Indenylruthenium(II) aminoallenylidenes: New building blocks for the synthesis of highly unsaturated alkynyl and allenylidene complexes

Article abstract of DOI:10.1021/om049413p

The synthesis of high unsaturated alkynyl and allenylidene complexes were carried out. Complexes were characterized by elemental analysis and spectroscopic techniques, which support the proposed hydrocarbon moieties. ¹H and ¹³C{

Full text of DOI:10.1021/om049413p

Organometallics 2004, 23, 6299-6310
6299
Indenylruthenium(II) Aminoallenylidenes: New Building
Blocks for the Synthesis of Highly Unsaturated Alkynyl
and Allenylidene Complexes
Salvador Conejero, Josefina D´ıez, Mar´ıa Pilar Gamasa, and Jose´ Gimeno*
Departamento de Quı´mica Orga´nica e Inorga´nica/IUQOEM, Facultad de Quı´mica,
Universidad de Oviedo-CSIC, 33071 Oviedo, Spain
Received July 29, 2004
The allenylidene complexes [Ru(dCdCdCRPh)(η5-C9H7)(PPh3)2][PF6] (R ) Ph (1); R ) H
(2)) react with the ynamines R′CtCNEt2 (R′ ) Me, SiMe3), yielding the aminoallenylidenes
[Ru{dCdCdC(NEt2)[C(R′)dC(R)Ph]}(η5-C9H7)(PPh3)2][PF6] (R ) Ph, R′ ) Me (3); R ) H,
R′ ) Me (4); R ) Ph, R′ ) SiMe3 (5)). The reactions proceed regio- and stereoselectively, the
insertion of the ynamine taking place exclusively at the CâdCγ bond of the unsaturated
chain. The analogous allenylidene complex 6 (R′ ) H, R ) Ph) is obtained by desylilation of
complex 5 with KF. The treatment of complex 3 with HBF4 leads to the formation of the
dicationic vinylidene [Ru{dCdC(H)C(dNEt2)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2]2+ (7). The
aminoallenylidene complex 3 undergoes regioselective nucleophilic additions of acetylides
and other carbanions at the Cγ atom, yielding (i) the disubstituted alkynylalkenylallen-
ylidenes [Ru{dCdCdC(CtCR)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2][BF4] (R ) Ph (8), SiMe3 (9))
from the addition of acetylides LiCtCR, (ii) the 3-alkenyl-3,4,5-hexatrien-1-ynyl derivatives
[Ru{CtCC(dCdCdCRR′)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2] (R ) R′ ) Me (10); R ) Ph, R′ )
H (11)) from the reaction with LiCtCCHRR′, and (iii) the 3-alkenyl-3-buten-1-ynyl species
[Ru{CtCC(dCHR)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2] (R ) H (12), R ) n-Pr (13)) and the
3-alkenyl-3,5-hexadien-1-ynyl complex [Ru{CtCC(dCHCHdCH2)[C(Me)dCPh2]}(η5-C9H7)-
(PPh3)2] (14) from the treatment with LiCH2R (R ) H, n-Pr) and BrMgCH2CHdCH2,
respectively. The secondary allenylidenes [Ru{dCdCdC(H)[C(R)dCPh2]}(η5-C9H7)(PPh3)2]-
[PF6] (R ) Me (16), R ) H (17)) are obtained in a one-pot synthesis from the reactions of
aminoallenylidenes 3 and 6 with LiBHEt3 and subsequent treatment with silica, respectively.
Highly unsaturated alkenylaminoallenylidenes of the general formula [Ru{dCdCdC(NEt2)-
[(CRdCH)nC(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (n ) 1, R ) Me (18), R ) SiMe3 (19); n ) 2,
R ) Me (22)) have been synthesized by regio- and stereoselective sequential insertion of
one or two ynamines RCtCNEt2 (R ) Me, SiMe3) into the CâdCγ bond of the cumulene
group of complexes [Ru{dCdCdC(H)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (16) and [Ru{d
CdCdC(H)[(CMedCH)C(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (21), respectively. Structures of
complexes 3 and 18 have been confirmed by X-ray crystallography.
Introduction
tant developments in a number of stoichiometric and
catalytic transformations. As part of the well-known
applications of ruthenium complexes in organic synthe-
sis, the reactivity of allenylidene and higher cumulen-
ylidene ruthenium(II) complexes has attracted special
attention.2 To date, a wide number of C-C and C-het-
eroatom coupling reactions are well represented. Allen-
ylidene and butatrienylidene complexes have emerged
as useful starting materials for the synthesis of metal-
bonded heterocycles.3 The rapid development of this
chemistry probably stems from the presence in the
carbon chain of both electrophilic and nucleophilic sites,
which provide an unusually versatile reactivity.4 An
interesting class of derivatives are those in which the
cumulenylidene chains dC(dC)ndCR1R2 also contain
other types of R,â-unsaturated functional groups (R1
and/or R2 unsaturated hydrocarbon chain). The presence
of such a type of highly unsaturated hydrocarbon moiety
should increase the scope of the reactive sites. However,
The applications in organic synthesis of unsaturated
Fischer type and other electrophilic carbenes continue
disclosing efficient synthetic alternatives to classical
procedures.1 In particular, during the past few years the
chemistry of the carbenes belonging to the cumulen-
ylidene series [M]dC(dC)ndCR1R2 has provided impor-
* To whom correspondence should be addressed. Fax: (+34)-
985103446. E-mail: jgh@fq.uniovi.es.
(1) (a) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043.
(b) Do¨rwald Zaragoza, F. Metal Carbenes in Organic Chemistry; Wiley-
VCH: Weinheim, Germany, 1999. (c) Do¨tz, K. H.; Jahr, H. C. In
Carbene Chemistry; Bertrand, G., Ed.; Marcel Dekker: New York,
2002; Chapter 8. (d) Cadierno, V.; Gamasa, M. P.; Gimeno, J. Coord.
Chem. Rev. 2004, 248, 1627-1657.
(2) For recent reviews see: (a) Werner, H.; Ilg, K.; Lass, R.; Wolf, J.
J. Organomet. Chem. 2002, 661, 137-147. (b) Cadierno, V.; Gamasa,
M. P.; Gimeno, J. Eur. J. Inorg. Chem. 2001, 571-591. (c) Touchard,
D.; Dixneuf, P. H. Coord. Chem. Rev. 1998, 178-180, 409-429. (d)
Bruce, M. I. Chem. Rev. 1998, 98, 2797-2858. (e) Werner, H. Chem.
Commun. 1997, 903-910. (f) Le Bozec, H.; Dixneuf, P. H. Russ. Chem.
Bull. 1997, 44, 801.
10.1021/om049413p CCC: $27.50 © 2004 American Chemical Society
Publication on Web 11/16/2004

6300 Organometallics, Vol. 23, No. 26, 2004
Conejero et al.
