4a react with a large excess
of triphenylphosphine, in refluxing methanol, to yield
the alkenyl-phosphonio derivatives 13a (72%) and 14a
(79%), respectively (Scheme 4). Since analytical and
spectroscopic data did not allow the structure to be
established unequivocally, an X-ray structural deter-
mination was carried out for complex 13a .
Crystals of 13a suitable for X-ray diffraction analysis
were obtained from a CH2Cl2/Et2O solution. The crystal
structure consists of (E)-[Ru{C(H)dC(PPh3)R}(η5-C9H7)-
(PPh3)2]+ (R ) 1-cyclohexenyl) cations, hexafluorophos-
phate anions, and CH2Cl2 and Et2O molecules of crys-
tallization (CH2Cl2/Et2O/solvate). A view of the molecular
structure is shown in Figure 2, and selected bond
distances and bond angles are listed in Table 8. The
geometry of the [Ru(η5-C9H7)(PPh3)2] moiety is similar
to that found in the vinylvinylidene complex 8a , showing
also a trans orientation of the indenyl ligand with
respect to the alkenyl moiety (CA ) 160.5(2)°).
The most remarkable feature is the presence of a
planar alkenyl-phosphonio fragment in which the
phosphine is bonded to the Câ atom of the alkenyl group
The indenyl group is η5-bonded to the metal, but the
structure shows important distortions of the five-carbon
ring from planarity with hinge angle (HA) and fold angle
(FA) values of 8.4(4) and 14.8(4)°, respectively (Table
5). The slippage of the indenyl ring is higher than that
shown in vinylidene or allenylidene derivatives (Table
7). These distortion parameters toward an η3 binding
mode, which appear to be maintained in solution (∆δ-
(C-3a,7a) ) -16.56 ppm) (see Experimental Section),
are the highest yet described for indenylruthenium(II)
complexes.
1
Analytical and spectroscopic data (IR and H, 31P{1H},
and 13C{1H} NMR) are in accordance with the proposed
formulations. The 31P{1H} NMR spectra show reso-
(19) Bruce, M. I.; Catlow, A.; Humphrey, M. G.; Koutsantonis, G.
A.; Snow, M. R.; Tiekink, E. R. T. J . Organomet. Chem. 1988, 338, 59.

Indenylruthenium(II) Vinylvinylidene Complexes
Organometallics, Vol. 16, No. 14, 1997 3185
moiety C13H20 This spiro bicycle results from the
nances which are consistent with an ABM system (13a ,
.
4
4
δ 11.92 (dd, J PP ) 6.0 Hz, J PP ) 3.8 Hz, C-PPh3),
formal addition of two molecules of the alkyn-1-ol via a
metal-promoted double dehydration of 1-ethynyl-1-
cyclohexanol.8 This selective synthetic route to give
either vinylvinylidene or allenylidene complexes dem-
onstrates that the activation of substituted propargyl
alcohols is clearly dependent on the nature of the
substituents. Since both unsaturated carbene vinylvi-
nylidene and allenylidene groups are tautomeric forms,
this behavior raises the question of the driving force that
governs the allenylidene vs vinylvinylidene formation
in the activation of 1-ethynyl-1-cycloalkanols.
2
4
43.18 (dd, J PP ) 29.6 Hz, J PP ) 6.0 Hz, Ru-PPh3),
2
4
46.24 (dd, J PP ) 29.6 Hz, J PP ) 3.8 Hz, Ru-PPh3);
2
14a , δ 12.33 (bs, C-PPh3), 43.11 (dbs, J PP ) 27.2 Hz,
Ru-PPh3), 46.41 (dbs, 2J PP ) 27.2 Hz, Ru-PPh3)). The
two nonequivalent PPh3 ligands are in accordance with
the structure in the solid state and seem to indicate that
the alkenyl group does not rotate around the Ru-CR
bond, due likely to the steric hindrance of the bulky
phosphine ligands.