Chart 1
Scheme 1
Results and Discussion
despite the potential synthetic applications only a few
examples are known.1d The main drawback to achieving
the desired unsaturated cumulenylidene precursors is
the lack of systematic synthetic routes. Herein, we
report an efficient and stereoselective synthetic meth-
odology of indenylruthenium(II) complexes containing
highly unsaturated hydrocarbon moieties, including (i)
polyalkenylallenylidene chains {dCdCdC(R)[(CR′d
CH)nC(Me)dCPh2]} (I: n ) 1, 2, R ) H, NEt2, R′ ) Me;
n ) 1, R ) NEt2, R′ ) SiMe3) (Chart 1), which are
obtained via sequential insertion of ynamines, RCt
CNEt2 (R ) Me, SiMe3), into the readily accessible
cationic allenylidene precursors [Ru(dCdCdCRPh)(η5-
C9H7)(PPh3)2]+ and (ii) unsaturated allenylidene and
alkynyl chains of the types II and III-V, respectively
(Chart 1), prepared through regio- and stereoselective
nucleophilic additions of carbanions onto the aminoal-
lenylidene [Ru{dCdCdC(NEt2)[C(Me)dCPh2]}(η5-C9H7)-
(PPh3)2]+. These processes are representative examples
of a new synthetic approach to building up unprec-
edented highly unsaturated hydrocarbon chains. Part
of this work has been communicated previously.5
Synthesis of Alkenylaminoallenylidene Com-
plexes [Ru{dCdCdC(NEt2)[C(R′)dC(R)Ph]}(η5-C9-
H7)(PPh3)2][PF6] (R ) Ph, R′ ) Me (3); R ) H, R′ )
Me (4); R ) Ph, R′ ) SiMe3 (5); R ) Ph, R′ ) H (6)).
Allenylidene complexes [Ru(dCdCdCRPh)(η5-C9H7)-
(PPh3)2][PF6] (R ) Ph (1), H (2))4h react rapidly with
6
an excess of the ynamine MeCtCNEt2 in tetrahydro-
furan at 0 °C, yielding regio- and stereoselectively the
alkenylaminoallenylidene complexes 3 and 4 (71-87%
yield) (Scheme 1).7 Similarly, the treatment of a solution
of complex 1 in tetrahydrofuran with Me3SiCtCNEt2,
at room temperature over 12 h, affords the analogous
allenylidene complex 5 (64% yield). The desilylated
complex 6 is readily obtained (96% yield) by the reaction
of 5 with KF in methanol at room temperature (Scheme
1).
Complexes 3-6 are isolated as crystalline air-stable
orange solids. Analytical and spectroscopic data (IR and
1H, 31P{1H}, and 13C{1H} NMR) of 3-6 support the
proposed formulation (see Experimental Section). The
most significant features of the spectroscopic data are
(i) the characteristic ν(CdCdC) strong absorption at
1980-1992 cm-1 in the IR spectra, (ii) the low-field
signals for the allenylidene carbon nuclei in the 13C-
{1H} NMR spectra, which appear in the ranges 195.87-
(3) (a) Buil, M. L.; Esteruelas, M. A.; Lo´pez, A. M.; On˜ate, E.
Organometallics 2003, 22, 5274-5284. (b) Harbort, R.-C.; Hartmann,
S.; Winter, R. F.; Klinkhammer, K. W. Organometallics 2003, 22,
3171-3174. (c) Buil, M. L.; Esteruelas, M. A.; Lo´pez, A. M.; On˜ate, E.
Organometallics 2003, 22, 162-171. (d) Cadierno, V.; Conejero, S.;
Gamasa, M. P.; Gimeno, J. Organometallics 2001, 20, 3175-3189. (e)
Bernard, D. J.; Esteruelas, M. A.; Lo´pez, A. M.; Oliva´n, M.; On˜ate, E.;
Puerta, M. C.; Valerga, P. Organometallics 2000, 19, 4327-4335. (f)
Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Oliva´n, M.; On˜ate, E.;
Ruiz, N. Organometallis 2000, 19, 4-14. (g) Esteruelas, M. A.; Go´mez,
A. V.; Lo´pez, A. M.; Oliva´n, M.; On˜ate, E.; Ruiz, N. Organometallics
1999, 18, 1606-1614. (h) Bruce, M. I.; Ke, M.; Kelly, B. D.; Low, P. J.;
Smith, M. E.; Skelton, B. W.; White, A. H. J. Organomet. Chem. 1999,
590, 184-201. (i) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Puerta,
M. C.; Valerga, P. Organometallics 1998, 17, 4959-4965. (j) Esteruelas,
M. A.; Go´mez, A. V.; Lo´pez, A. M.; On˜ate, E. Organometallics 1998,
17, 3567-3573. (k) Bruce, M. I.; Hinterding, P.; Ke, M.; Low, P. J.;
Skelton, B. W.; White, A. H. Chem. Commun. 1997, 715-716.
(4) (a) Auger, N.; Touchard, D.; Rigaut, S.; Halet, J. F.; Saillard, J.
Y. Organometallics 2003, 22, 1638-1644. (b) Marrone, A.; Re, N.
Organometallics 2002, 21, 3562-3571. (c) Winter, R. F.; Klinkhammer,
K. W.; Za´lis, S. Organometallics 2001, 20, 1317-1333. (d) Baya, M.;
Crochet, P.; Esteruelas, M. A.; Gutierrez-Puebla, E.; Lo´pez, A. M.;
Modrego, J.; On˜ate, E.; Vela, N. Organometallics 2000, 19, 2585-2596.
(e) Re, N.; Sgamellotti, A.; Floriani, C. Organometallics 2000, 19, 1115-
1122. (f) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Modrego, J.;
On˜ate, E. Organometallics 1997, 16, 5826-5835. (g) Edwards, A. J.;
Esteruelas, M. A.; Lahoz, F. J.; Modrego, J.; Oro, L. A. Organometallics
1996, 15, 3556-3562. (h) Cadierno, V.; Gamasa, M. P.; Gimeno, J.;
Gonza´lez-Cueva, M.; Lastra, E.; Borge, J.; Garc´ıa-Granda, S.; Pe´rez-
Carren˜o, E. Organometallics 1996, 15, 2137-2147. (i) Berke, H.;
Huttner, G.; Von Seyerl, J. Z. Naturforsch., B 1981, 36, 1277-1288.
(j) Schilling, B. E. R.; Hoffmann, R.; Lichtenberger, D. L. J. Am. Chem.
Soc. 1979, 101, 585-591.
2
206.68 (t, JCP ) 20.6-21.4 Hz, CR), 149.95-156.79 (s,
Cγ), and 121.11-122.76 (s, Câ) ppm, (iii) the hydrogen
of the alkenyl group in the 1H NMR spectrum as a
singlet at 5.91 (4) and 6.20 ppm (6), and (iv) 2D NMR
(NOESY) experiments for complex 4, which are in
accord with a trans arrangement of the hydrogen and
methyl substituents in solution. Although the spectro-
scopic data of these aminoallenylidene complexes can
be compared with those of the precursors 1 and 2, some
significant differences can be observed, in particular (i)
the ν(CdCdC) absorption in the IR spectra, which
appears at 1980-1992 cm-1, between that shown by all-
carbon-substituted allenylidenes and alkynylruthenium-
(II) complexes,2 (ii) the higher field of the CR (195.87-
(5) Conejero, S.; D´ıez, J.; Gamasa, M. P.; Gimeno, J.; Garcı´a-Granda,
S. Angew. Chem., Int. Ed. 2002, 41, 3439-3442.
(6) Brandsma, L. Preparative Acetylenic Chemistry; Elsevier: Am-
sterdam, The Netherlands, 1988; p 235.
(7) Other vinylallenylidene complexes are known: (a) Pe´ron, D.;
Romero, A.; Dixneuf, P. H. Organometallics 1995, 14, 3319-3326. (b)
Touchard, D.; Pirio, N.; Toupet, L.; Fettouhi, M.; Ouahab, L.; Dixneuf,
P. H. Organometallics 1995, 14, 5263-5272.

Indenylruthenium(II) Aminoallenylidenes
Organometallics, Vol. 23, No. 26, 2004 6301
Table 1. 13C{1H} NMR Selected Data for the Allenylidene Complexesa
compd
CR
Câ
Cγ
[Ru{dCdCdC(NEt2)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (3)
[Ru{dCdCdC(NEt2)[C(Me)dC(H)Ph]}(η5-C9H7)(PPh3)2][PF6] (4)b
[Ru{dCdCdC(NEt2)[C(SiMe3)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (5)
[Ru{dCdCdC(NEt2)[C(H)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (6)
199.39 dd (20.7, 20.7)
206.68 t (21.4)
195.87 t (20.6)
202.33 t (22.0)
202.21 t (21.2)
201.50 dd (21.7, 19.9)
202.61 t (21.5)
281.78 t (18.7)
280.17 t (19.5)
295.05 t (19.7)
292.66 t (18.9)
290 93 t (19.2)
121.72 s
122.76 s
121.11 s
122.27 s
121.07 s
121.27 s
121.14 s
222.68 s
221.88 s
208.84 s
215.69 s
203.50 s
155.26 s
156.79 s
156.83 s
149.95 s
156.21 s
159.14 s
157.11 s
156.86 s
152.95 s
150.61 s
146.60 s
152.32 s
[Ru{dCdCdC(NEt2)[(CRdCH)C(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (18; R ) H)
[Ru{dCdCdC(NEt2)[(CRdCH)C(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (19; R ) SiMe3)
[Ru{dCdCdC(NEt2)[(CMe)CH)2C(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (22)
[Ru{dCdCdC(CtCPh)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2][BF4] (8)
[Ru{dCdCdC(CtCSiMe3)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2][BF4] (9)b
[Ru{dCdCdC(H)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (16)
[Ru{dCdCdC(H)[C(H)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (17)b
[Ru{dCdCdC(H)[(CMe)CH)C(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (21)
2
a Spectra recorded in CDCl3. δ in ppm and J in Hz. Abbreviations: s, singlet; dd, doublet of doublets; t, triplet. JCP values are given
in parentheses. b Spectrum recorded in CD2Cl2.
Table 2. Selected Bond Lengths and Slip
Parameter ∆a (Å) and Bond Angles, Torsion
Angles, and Dihedral (CAb) Angles (deg) for
3‚EtOH
Distances
Ru-C*
1.9348(4)
1.956(5)
1.235(6)
1.392(6)
1.520(6)
1.353(6)
1.314(6)
0.13(4)
Ru-P(1)
2.3402(12)
2.2943(12)
2.207(4)
2.220(4)
2.352(4)
2.377(5)
2.249(4)
Ru-C(1)
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
C(3)-N(1)
∆
Ru-P(2)
Ru-C(23)
Ru-C(24)
Ru-C(25)
Ru-C(30)
Ru-C(31)
Angles
P(1)-Ru-P(2)
P(1)-Ru-C(1)
P(2)-Ru-C(1)
C*-Ru-C(1)
C*-Ru-P(1)
C*-Ru-P(2)
Ru-C(1)-C(2)
C(1)-C(2)-C(3)
C(2)-C(3)-N(1)
CA
98.64(4)
96.01(13)
95.21(12)
119.73(12)
122.23(13)
119.22(3)
168.0(4)
C(4)-C(3)-N(1)
C(3)-N(1)-C(7)
C(3)-N(1)-C(9)
C(7)-N(1)-C(9)
C(2)-C(3)-C(4)
C(5)-C(4)-C(6)
C(5)-C(4)-C(3)
C(6)-C(4)-C(3)
C(17)-C(5)-C(11)
C(6)-C(4)-C(3)-N(1)
120.4(4)
119.7(4)
123.5(4)
116.7(4)
116.2(4)
125.0(4)
123.7(4)
111.3(4)
116.3(4)
99.0(5)
Figure 1. ORTEP view of the molecular structure of the
cation of [Ru{dCdCdC(NEt2)[C(Me)dCPh2]}(η5-C9H7)-
(PPh3)2][PF6]‚EtOH (3‚EtOH), drawn at the 10% prob-
ability level. The hexafluorophosphate anion, EtOH mol-
ecule, and phenyl groups of PPh3 have been omitted for
clarity. Only the ipso carbon atoms of the aryl groups are
depicted.
174.7(5)
123.2(5)
69.78(12)
a ∆ ) d[Ru-C(25),C(30)] - d[Ru-C(24),C(31)]. b CA (confor-
mational angle) ) angle between normals to least-squares planes
defined by [C**, C*, Ru] and [C*, Ru, C(1)]. C* ) centroid of C(30),
C(31), C(23), C(24), C(25). C** ) centroid of C(30), C(29), C(28),
C(27), C(26), C(25).
206.68 ppm) and Câ resonances (121.11-122.76 ppm)
in the 13C NMR spectra (see Table 1), and (iii) the
nonequivalence of the ethyl substituents in the NEt2
group (two resonance signals, one of the Et group
pointing toward and one away from the metal) in the
1H and 13C NMR spectra. These facts point to a
dominant contribution of the alkynyl resonance form.3b,4c,8
To assess the existence of this contribution in the
alkenylallenylidene complexes 3-6, an X-ray diffraction
study of complex 3 was undertaken.
An ORTEP type view of the cation complex 3 is shown
in Figure 1, and selected bond distances and angles are
listed in Table 2. The molecular structure shows the
typical pseudooctahedral three-legged piano-stool coor-
dination around the ruthenium atom, which is η5
bonded to the indenyl group, the two phosphorus atoms
of PPh3 ligands, and the C(1) of the alkenylaminoallen-
ylidene group. Bond lengths in the aminoallenylidene
chain (Ru-C(1) ) 1.956(5) Å, C(1)-C(2) ) 1.235(6) Å,
C(2)-C(3) ) 1.392(6) Å, and C(3)-N(1) ) 1.314(6) Å)
show an important contribution of the iminium-alkynyl
resonance form [Ru]-CtCC(dN+Et2)[C(Me)dCPh2].2b
In addition, the coordination environment of the nitro-
gen atom is similar to that expected for a typical N(sp2)
hybridization (angles C(3)-N(1)-C(7) ) 119.7(4)°, C(7)-
N(1)-C(9) ) 116.7(4)°, and C(3)-N(1)-C(9) ) 123.5-
(4)°). It is also worth noting the orientation of the methyl
substituent with respect to the amino group of the
alkenylaminoallenylidene chain, defined by the torsion
angle C(6)-C(4)-C(3)-N(1) (99.0(5)°), which deviates
notably from the s-trans stereochemistry (torsion angle
of 180°). The orientation of the alkenylaminoallen-
ylidene group with respect to the benzo ring of the
indenyl ligand is established by the conformational
angle (CA) of 69.78(12)° (CA ) 0° for the cis orientation).
The rest of the main structural parameters are rather
similar to those found for analogous indenylruthenium-
(II) complexes reported by us and therefore do not merit
further comments (see Table 2).
(8) (a) Fischer, H.; Szesni, N.; Roth, G.; Burlaff, N.; Weibert, B. J.
Organomet. Chem. 2003, 683, 301-312. (b) Winter, R. F.; Hartmann,
S.; Za´lis, S.; Klinkhammer, K. W. Dalton 2003, 2342-2352. (c)
Slageren, J.-V.; Winter, R. F.; Klein, A.; Hartmann, S. J. Organomet.
Chem. 2003, 670, 137-143. (d) Roth, G.; Reindl, D.; Gockel, M.; Troll,
C.; Fischer, H. Organometallics 1998, 17, 1393-1401. (e) Bruce, M.