The H and 13C{1H} NMR spectra also support the
1
Studies carried out in our laboratory indicate that the
stability of vinylidene and allenylidene moieties are also
strongly influenced by the electrophilicity of the ruthe-
nium substrate, e.g. [Ru(1,2,3-Me3C9H4)(CO)L] (L )
PPh3, PiPr3).21 Further reactivity and theoretical
(EHMO) studies on these unsaturated carbene com-
plexes and related derivatives are in progress.
(E)-alkenyl configuration. We note in particular (i) the
typical downfield resonance of the vinylic hydrogen,
1
which appears in the H NMR spectra as a doublet of
virtual triplets, due to the coupling with the phospho-
nium phosphorus nucleus (13a , δ 10.25 (3J HP ) 35.0 Hz);
14a , δ 10.20 (3J HP ) 34.9 Hz)) and with the two
nonequivalent phosphorus nuclei bonded to ruthenium
3
3
3
3
(13a , J HP ) J HP′ ) 10.3 Hz; 14a , J HP ) J HP′ ) 10.1
Hz) and (ii) the typical low-field resonance for the Ru-
CR atom in alkenyl complexes in the 13C{1H} NMR
spectra, which appears as a multiplet at δ 198.30 (13a )
and 196.51 (14a ).
Exp er im en ta l Section
The manipulations were performed under dry nitrogen
using vacuum-line and standard Schlenk techniques. All
reagents were obtained from commercial suppliers and used
without further purification. Solvents were dried by standard
methods and distilled under nitrogen before use. The com-
plexes [RuCl(η5-C9H7)L2] (L ) PPh3,22 L2 ) dppe23 ) were
prepared by following the methods reported in the literature.
Infrared spectra were recorded on a Perkin-Elmer 1720-XFT
spectrometer. Mass spectra (FAB) were recorded using a VG-
Autospec spectrometer, operating in the possitive mode; 3-ni-
trobenzyl alcohol (NBA) was used as the matrix. The conduc-
tivities were measured at room temperature, in ca. 10-3 mol
dm-3 acetone solutions, with a J enway PCM3 conductometer.
The C and H analyses were carried out with a Perkin-Elmer
240-B microanalyzer. NMR spectra were recorded on a Bruker
AC300 instrument at 300 MHz (1H), 121.5 MHz (31P), or 75.4
MHz (13C) using SiMe4 or 85% H3PO4 as standard. 1H, 13C-
{1H}, and 31P{1H} NMR spectroscopic data for the vinylvi-
nylidene and enynyl complexes are collected in Tables 1-4.
Providing that a formal addition of PPh3 to the Câ
atom of the vinylidene chain is found, we have examined
the reactivity of the neutral enynyl complexes 6a and
7a toward triphenylphosphine. Similarly, the treat-
ment of 6a and 7a with an excess of PPh3 in refluxing
methanol and in the presence of NaPF6 also affords
complexes 13a and 14a (Scheme 4). The formation of
13a and 14a is unusual, since typical nucleophilic
additions to the CR atom of the vinylidene group should
be expected. The reactions were monitored by 31P{1H}
NMR spectroscopy, but no further resonances besides
those of the enynyl complexes 6a and 7a and the final
products 13a and 14a were observed. Since the mech-
anism of these atypical reactions is still unknown,
further work using nucleophilic attacks on a series of
ruthenium(II) vinylidene complexes is in progress.20
Syn th esis of [Ru {dCdC(H)CdCHCH2(CH2)n CH2}(η5-
C9H7)L2][P F 6] (n ) 1, L ) P P h 3 (2a ), L2 ) d p p e (2b); n )
2, L ) P P h 3 (3a ), L2 ) d p p e (3b); n ) 3, L ) P P h 3 (4a ), L2
) d p p e (4b)). Gen er a l p r oced u r e. To a solution of [RuCl-
(η5-C9H7)L2] (1a ,b; 1 mmol) in 50 mL of MeOH were added
NaPF6 (336 mg, 2 mmol), MgSO4 (3 g, 25 mmol), and the
corresponding propargylic alcohol (2 mmol). The reaction
mixture was heated under reflux for 30 min. The solvent was
then removed under vacuum, the crude product extracted with
CH2Cl2, and the extract filtered. Concentration of the result-
ing solution to ca. 5 mL followed by the addition of 50 mL of
diethyl ether precipitated a brown solid, which was washed
with diethyl ether (2 × 20 mL) and dried in vacuo. Yield (%),
IR (KBr, ν(PF6-), cm-1), analytical data, conductivity (acetone,
20 °C, Ω-1 cm2 mol-1), and mass spectral data (FAB, m/e) are
as follows. 2a : 68; 838. Anal. Calcd for RuC52H45F6P3: C,
63.86; H, 4.64. Found: C, 63.45; H, 4.58. 125. 2b: 56; 838.
Anal. Calcd for RuC42H39F6P3: C, 59.22; H, 4.61. Found: C,
59.67; H, 4.96. 115. 3a : 66; 840. Anal. Calcd for
RuC53H47F6P3: C, 64.17; H, 4.77. Found: C, 63.82; H, 4.98.
123. [M+] ) 847, [M+ - C8H10] ) 741. 3b: 76; 837. Anal.
Calcd for RuC43H41F6P3: C, 59.65; H, 4.77. Found: C, 59.01;
H, 4.69. 122. 4a : 80; 838. Anal. Calcd for RuC54H49F6P3: C,
64.47; H, 4.91. Found: C, 63.87; H, 5.11. 113. 4b: 89; 837.
Con clu sion s
We have recently reported that the activation of
2-propyn-1-ol derivatives containing aromatic substit-
uents by indenylruthenium(II) complexes [RuCl(η5-
C9H7)L2] (L ) PPh3; L2 ) dppe, dppm) selectively affords
allenylidene complexes [Ru(dCdCdCR2)(η5-C9H7)L2]-
[PF6].5d In this work it is shown that the activation of
1-ethynyl-1-cycloalkanols by indenylruthenium(II) com-
plexes gives selectively the vinylvinylidene complexes
[Ru{dCdC(H)CdCHCH2(CH2)nCH2}(η5-C9H7)L2][PF6]
(L ) PPh3; L2 ) 1,2-bis(diphenylphosphino)ethane
(dppe)). This behavior can be compared to that shown
by the similar ruthenium(II) complex [RuCl(η5-C5H5)-
(PPh3)2].6a In contrast, we have also reported that the
activation of 1-ethynyl-1-cyclohexanol by [RuCl(η5-C9H7)-
(PPh3)2] gives an unprecedented allenylidene complex,
namely [Ru(dCdCdC(C13H20))(η5-C9H7)(PPh3)2][PF6],
which contains the bicyclic [3.3.1]non-2-en-9-ylidene
(20) A reviewer has brought to our attention that alkenyl-phos-
phonio complexes (13a and 14a ) could be formally generated from the
nucleophilic attack of PPh3 the π-alkyne complexes [Ru(η2-HCtCR)-
(η5-C9H7)(PPh3)2][PF6] (R ) 1-cyclohexenyl, 1-cycloheptenyl). Theoreti-
cal and experimental studies focused on the potential equilibrium
between these complexes and the corresponding vinylidene tautomers
will be undertaken.
(21) Gamasa, M. P.; Gimeno, J .; Gonza´lez-Bernardo, C.; Borge, J .;
Garc´ıa-Granda, S. Organometallics, in press.
(22) Oro, L. A.; Ciriano, M. A.; Campo, M.; Foces-Foces, C.; Cano,
F. H. J . Organomet. Chem. 1985, 289, 117.
(23) Gamasa, M. P.; Gimeno, J .; Gonza´lez-Bernardo, C.; Mart´ın-
Vaca, B. M.; Monti, D.; Bassetti, M. Organometallics 1996, 15, 302.

3186 Organometallics, Vol. 16, No. 14, 1997
Cadierno et al.
Anal. Calcd for RuC44H43F6P3: C, 60.06; H, 4.90. Found: C,
59.79; H, 5.03. 120.
5J PP ) 3.9 Hz, Ru-PPh3); 1H (CD2Cl2) δ 1.47 (m, 2H, CH2),
1.56 (m, 2H, CH2), 1.82 (m, 4H, 2 CH2), 2.34 (m, 2H, CH2),
4.48 (m, 3H, H-1,3 and H-2), 5.63 (m, 2H, Ind6), 6.82-7.74
Syn th esis of [Ru {CtCCdCHCH2(CH2)n CH2}(η5-C9H7)-
L2] (n ) 1, L ) P P h 3, (5a ), L2 ) d p p e (5b); n ) 2, L ) P P h 3
(6a ), L2 ) d p p e (6b); n ) 3, L ) P P h 3 (7a ), L2 ) d p p e (7b)).