I.; Hinterding, P.; Low, P. J.; Skelton, B. W.; White, A. H. J. Chem.
Soc., Dalton Trans 1998, 467-473. (f) Winter, R. F.; Hornung, F. M.
Organometallics 1997, 16, 4248-4250. (g) Fischer, H.; Leroux, F.;
Stumpf, R.; Roth, G. Chem. Ber. 1996, 129, 1475-1482. (h) Touchard,
D.; Haquette, P.; Daridor, A.; Toupet, L.; Dixneuf, P. H. J. Am. Chem.
Soc. 1994, 116, 11157-11158.
On the basis of this structural information, we then
wondered whether the addition of electrophiles at the
Câ atom would be feasible, in accordance with the
reactivity generally observed by transition-metal alky-

6302 Organometallics, Vol. 23, No. 26, 2004
Conejero et al.
Scheme 2
Scheme 3
nyls. As expected, the treatment of complex 3 with
HBF4‚OEt2, in dichloromethane at room temperature,
leads to the dicationic vinylidene complex 7 in 96% yield
(Scheme 2).
Complex 7 has been spectroscopically characterized
(1H and 13C{1H} NMR), showing the expected reso-
nances of typical vinylidene groups attached to inde-
nylruthenium(II) fragments10 as well as those of the
vinylidene-iminium group (13C{1H} NMR δ 334.81 (t,
2JCP ) 14.7 Hz, CR), 110.49 (s, Câ), and 171.84 (s, Cγd
N); 1H NMR δ 5.17 (s, br, dCdCH)). However, all
attempts to isolate complex 7 with analytical purity
failed, since it easily reverts to its allenylidene precursor
3 by loss of the Câ proton. The selective formation of
the vinylidene 7 corroborates the dominant contribution
of the alkynyl resonance form [Ru]-CtCC(dN+Et2)-
[C(Me)dCPh2] vs [Ru]+dCdCdC(NEt2)[C(Me)dCPh2]
and contrasts with the typical electrophilic additions to
the Câ atom of an allenylidene chain to give carbyne
complexes.11 The analogous aminoallenylidene complex
trans-[RuCl{dCdCdC(NMe2)(CH2R)}(dppm)2]+ is also
prone to undergo this favored protonation, affording the
dicationic iminium-substituted vinylidene complex trans-
[RuCl{dCdC(H)C(dNMe2)(CH2R)}(dppm)2]2+ (R ) C5-
H5S).3b
The formation of complexes 3-5 probably proceeds
through an initial nucleophilic addition of the ynamine
at the Cγ atom of the cumulene moiety, leading to the
formation of a cationic alkynyl intermediate complex.
Further ring closure, involving the Câ atom, gives the
[2 + 2] vinylidene cycloadduct. A subsequent cyclor-
eversion would yield the alkenylaminoallenylidenes 3-5
(Scheme 3). It is worth noting that the synthesis of
complex 5 requires a longer reaction time (12 h), proba-
bly due to the presence of a sterically demanding group
(R′ ) SiMe3) in the nucleophilic carbon of the ynamine.
An analogous mechanism has been also proposed in
the cycloaddition reactions of ynamines with group 6
allenylidene complexes8d [M{dCdCdC(C6H4R-p)2}-
(CO5)] (M ) Cr, W; R ) H, Me, OMe, NMe2). However,
a mixture of two products, [M{dCdCdC(NEt2)[C(R′)d
NMe2, R′ ) Ph, Me), are formed as a consequence of
the insertion of the CtC bond of the ynamine into both
CRdCâ and CâdCγ bonds of the cumulene moiety.
The formal insertion selectivity promoted by allen-
ylidene complexes 1 and 2 stems from the regioselec-
tivity of the nucleophilic additions in these systems (see
below).
Nucleophilic Additions onto the Aminoalle-
nylidene Complex [Ru{dCdCdC(NEt2)[C(Me)d
CPh2]}(η5-C9H7)(PPh3)2][PF6] (3): At present, it is
well established that the reactivity of cationic transition-
metal allenylidene complexes is dominated by the
nucleophilic additions at the CR and Cγ atoms of the
cumulene chain.2 During our investigations on the
reactivity of allenylideneindenylruthenium(II) com-
plexes [Ru(dCdCdCR1R2)(η5-C9H7)(L)(L′)][PF6], we have
shown that the addition of nucleophiles to the unsatur-
ated chain takes place regioselectively at the Cγ
atom.10a,12 The efficient and systematic accessibility to
R,â-unsaturated allenylidene ruthenium complexes 3-5
prompted us to use them as precursors of highly
unsaturated alkynyls through the corresponding nu-
cleophilic additions of carbanions. To undertake a
systematic reactivity study, the alkenylaminoallen-
ylidene complex 3 was selected as the precursor model.
Reactions with Acetylides CtCR- (R ) Ph,
SiMe3, Me2CH, PhCH2): Synthesis of [Ru{dCdCd
C(CtCR)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2][BF4] (R
) Ph (8), SiMe3 (9)) and [Ru{CtCC(dCdCdCRR′)-
[C(Me)dCPh2]}(η5-C9H7)(PPh3)2] (R ) R′ ) Me (10);
R ) Ph, R′ ) H (11)). Complex 3 reacts with an excess
of LiCtCR (R ) Ph, SiMe3; prepared in situ from the
terminal alkyne and LinBu) in tetrahydrofuran at -20
°C for 30 min. After removal of the solvent and extrac-
tion with diethyl ether, the subsequent addition of HBF4
to the resulting solution leads to the formation of a solid
precipitate, identified as the disubstituted alkynylalk-
enylallenylidene complexes 8 and 9 (Scheme 4). Com-
plexes 8 and 9 were isolated after workup as air-stable
blue-violet powders in 90 and 94% yields, respectively.
C(C6H4R-p)2]}(CO5)] and [M{dCC(R′)dC(NEt2)Cd
C(C6H4R-p)2}(CO)5] (M ) Cr, W; R ) H, Me, OMe,
(9) Cadierno, V.; D´ıez, J.; Gamasa, M. P.; Gimeno, J.; Lastra, E.
Coord. Chem. Rev. 1999, 193-195, 147-205.
(10) See for example: (a) Cadierno, V.; Conejero, S.; Gamasa, M.
P.; Gimeno, J. Dalton 2003, 3060-3066. (b) Cadierno, V.; Conejero,
S.; D´ıez, J.; Gamasa, M. P.; Gimeno, J.; Garc´ıa-Granda, S. Chem.
Commun. 2003, 840-841. (c) Cadierno, V.; Conejero, S.; Gamasa, M.
P.; Gimeno, J. Organometallics 2002, 21, 3837-3840. (d) Cadierno,
V.; Conejero, S.; Gamasa, M. P.; Gimeno, J.; Falvello, L. R.; Llusar, R.
M. Organometallics 2002, 21, 3716-3726.
(11) (a) Rigaut, S.; Touchard, D.; Dixneuf, P. H. Organometallics
2003, 22, 3980-3984. (b) Bustelo, E.; Jimenez-Tenorio, M.; Mereiter,
K.; Puerta, M. C.; Valerga, P. Organometallics 2002, 21, 1903-1911.
(c) Jung, S.; Brandt, C. D.; Werner, H. New J. Chem. 2001, 25, 1101-
1103. (d) Baya, M.; Crochet, P.; Esteruelas, M. A.; Gutierrez-Puebla,
E.; Lo´pez, A. M.; Modrego, J.; On˜ate, E.; Vela, N. Organometallics 2000,
19, 2585-2596.