Gen er a l p r oced u r e. A mixture of the corresponding vinylvi-
nylidene complex 2-4 (1 mmol) and Al2O3 (10 mL) in 50 mL
of CH2Cl2 was stirred at room temperature for 2 h. The
mixture was then evaporated under reduced pressure, the
residue extracted with diethyl ether, and the extract filtered.
Evaporation of the diethyl ether gave 5-7 as orange solids.
Yield (%), IR (KBr, ν(CtC), cm-1), analytical data, and mass
spectral data (FAB, m/e) are as follows. 5a : 88; 2069. Anal.
Calcd for RuC52H44P2: C, 75.07; H, 5.33. Found: C, 75.27; H,
5.42. 5b: 97; 2068. Anal. Calcd for RuC42H38P2: C, 71.47;
H, 5.42. Found: C, 70.89; H, 5.88. 6a : 84; 2051. Anal. Calcd
for RuC53H46P2: C, 75.25; H, 5.48. Found: C, 74.71; H, 5.73.
[M+] ) 846, [M+ - C8H9] ) 741, [M+ - C8H9 - C9H7] ) 625,
[M+ - PPh3] ) 583. 6b : 91; 2062. Anal. Calcd for
RuC43H40P2: C, 71.75; H, 5.60. Found: C, 71.03; H, 5.81. 7a :
94; 2066. Anal. Calcd for RuC54H48P2: C, 75.42; H, 5.62.
Found: C, 74.84; H, 5.68. 7b : 92; 2058. Anal. Calcd for
RuC44H42P2: C, 72.01; H, 5.77. Found: C, 71.21; H, 6.01.
2
(m, 47H, Ph, Ind6); 13C{1H} (CD2Cl2) δ 21.90 (d, J CP ) 10.9
Hz, 2 CH2), 21.18 (s, CH2), 34.73 (s, 2 CH2), 44.22 (d, J CP
45.3 Hz, Cγ), 73.39 (s, C-1,3), 95.29 (s, C-2), 103.84 (d, J CP
)
)
2
6.8 Hz, Câ), 110.81 (s, C-3a,7a), 113.19 (m, Ru-CR), 119.07-
138.99 (m, Ph, Ind6); ∆δ(C-3a,7a) ) -19.89.
Syn t h esis
of
(E)-[R u {C(H )dC(P P h 3)CdCH CH 2-
(CH2)n CH2}(η5-C9H7)(P P h 3)2] [P F 6] (n ) 2 (13a ), 3 (14a )).
Gen er a l p r oced u r e. A mixture of the corresponding vinylvi-
nylidene complex 3a and 4a (1 mmol) and PPh3 (2.623 g, 10
mmol) in 50 mL of MeOH was heated under reflux for
approximately 1 h. The solution was then evaporated to
dryness, the solid residue was extracted with CH2Cl2 (ca. 20
mL), and the extracts were filtered into 100 mL of stirred
diethyl ether, giving a yellow precipitate. The solution was
decanted and the solid washed with diethyl ether (2 × 20 mL)
and vacuum-dried. Yield (%), IR (KBr, ν(PF6-), cm-1), analyti-
cal data, NMR spectroscopic data (ppm), and mass spectral
data (FAB, m/e) are as follows. 13a : 72; 841. Anal. Calcd for
RuC71H62F6P4: C, 67.99; H, 4.98. Found: C, 67.59; H, 4.85.
4
4
31P{1H} (CDCl3) δ 11.92 (dd, J PP ) 6.0 Hz, J PP ) 3.8 Hz,
C-PPh3), 43.18 (dd, 2J PP ) 29.6 Hz, 4J PP ) 6.0 Hz, Ru-PPh3),
46.24 (dd, 2J PP ) 29.6 Hz, 4J PP ) 3.8 Hz, Ru-PPh3); 1H (CDCl3)
Syn th esis of [Ru {dCdC(Me)CdCHCH2(CH2)2CH2}(η5-
C9H7)(P P h 3)2][CF 3SO3] (8a ). A stirred solution of 6a (846
mg, 1 mmol) in diethyl ether (50 mL), at room temperature,
was treated dropwise with a dilute solution of MeOSO2CF3 in
diethyl ether. Inmediately, an insoluble solid precipitated but
the addition was continued until no further solid was formed.
The solution was decanted and the solid washed with diethyl
ether (2 × 25 mL) and vacuum-dried. Slow crystallization in
a CH2Cl2/hexane (1:4) mixture gave 8a as orange-brown
crystals. Yield (%), IR (KBr, ν(CF3SO3), cm-1), analytical data,
conductivity (acetone, 20 °C, Ω-1 cm2 mol-1), and NMR
spectroscopic data (ppm) are as follows. 63; 1270, 1225, 1156.
Anal. Calcd for RuC54H45F3O3P2S: C, 65.24; H, 4.56. Found:
C, 64.52; H, 4.70. 104. 31P{1H} (CD2Cl2) δ 39.35 (s); 1H (CD2-
Cl2) δ 0.85 (m, 2H, CH2), 1.32 (m, 2H, CH2), 1.47 (m, 2H, CH2),
1.50 (s, 3H, CH3), 2.24 (m, 2H, CH2), 5.30 (bs, 2H, H-1,3), 5.54
and 7.11 (m, 2H each, H-4,7 and H-5,6), 5.68 (bs, 1H, H-2),
5.96 (bs, 1H, dCH), 6.69-7.45 (m, 30H, Ph); 13C{1H} (CD2-
Cl2) δ 10.38 (s, CH3), 22.62 (s, CH2), 23.50 (s, CH2), 26.81 (s,
CH2), 26.84 (s, CH2), 81.04 (s, C-1,3), 100.12 (s, C-2), 116.95
(s, C-3a,7a), 123.98-135.37 (m, Ph, Câ, dC, dCH, Ind6), 352.77
δ 1.23 (m, 4H, 2 CH2), 1.60 (m, 4H, 2 CH2), 4.92, 5.00, and
4
5.05 (bs, 1H each one, H-1, H-2 and H-3), 5.27 (d, 1H, J HP
)
7.2 Hz, dCH), 6.16 (m, 2H, Ind6), 6.55-7.67 (m, 47H, Ph, Ind6),
10.25 (dvt, 1H, J HP ) 35.0 Hz, J HP ) 3J HP′) 10.3 Hz, dCH);
3
3
13C{1H} (CDCl3) δ 20.64 (s, CH2), 22.04 (s, CH2), 25.45 (s, CH2),
2
31.34 (s, CH2), 73.22 (d, J CP ) 9.7 Hz, C-1 or C-3), 74.79 (d,
2J CP ) 7.1 Hz, C-1 or C-3), 92.33 (s, C-2), 109.48 and 118.79
(s, C-3a and C-7a), 117.53-138.53 (m, Ph, Ind6, dCH, dC),
198.30 (m, Ru-CR) ppm; ∆δ(C-3a,7a) ) -16.56. [M+] ) 1109,
[M+ - PPh3] ) 847, [M+ - 2PPh3] ) 585. 14a : 79; 839. Anal.
Calcd for RuC71H62F6P4: C, 68.19; H, 5.09. Found: C, 68.22;
H, 4.98. 31P{1H} (CDCl3) δ 12.33 (bs, C-PPh3), 43.11 (dbs,
2J PP ) 27.2 Hz, Ru-PPh3), 46.41 (dbs, J PP ) 27.2 Hz, Ru-
2
1
PPh3); H (CDCl3) δ 1.47 (m, 2H, CH2), 1.69 (m, 4H, 2 CH2),
2.23 (m, 2H, CH2), 2.41 (m, 2H, CH2), 4.91 (m, 2H, dCH and
Ind5), 5.10 and 5.27 (bs, 1H each, Ind5), 6.24 (m, 2H, Ind6),
3
6.52-7.62 (m, 47H, Ph, Ind6), 10.20 (dvt, 1H, J HP ) 34.9 Hz,
3J HP ) 3J HP′ ) 10.1 Hz, dCH); 13C{1H} (CDCl3) δ 24.96 (s, CH2),
25.80 (s, CH2), 28.92 (s, CH2), 29.67 (s, CH2), 37.42 (s, CH2),
72.85 (d, 2J CP ) 5.2 Hz, C-1 or C-3), 74.94 (s, C-1 or C-3), 92.61
(s, C-2), 109.16 and 118.19 (s, C-3a and C-7a), 120.91-142.42
(m, Ph, Ind6, dCH, dC), 196.51 (m, Ru-CR); ∆δ(C-3a,7a) )
-17.02.