(12) Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Lo´pez-Gonza´lez, M.
C.; Borge, J.; Garc´ıa-Granda, S. Organometallics 1997, 16, 4453-4463.

Indenylruthenium(II) Aminoallenylidenes
Organometallics, Vol. 23, No. 26, 2004 6303
Scheme 4
Scheme 6
Scheme 5
R ) Ph, R′ ) H) (prepared in situ from the correspond-
ing terminal alkynes and Li-n-Bu) in tetrahydrofuran
at -20 °C. After 1 h of reaction at room temperature,
evaporation of the solvent followed by extraction of the
solid residue with diethyl ether and treatment with
neutral alumina gives rise to the amine elimination.
Removal of the solvent affords the 3-alkenyl-3,4,5-
hexatrien-1-ynyl complexes 10 and 11, isolated as red-
orange air-stable solids in 83 and 89% yields, respec-
tively (Scheme 6). The structures of 10 and 11 are fully
supported by their spectroscopic data and elemental
analyses. In particular, IR spectra exhibit the expected
ν(CdCdCdC) and ν(CtC) absorption bands at 1987-
2008 and 2059-2062 cm-1, respectively. 13C{1H} NMR
spectra display (i) the typical triplet resonance for Ru-
CR at δ 121.03-138.71, which compares well with that
of other unsaturated alkynyl complexes,14 (ii) singlet
signals for Câ at δ 113.57-114.64, and (iii) carbon nuclei
resonances of the CdCdCdC side chain in the range δ
101.48-158.58. NMR spectra of 11 indicate that a
mixture of the two E/Z isomers in a ca. 60:40 ratio is
obtained. Significantly, two proton resonances of dCH
1
Spectroscopic data (IR and H, 31P{1H}, and 13C{1H}
NMR), elemental analyses, and mass spectra are in
accordance with the proposed structures (see the Ex-
perimental Section). The most significant features of the
spectroscopic data are (i) the characteristic ν(CdCdC)
and ν(CtC) absorptions in the IR spectra at 1918-1922
and 2131-2167 cm-1, respectively, and (ii) the three
low-field signals for the allenylidene carbon nuclei in
the 13C{1H} NMR spectra, which appear in the ranges
1
appear in the H NMR spectrum of 11 at δ 5.97 and
6.03. All attempts to form these compounds stereose-
lectively were unsuccessful.
Although we have not undertaken mechanistic stud-
ies, it is likely that the reaction takes place through the
formation of the corresponding intermediate amino-
substituted alkynyl complex (analogous to A in Scheme
5), which in the presence of Al2O3 eliminates NHEt2
intramolecularly, generating 10 and 11.
Reactions with Alkyl Carbanions: Synthesis of
[Ru{CtCC(dCHR)[C(Me)dCPh2]}(η5-C9H7)(PP-
h3)2] (R ) H (12), R ) n-Pr (13), R ) CHdCH2 (14).
The addition of LiMe or Li-n-Bu to a solution of alkenyl-
(amino)allenylidene 3 in tetrahydrofuran at -20 °C
leads, after treatment with Al2O3, to the corresponding
butadiene-alkynyl complexes 12 and 13, isolated as air-
stable orange solids in 76 and 87% yields, respectively
(Scheme 7). Similarly, allylmagnesium bromide reacts
with complex 3 in tetrahydrofuran. After treatment with
Al2O3 and workup of the resulting solution, the hexatri-
ene-alkynyl complex 14 is obtained (74%) as an air-
stable orange solid (Scheme 7).
2
280.17-281.78 (t, JCP ) 18.7-19.5 Hz, CR), 221.88-
222.68 (s, Câ), and 152.95-156.86 (s, Cγ) ppm.
Likely, the reaction proceeds through the regioselec-
tive nucleophilic addition of lithium acetylide to the Cγ
of the allenylidene chain of 3 to give the transient
alkynyl-like complex A, which undergoes the electro-
philic addition of a proton to form the vinylidene
derivative B (Scheme 5). Finally, the spontaneous loss
of diethylamine generates the difunctionalized allen-
ylidene complexes. The overall processes formally result
in an exchange reaction of the diethylamide substituent
in the precursor complex by the acetylide group.13
Provided the effective attachment of alkynyl groups
to the allenylidene chain through a regioselective coup-
ling, we then explored the generalization of this meth-
odology. To promote the amine elimination avoiding the
protonation step, terminal alkynes containing an Hγ
atom (i.e. R2C(H)CtCH) were used, expecting that an
intramolecular elimination of NHEt2 could be favored.
In a way similar to that described above, complex 3
reacts with an excess of LiCtCCHRR′ (R ) R′ ) CH3;
Complexes 12-14 have been characterized by elemen-
tal analyses and spectroscopic techniques, which sup-
port the proposed hydrocarbon moieties. Relevant spec-
troscopic features are as follows: (i) in the IR spectra
(KBr), a weak ν(CtC) stretching absorption at 2041-
2096 cm-1; (ii) in the 1H NMR spectra, dCH resonances
(13) We have previously noted that addition of acids to the alkynyl
complexes of general formula [Ru{CtCCPh2(NHCHMeR′′)}(η5-1,2,3-
R3C9H4)(CO)(PR3′)] (R ) H, R′ ) i-Pr, R′′ ) Ph, Cy; R ) Me, R′) i-Pr,
Ph, R′′ ) Ph, Cy) led to the formation of the allenylidene derivative
[Ru(dCdCdCPh2)(η5-1,2,3-R3C9H4)(CO)(PR3)]+ along with the elimina-
tion of NHR2: Gamasa, M. P.; Gonza´lez-Bernardo, C.; Gimeno, J.
Unpublished results.
(14) Cadierno, V.; Conejero, S.; Gamasa, M. P.; Gimeno, J.; Assel-
berghs, I.; Houbrechts, S.; Clays, K.; Persoons, A.; Borge, J.; Garc´ıa-
Granda, S. Organometallics 1999, 18, 582-597.

6304 Organometallics, Vol. 23, No. 26, 2004
Conejero et al.
Scheme 7
it has been characterized by NMR spectroscopy. The
most characteristic resonances are as follows: (i) in the
31P{1H} NMR, the two doublets δ 52.43 and 52.73 (2JPP
) 34.0 Hz), in agreement with the AB system arising
from the presence of a stereogenic center at Cγ; (ii) in
the 1H NMR, the singlet signal at δ 4.42 for the CHNEt2
proton; (iii) the low-field signals at δ 93.60 (CR) and
58.79 (Cγ) in the 13C{1H} NMR spectrum.
One-pot synthesis of alkenylallenylidene complexes
16 and 17 is achieved by the treatment of 3 and 6 with
LiBHEt3 after elimination of the resulting lithium salt
and NHEt2 on a short silica column15 (see Scheme 8).
Therefore, the overall process results in the formal
substitution of the NEt2 group by hydrogen. Complexes
16 (82%) and 17 (86%) have been isolated as violet air-
stable powders.16
As was described above for the allenylidene complex
2, the secondary allenylidene 16 also reacts with the
ynamines RCtCNEt2 (R ) Me, SiMe3) in tetrahydro-
furan, affording the butadienylaminoallenylidene com-
plexes 18 (60%) and 19 (80%), which are isolated as air-
stable orange solids (Scheme 9).
as two doublets (δ 4.94 (d) and 5.05 (d); JHH ) 2.6 Hz)
(12), one triplet (4.95 (t); JHH ) 7.1 Hz) (13), and a
doublet (δ 6.11 (d); JHH ) 10.8 Hz) (14) signals and, in
addition, the dCH2 resonances of 14 as two doublets of
doublets at δ 4.88 and 5.00 (JHH ) 10.3-17.1 Hz, JHH
) 1.9 Hz); (iii) in the 13C{1H} NMR spectra, a Ru-CR
triplet (δ 112.07 (12), 113.00 (13), and 120.94 (14), 2JCP
) 23.8-24.5 Hz) and a single Câ resonance (δ 113.12-
114.90).