2
(t, J CP ) 17.7 Hz, RudCR); ∆δ(C-3a,7a) ) -13.75.
Syn th esis of [Ru {CtCC(P P h 3)CH2CH2(CH2)n CH2}(η5-
C9H7)(P P h 3)2][P F 6] (n ) 1 (11a ), 2 (12a )). Gen er a l p r o-
ced u r e. A mixture of [RuCl(η5-C9H7)(PPh3)2] (776 mg, 1
mmol), NaPF6 (336 mg, 2 mmol), PPh3 (2.623 g, 10 mmol), and
the corresponding propargylic alcohol (2 mmol) in 50 mL of
MeOH was stirred at room temperature for 8 h. A yellow
suspension was formed. The solvent was then decanted, the
residue dissolved in CH2Cl2 (ca. 40 mL), and this solution
filtered. The resulting solution was evaporated to dryness
and the yellow solid obtained washed with diethyl ether (2 ×
20 mL) and vacuum-dried. Yield (%), IR (KBr, ν(CtC),
ν(PF6-), cm-1), analytical data, and NMR spectroscopic data
(ppm) are as follows. 11a : 73; 2054, 837. Anal. Calcd for
RuC70H60F6P4: C, 67.79; H, 4.87. Found: C, 67.61; H, 4.80.
X-r a y Diffr a ction Stu d ies. Com p lex 8a . Data collection,
crystal, and refinement parameters are collected in Table 9.
The unit cell parameters were obtained from the least-squares
fit of 25 reflections (with θ between 15 and 18°). Data were
collected with the ω-2θ scan technique and a variable scan
rate, with a maximum scan time of 60 s per reflection. The
final drift correction factors were between 0.99 and 1.76. On
all reflections, profile analysis24,25 was performed. Lorentz and
polarization corrections were applied, and the data were
reduced to |Fo| values.
The structure was solved by SHELXS8626 (Patterson meth-
ods) and DIRDIF27 (phase expansion). Isotropic least-squares
refinement, using SHELX76,28,29 converged to R ) 0.083. At
5
31P{1H} (CD2Cl2) δ 28.85 (t, J PP ) 3.8 Hz, C-PPh3), 49.34 (d,
5J PP ) 3.8 Hz, Ru-PPh3); 1H (CD2Cl2) δ 1.37 (m, 2H, CH2),
1.68 (m, 2H, CH2), 2.08 (m, 2H, CH2), 2.38 (m, 2H, CH2), 4.30
(d, 2H, J HH ) 2.2 Hz, H-1,3), 4.47 (t, 1H, J HH ) 2.2 Hz, H-2),
5.66 and 6.73 (m, 2H each, H-4,7 and H-5,6), 6.83-7.94 (m,
(24) Grant, D. F.; Gabe, E. J . J . Appl. Crystallogr. 1978, 11, 114.
(25) Lehman, M. S.; Larsen, F. K. Acta Crystallogr., Sect. A 1974,
30, 580.
(26) Sheldrick, G. M. SHELX86. In Crystallographic Computing 3;
Sheldrick, G. M., Kruger, C., Goddard, R., Eds.; Clarendon Press:
Oxford, U.K., 1985.
(27) 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; Technical Report; Crystallographic Labora-
tory, University of Nijmegen: Nijmegen, The Netherlands, 1992.