It is interesting to note that the formation of complex
13 proceeds in a stereoselective manner, although the
spectroscopic data do not allow establishing the cis-
trans disposition.
Scheme 9
Synthesis of Alkenylallenylidenes [Ru{dCdCd
C(H)[C(R)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (R ) Me
(16), H (17)), Butadienylaminoallenylidenes [Ru{d
CdCdC(NEt2)[(CRdCH)C(Me)dCPh2]}(η5-C9H7)-
(PPh3)2][PF6] (R ) Me (18), SiMe3 (19)), and Buta-
dienylallenylidene [Ru{dCdCdC(H)[(CMe)CH)C-
(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (21). The ability
of the allenylidene precursors 1 and 2 to undergo the
insertion of one molecule of ynamines R′CtCNEt2
prompted us to use the new alkenylaminoallenylidenes
[Ru{dCdCdC(NEt2)[C(R′)dC(R)Ph]}(η5-C9H7)(PPh3)2]-
[PF6] (3-5) as precursors in further insertion reactions.
However, the treatment of complexes 3-5 with an
excess of the ynamine in tetrahydrofuran, even under
reflux conditions for several hours, gives the starting
complexes unchanged. This fact probably arises from
the dominant alkynyl resonance form [Ru]-CtC-C(d
N+Et2)[CMedCPh2] (see above, X-ray discussion), which
precludes the insertion reaction. Since the presence of
the diethylamino substituent favors the stabilization of
the CtC bond, we sought the transformation of the
alkenylaminoallenylidene complex into the correspond-
ing secondary derivative.
The transformation of the butadienylaminoallenyl-
idene complex into the corresponding secondary allen-
ylidene derivative is straightforward, following the
methodology used above for the synthesis of 16. Thus,
the reaction of 18 with a slight excess of LiBHEt3 in
tetrahydrofuran, followed by purification of the concen-
trated solution on a silica column, yields the desired
secondary butadienylallenylidene complex 21, isolated
as a violet solid in 83% yield after workup (Scheme 10).
The formation of the intermediate alkynyl species 20
is observed in situ by NMR spectroscopy (see the
Experimental Section for details).
Complexes 16-19 and 21 have been fully character-
ized by elemental analysis, spectroscopic techniques (IR
and multinuclear NMR spectroscopy), and X-ray crys-
tallography for complex 18. Selected bond lengths (Å)
and angles (deg) are collected in Figure 2. For further
structural data see ref 5.
IR spectra (KBr) show the expected ν(CdCdC) ab-
sorptions, in accordance with the type of allenylidene
chain: (i) secondary allenylidenes 16, 17, and 21 (1932-
1938 cm-1) and (ii) aminoallenylidenes 18 and 19
(1987-1992 cm-1). 1H and 13C{1H} NMR spectra of
complexes 16-19 and 21 display resonances, in ac-
The treatment of complex 3 with LiBHEt3 in tetrahy-
drofuran at 0 °C affords the alkynyl derivative 15,
generated by the nucleophilic addition of the hydride
to the Cγ atom of the allenylidene chain (Scheme 8).
Complex 15 is isolated as an orange unstable solid.
Although no analytically pure sample could be obtained,
Scheme 8

Indenylruthenium(II) Aminoallenylidenes
Organometallics, Vol. 23, No. 26, 2004 6305
Scheme 10
Synthesis of the Hexatrienylaminoallenylidene
Complex [Ru{dCdCdC(NEt2)[(CMedCH)2C(Me)d
CPh2]}(η5-C9H7)(PPh3)2][PF6] (22). The secondary
alkenylallenylidene 21 is also able to insert one further
molecule of ynamine. Thus, when a solution of 21 in
tetrahydrofuran is reacted with an excess of MeCt
CNEt2 at 0 °C, the violet color turns immediately to
orange. After workup of the resulting solution the
hexatrienylaminoallenylidene complex 22 is obtained
regio- and stereoselectively (45% yield) as an orange air-
stable solid (Scheme 10).
Analytical and spectroscopic data support the pro-
posed formulation (see the Experimental Section for
details). 1H and 13C{1H} NMR spectra display reso-
nances in accord with the presence of the allenylidene
and hexatrienyl groups, although unambiguous stere-
ochemical information cannot be obtained. Since these
data can be compared with those by the analogous
alkenyl allenylidenes 18 and 19, no further comments
are warranted.
Final Remarks
Figure 2. ORTEP view of the molecular structure of the
cation of [Ru{dCdCdC(NEt2)[(CMedCH)C(Me)dCPh2]}-
(η5-C9H7)(PPh3)2][PF6] (18), drawn at the 10% probability
level. The hexafluorophosphate anion and phenyl groups
of PPh3 have been omitted for clarity. Only the ipso carbon
atoms of the aryl groups are depicted. Selected bond
lengths (Å), bond angles (deg), and torsion angles (deg):
Ru-P(1) ) 2.299(9), Ru-P(2) ) 2.305(9), Ru-C(1) ) 1.946-
(4), C(1)-C(2) ) 1.229(5), C(2)-C(3) ) 1.390(5), C(3)-C(4)
) 1.500(5), C(4)-C(5) ) 1.340(6), C(5)-C(6) ) 1.510(5),
C(6)-C(7) ) 1.355(5), C(3)-N(1) ) 1.319(5); Ru-C(1)-C(2)
) 174.6(3), C(1)-C(2)-C(3) ) 177.8(4), C(2)-C(3)-N(1) )
122.1(3), C(4)-C(3)-N(1) ) 119.0(3), C(2)-C(3)-C(4) )
118.4(2), C(3)-N(1)-C(24) ) 121.7(3), C(3)-N(1)-C(22) )
122.1(4), C(24)-N(1)-C(22) ) 116.2(4); C(20)-C(6)-C(5)-
H(5) ) 162.8(3), N(1)-C(3)-C(4)-C(21) ) 78.8(5).
Organometallic complexes bearing highly unsaturated
hydrocarbon chains are one of the most challenging
goals in organometallic chemistry, since they can pro-
vide unusual approaches to organic synthesis. Despite
this fact, the construction of a desired unsaturated chain
in a chemo- and regioselective manner is not always
straightforward. In this context, the chemistry of cu-
mulenylidene complexes has provided a general ap-
proach to achieve long cumulenic hydrocarbon chains.1
However, only a few ruthenium complexes bearing
unsaturated substituents are known.1d Since the gen-
eration of these cumulenic chains attached to metal
fragments are generally achieved using the correspond-
ing unsaturated propargyl alcohol, the metallacumu-
lenic complex is only accessible, providing the availabil-
ity of the appropriate alcohol. This synthetic drawback
limits the access to this type of derivative.
cordance with the presence of the methyl, ethyl, and
phenyl substituents of the alkenyl groups (see Experi-
mental Section). The most remarkable features arise
from the carbon resonances of the allenylidene chain
in the 13C{1H} NMR spectra (see Table 1), which appear
at δ 290.93-295.05 (CR), 203.50-215.69 (Câ), and
146.60-152.32 (Cγ) (complexes 16, 17, and 21) and δ
201.50-202.21 (CR), 121.07-121.27 (Câ), and 156.21-
159.14 (Cγ) (complexes 18 and 19). The latter values can
be compared to those shown by the parent aminoalle-
nylidene 3.
(15) The synthesis of allenylidene complexes by dehydration of
hydroxivinylidene species in the presence of SiO2 or Al2O3 has been
previously described: (a) Werner, H.; Rappert, T.; Wiedemann, R.;
Wolf, J.; Mahr, N. Organometallics 1994, 13, 2721-2727. (b) Gauss,
C.; Veghini, D.; Orama, O.; Berke, H. J. Organomet. Chem. 1997, 541,
19-38.
(16) The reaction of 3 with NaBH4 proceeds in a different way, giving
instead the alkynyl complex [Ru{CtCCH2[C(Me)dCPh2]}(η5-C9H7)-
(PPh3)2] (23), which has been isolated as an air-stable yellow powder
in 77% yield. Characterization follows from elemental analysis and
NMR spectroscopy (see the Supporting Information).

6306 Organometallics, Vol. 23, No. 26, 2004
Conejero et al.
(d, JPP ) 27.5 Hz). H NMR (CDCl3): δ 0.94 and 1.06 (t, 3H
2
1
Herein an unprecedented synthetic methodology of
highly unsaturated allenylidenes is described. The
synthetic approach is based on the regio- and stereose-
lective sequential insertions of ynamines into the allen-
ylidene moieties. The systematic and efficient method
allows the synthesis of alkenyl-, butadienyl- and hexatrie-
nylallenylidene complexes of the types [Ru{dCdCd
C(NEt2)[(CRdCH)nC(R′)dC(R′′)Ph]}(η5-C9H7)(PPh3)2]-
[PF6] (n ) 0-2; 3-6, 18, 19, and 22), [Ru{dCdCd
C(H)[(CMedCH)nC(R)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (n
) 0, 1; 16, 17, and 21), and [Ru{dCdCdC(CtCR)-
[C(Me)dCPh2]}(η5-C9H7)(PPh3)2][BF4] (8 and 9). The
ability of the aminoallenylidene 3 to undergo regiose-
lective C-C coupling with carbanions is also exploited
to build up organometallic species bearing unusual
highly unsaturated alkynyl complexes of the typew [Ru-
{CtCC(dCHR)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2] (12-
14) and [Ru{CtCC(dCdCdCRR′)[C(Me)dCPh2]}(η5-
C9H7)(PPh3)2] (10 and 11), the latter showing three
distinct unsaturated carbon-carbon chains arising from
the presence of alkynyl, alkenyl, and butatrienyl groups.
The utility of this synthetic methodology in organic
synthesis through demetalation processes is currently
being investigated. We have recently shown an efficient
approach to synthesizing functionalized terminal alkynes
starting from the appropriate alkynylruthenium(II)
complexes.10a
3
3
each, JHH ) JHH′ ) 7.1 Hz, CH2CH3), 1.79 (s, 3H, dCCH3),
3.17, 3.45, 3.73, and 4.12 (m, 1H each, CH2CH3), 4.82 and 4.88
(br, 1H each, H-1 and H-3), 5.26 (br, 1H, H-2), 6.06 and 6.28
(d, 1H each, 3JHH ) 7.7 Hz, H-4, H-5, H-6, or H-7), 6.99-7.78
(m, 42H, Ph, H-4, H-5, H-6, or H-7). 13C{1H} NMR (CDCl3): δ
11.74 and 12.94 (s, CH2CH3), 20.22 (s, dCCH3), 45.75 and
47.11 (s, CH2CH3), 76.09 and 76.73 (s, C-1 and C-3), 95.88 (s,
C-2), 109.75 and 111.72 (s, C-3a and C-7a), 121.72 (s, Câ),
122.86 and 123.76 (s, C-4, C-5, C-6, or C-7), 126.05-142.20
(m, Ph, dCCH3, dCPh2, C-4, C-5, C-6, or C-7), 155.26 (s, CγN),
2
2
199.39 (dd, JCP ) JCP′ ) 20.7 Hz, RudCR). Anal. Calcd for
C67H60F6NP3Ru: C, 67.76; H, 5.10; N, 1.33. Found: C, 67.50;
H, 5.33; N, 1.18. ΛM ) 121 Ω-1 cm2 mol-1 (acetone). Data for
4 are as follows. Yield: 0.79 g (71%). IR (KBr, cm-1): ν(Cd
CdC) 1989, ν(CdN) 1540, ν(PF6-) 840. 31P{1H} NMR (CD2-
Cl2): δ 49.58 (s). 1H NMR (CD2Cl2): δ 1.33 and 1.41 (t, 3H
each, 3JHH ) 6.9 Hz, CH2CH3), 1.88 (s, 3H, dCCH3), 3.62 and
3.91 (q, 2H each, 3JHH ) 6.9 Hz, CH2CH3), 4.90 (d, 2H, 3JHH
)
3
2.6 Hz, H-1 and H-3), 5.21 (t, 1H, JHH ) 2.6 Hz, H-2), 6.18
(m, 2H, H-4, H-5, H-6, or H-7), 6.20 (s, 1H, dCH), 6.99-7.35
(m, 37H, Ph, H-4, H-5, H-6, or H-7). 13C{1H} NMR (CD2Cl2):
δ 13.35 and 14.14 (s, CH2CH3), 17.54 (s, dCCH3), 46.72 and
47.78 (s, CH2CH3), 77.42 (s, C-1 and C-3), 95.93 (s, C-2), 111.00
(s, C-3a and C-7a), 122.76 (s, Câ), 123.63 (s, C-4, C-5, C-6, or
C-7), 127.39-136.92 (m, Ph, dCCH3, dCH, C-4, C-5, C-6, or
C-7), 156.79 (s, CγN), 206.68 (t, 2JCP ) 21.4 Hz, RudCR). Anal.
Calcd for C61H56F6NP3Ru: C, 65.94; H, 5.08; N, 1.26. Found:
C, 65.59; H, 4.78; N, 0.98. ΛM ) 124 Ω-1 cm2 mol-1 (acetone).
[Ru{dCdCdC(NEt2)[C(SiMe3)dCPh2]}(η5-C9H7)(PPh3)2]-
[PF6] (5). Me3SiCtCNEt2 (0.26 mL, 2 mmol) was added, at
room temperature, to a solution of allenylidene [Ru(dCdCd
CPh2)(η5-C9H7)(PPh3)2][PF6] (1.08 g, 1 mmol) in 40 mL of
tetrahydrofuran. The reaction mixture was stirred for 12 h,
and the solvent was removed in vacuo. The solid residue was
transferred to a silica chromatography column and washed
with diethyl ether, and compound 5 was eluted with a diethyl
ether/dichloromethane (3/1) mixture. Removal of the solvents
Experimental Section
General Procedures. The manipulations were performed
under an atmosphere of dry nitrogen using vacuum-line and
standard Schlenk techniques. Solvents were dried by standard
methods and distilled under nitrogen before use. All reagents
were obtained from commercial suppliers and used without
further purification, with the exception of the compounds Me3-
SiCtCNEt217 and [Ru(dCdCdCRPh)(η5-C9H7)(PPh3)2][PF6] (R
) Ph, H),4h which were prepared by following the methods
reported in the literature. Infrared spectra were recorded on
a Perkin-Elmer 1720-XFT spectrometer. The C, H, and N
analyses were carried out with a Perkin-Elmer 2400 mi-
croanalyzer (inconsistent analyses were found for complexes
8 and 9 due to incomplete combustion). Mass spectra (FAB)
were recorded using a VG-Autospec spectrometer, operating
in the positive mode; 3-nitrobenzyl alcohol (NBA) was used
as the matrix. NMR spectra were recorded on a Bruker DPX-
300 instrument at 300 MHz (1H), 121.5 MHz (31P), or 75.4 MHz
(13C) using SiMe4 or 85% H3PO4 as standard. DEPT experi-
ments have been carried out for all the compounds reported.