(28) Sheldrick, G. M. SHELX76: Program for Crystal Structure
Determination; University of Cambridge: Cambridge, U.K., 1976.
2
45H, Ph); 13C{1H} (CD2Cl2) δ 25.56 (d, J CP ) 9.9 Hz, 2 CH2),
40.44 (s, 2 CH2), 44.96 (d, J CP ) 49.0 Hz, Cγ), 73.94 (s, C-1,3),
2
95.17 (s, C-2), 107.12 (d, J CP ) 3.5 Hz, Câ), 110.22 (s, C-3a,-
7a), 112.15 (m, Ru-CR), 119.61-138.72 (m, Ph, Ind6); ∆δ(C-
3a,7a) ) -20.48. 12a : 61; 2050, 840. Anal. Calcd for
RuC71H62F6P4: C, 67.99; H, 4.98. Found: C, 67.42; H, 4.89.
5
31P{1H} (CD2Cl2) δ 25.42 (t, J PP ) 3.9 Hz, C-PPh3), 49.02 (d,

Indenylruthenium(II) Vinylvinylidene Complexes
Organometallics, Vol. 16, No. 14, 1997 3187
Ta ble 9. Cr ysta llogr a p h ic d a ta for Com p lexes 8a
a n d 13a
θ between 10 and 12°). Data were collected with the ω-2θ
scan technique and a variable scan rate, with a maximum scan
time of 60 s per reflection. The final drift correction factors
were between 0.97 and 1.14. On all reflections, profile
analysis24,25 was performed. Lorentz and polarization correc-
8a
13a
formula
a, Å
b, Å
C55H49F3O3P2RuS
37.29(1)
14.123(3)
17.912(9)
97.99(4)
1010.06
9342(7)
C76H74Cl2F6OP4Ru
11.335(5)
29.62(5)
20.116(9)
93.03(4)
1413.20
2
tions were applied, and the data were reduced to |Fo| values.
The structure was solved by DIRDIF27 (Patterson methods
and phase expansion). Isotropic full-matrix least-squares
c, Å
â, deg
mol wt
V, Å3
2
refinement on |Fo| using SHELXL9334 converged to R ) 0.127.
At this stage an empirical absorption correction was applied
using XABS2.35 Maximum and minimum transmission factors
were 1.00 and 0.78, respectively.
6745(12)
1.392
D
calcd, g cm-3
1.43
F(000)
4160
2920
wavelength, Å
temp, K
0.71073
200
0.71073
200
Finally, all hydrogen atoms (except H(1)) were geometrically
placed. During the final stages of the refinement, the posi-
tional parameters and the anisotropic thermal parameters of
the non-H atoms were refined. The geometrically placed
hydrogen atoms were isotropically refined, riding on their
parent atoms, with two common thermal parameters; one
for the hydrogen atoms bonded to aromatic rings and the
other for the hydrogen atoms bonded to the cyclohexenyl ring.
H(1) was independently (and also isotropically) refined. The
function minimized was [∑w(Fo2 - Fc2)2/∑w(Fo2)2]1/2 (w ) 1/[σ2
(Fo2) + (0.0777P)2 + 19.62P], where P ) (Max(Fo2, 0) + 2Fc2)/3
with σ2 (Fo2) from counting statistics).
The CH2Cl2 solvent molecule was affected by strong struc-
tural disorder. Its hydrogen atoms were omitted during the
refinement. C and Cl atoms were anisotropically refined. Cl-
(2) was found in two disordered positions (occupation factors
0.515(8) and 0.485(8)).
The Et2O solvent molecule was also affected by very strong
structural disorder and could not be located exactly; instead,
it was omitted from the parameter set of the refined discrete-
atom model. It was taken into account in the structure factor
calculations by direct Fourier transformation of the electron
density in the corresponding cavity, using the BYPASS36
procedure.
radiation
Mo KR
Mo KR
monochromator
space group
cryst syst
graphite cryst
C2/c
graphite cryst
P21/c
monoclinic
0.39, 0.33, 0.19
0.49
0.60-1.00
ω-2θ
1.00-25.00
-44 e h e +43
0 e k e +16
0 e l e +21
9253
monoclinic
0.52, 0.40, 0.33
0.468
0.78-1.00
ω-2θ
1.22-22.99
-12 e h e +12
0 e k e +32
0 e l e +22
9922
cryst size, mm
µ, mm-1
range of abs
diffraction geom
θ range, deg
index ranges for
data collecn
no. of rflns measd
no. of indep rflns
no. of variables
agreement between
equiv rflnsa
8221
587
0.027
9367
782
0.026
final R factors
R(I > 3σ(I))
R ) 0.040
Rw ) 0.041
final R factors
R(I > 2σ(I))
R1 ) 0.053
Rw2 ) 0.146
R1 ) 0.080
Rw2 ) 0.156
final R factors
R(all data)
a
Rint ) ∑(I - I )/∑I.
The maximum shift to esd ratio in the last full-matrix least-
squares cycle was 0.201. The final difference Fourier map
showed no peaks higher than 1.01 e Å-3 (near the disordered
CH2Cl2 solvent molecule) or deeper than -0.78 e Å-3. Atomic
scattering factors were taken from ref 31. Geometrical
calculations were made with PARST.32 The crystallographic
plots were made with EUCLID.33 All calculations were
performed at the University of Oviedo on the Scientific
Computer Center and X-ray group VAX computers.
this stage additional empirical absorption correction was
applied using DIFABS,30 resulting in a further decrease of R
to 0.075. The maximum and minimum absorption correction
factors were respectively 1.00 and 0.60. Hydrogen atoms were
geometrically placed.
During the final stages of the refinement the positional
parameters and the anisotropic thermal parameters of the
non-H atoms were refined. The hydrogen atoms were isotro-
pically refined with
a common thermal parameter. The
function minimized was ∑w(Fo - Fc)2 (w ) 1/[σ2(Fo) + (0.0004
Fo2)], with σ(Fo) from counting statistics). The maximum shift
to esd ratio in the last full-matrix least-squares cycle was
0.008. The final difference Fourier map showed no peaks
higher than 0.43 e Å-3 or deeper than -0.40 e Å-3. Atomic
scattering factors were taken from ref 31. Geometrical
calculations were made with PARST.32 The crystallographic
plots were made with EUCLID.33 All calculations were
performed at the University of Oviedo on the Scientific
Computer Center and X-ray group VAX computers.
Ack n ow led gm en t. This work was supported by the
Direccio´n General de Investigacio´n Cient´ıfica y Te´cnica
(Project PB93-0325) and the EU (Human Capital Mobil-
ity program, Project ERBCHRXCT 940501). We thank
the Fundacio´n para la Investigacio´n Cient´ıfica y Te´cnica
de Asturias (FICYT) for a fellowship to V.C.
Su p p or tin g In for m a tion Ava ila ble: Crystal structure
data for 8a and 13a , including tables of atomic parameters,
anisotropic thermal parameters, bond distances, and bond
angles (33 pages). Ordering information is given on any
current masthead page.
Com p lex 13a . Data collection, crystal, and refinement
parameters are collected in Table 9. The unit cell parameters
were obtained from the least-squares fit of 25 reflections (with
OM970146F
(29) van der Maelen Ur´ıa, J . F. Ph.D. Thesis, University of Oviedo,
1991.
(30) Walker, N.; Stuart, D. Acta Crystallogr., Sect. A 1983, 39, 158.
(31) International Tables for X-Ray Crystallography; Kynoch
Press: Birminghan, U.K., 1974; Vol. IV.
(34) Sheldrick, G. M. SHELXL93. In Crystallographic Computing
6; Flack, P., Parkanyi, P., Simon, K., Eds.; IUCr/Oxford University
Press: Oxford, U.K., 1993.
(35) Parkin, S.; Moezzi, B.; Hope, H. J . Appl. Crystallogr. 1995, 28,
53.
(32) Nardelli, M. Comput. Chem. 1983, 7, 95.
(33) Spek, A. L. The EUCLID Package. In Computional Crystal-
lography; Sayre, D., Ed.; Clarendon Press: Oxford, U.K., 1982; p 528.
(36) van der Sluis, P.; Spek, A. L. Acta Crystallogr., Sect. A 1990,
46, 194.