Legend for atoms of the indenyl group:
led to the title compound as an orange solid. Yield: 0.79 g
-
(64%). IR (KBr, cm-1): ν(CdCdC) 1980, ν(CdN) 1519, ν(PF6
)
840. 31P{1H} NMR (CDCl3): δ 47.71 s. 1H NMR (CDCl3): δ
3
0.09 (s, 9H, Si(CH3)3), 0.71 (dd, 3H, JHH
)
3JHH′ ) 7.0 Hz,
3
3
NCH2CH3), 1.10 (dd, 3H, JHH ) JHH′ ) 7.2 Hz, NCH2CH3),
3.43, 3.50, 3.64, and 3.82 (m, 1H each, N(CH2CH3)2), 4.75 and
3
5.00 (br, 1H each, H-1 and H-3), 5.47 (t, 1H, JHH ) 2.4 Hz,
3
H-2), 5.81 (d, 1H, JHH ) 8.3 Hz, H-4, H-5, H-6, or H-7), 5.99
3
(d, 1H, JHH ) 7.9 Hz, H-4, H-5, H-6, or H-7), 6.74-7.48 (m,
42H, Ph, H-4, H-5, H-6, or H-7). 13C{1H} NMR (CDCl3): δ 1.41
(s, Si(CH3)3), 11.96 and 12.44 (s, N(CH2CH3)2), 44.78 and 45.24
(s, N(CH2CH3)2), 74.37 and 76.05 (s, C-1 and C-3), 95.97 (s,
C-2), 109.98 and 114.34 (s, C-3a and C-7a), 121.11 (s, Câ),
122.28, 124.35, and 127.03 (s, C-4, C-5, C-6, or C-7), 127.52-
140.95 (m, Ph, dCSiMe3, C-4, C-5, C-6, or C-7), 155.58 (s, d
CPh2), 156.83 (s, CγN), 195.87 (t, 2JCP ) 20.6 Hz, RudCR). Anal.
Calcd for C69H66F6NP3SiRu: C, 66.55; H, 5.34; N, 1.12.
Found: C, 66.20; H, 5.55; N, 1.19. ΛM ) 120 Ω-1 cm2 mol-1
(acetone).
[Ru{dCdCdC(NEt2)(CHdCPh2)}(η5-C9H7)(PPh3)2]-
[PF6] (6). KF (0.035 g, 0.6 mmol) was added, at room
temperature, to a solution of 5 (0.59 g, 0.5 mmol) in 40 mL of
methanol. The resulting solution was stirred for 1 h. The
solvent was then removed under vacuum, the solid residue was
extracted with dichloromethane, and the extract was filtered
off. Removal of the solvent under vacuum led to the title
compound as an orange solid. Yield: 0.56 g (96%). IR (KBr,
cm-1): ν(CdCdC) 1992, ν(CdN) 1531, ν(PF6-) 837. 31P{1H}
NMR (CDCl3): δ 49.66 s. 1H NMR (CDCl3): δ 0.86 (t, 3H, 3JHH
[Ru{dCdCdC(NEt2)[C(Me)dC(R)Ph]}(η5-C9H7)(PPh3)2]-
[PF6] (R ) Ph (3), H (4)). The addition of a solution of the
allenylidene complex [Ru(dCdCdCRPh)(η5-C9H7)(PPh3)2][PF6]
(R) Ph (1), H (2); 1 mmol) in tetrahydrofuran (40 mL) to a
solution of the ynamine MeCtCNEt2 (2 mmol) in tetrahydro-
furan (10 mL) at 0 °C gave an orange solution, which was
stirred for 15 min. The solvent was then removed under
vacuum, and the orange solid was washed with diethyl ether
(2 × 30 mL) and dried in vacuo. Data for 3 are as follows.
Yield: 1.03 g (87%). IR (KBr, cm-1): ν(CdCdC) 1989, ν(Cd
N) 1532, ν(PF6-) 840. 31P{1H} NMR (CDCl3): δ 49.50 and 49.35
3
) 7.1 Hz, NCH2CH3), 1.21 (t, 3H, JHH ) 7.0 Hz, NCH2CH3),
3.33 (q, 2H, 3JHH ) 7.1 Hz, NCH2CH3), 3.84 (q, 2H, 3JHH ) 7.0
Hz, NCH2CH3) 4.79 (d, 2H, 3JHH ) 2.3 Hz, H-1 and H-3), 5.09
3
(17) Himbert, G.; Nabhan, H.; Gerulet, O. Synthesis 1997, 293.
(t, 1H, JHH ) 2.3 Hz, H-2), 5.91 (s, 1H, dCH), 6.10 (m, 2H,

Indenylruthenium(II) Aminoallenylidenes
Organometallics, Vol. 23, No. 26, 2004 6307
2
H-4, H-5, H-6, or H-7), 6.89-7.44 (m, 42H, Ph, H-4, H-5, H-6,
or H-7). 13C{1H} NMR (CDCl3): δ 12.31 (s, N(CH2CH3)2), 46.18
and 47.20 (s, N(CH2CH3)2), 77.35 (s, C-1 and C-3), 94.91 (s,
C-2), 110.27 (s, C-3a and C-7a), 121.42 and 123.02 (s, C-4, C-5,
C-6, and C-7), 122.27 (s, Câ), 127.49-140.03 (m, Ph and dCH),
Câ), 280.17 (t, JCP ) 19.5 Hz, RudCR). MS (FAB): m/z 1067
[M+], 741 [M+ - R], 479 [M+ - R - PPh3], 363 [M+ - R -
PPh3 - C9H8] (R ) [CdCdC(CtCSiMe3){C(Me)dCPh2}]). ΛM
) 122 Ω-1 cm2 mol-1 (acetone).
[Ru{CtCCR[C(Me)dCPh2]}(η5-C9H7)(PPh3)2] (10-14).
General Procedure. LiCtCCHMe2 (3 mmol), LiCtCCH2Ph
(3 mmol; generated in situ by addition of Li-n-Bu (1.6 M) to a
solution of the corresponding alkyne in 10 mL of tetrahydro-
furan, at -20 °C), LiMe (1.6 M; 1.56 mL, 2.5 mmol), Li-n-Bu
(1.6 M; 1.56 mL, 2.5 mmol), or BrMgCH2CHdCH2 (1.0 M; 1.25
mL, 2 mmol) was added, at -20 °C, to a solution of [Ru{dCd
CdC(NEt2)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (3; 1.19 g, 1
mmol) in 50 mL of tetrahydrofuran. The reaction mixture was
brought to room temperature and stirred for further 1 h. The
solvent was then removed under vacuum, the solid residue was
extracted with diethyl ether (ca. 10 mL), and the resulting
solution was transferred to an Al2O3 (neutral: activity grade
I) chromatography column. Elution with diethyl ether and
removal of the solvent under vacuum led to the title com-
pounds.
2
148.22 (s, dCPh2), 149.95 (s, CγN), 202.33 (t, JCP ) 22.0 Hz,
RudCR). Anal. Calcd for C66H58F6NP3Ru: C, 67.59; H, 4.98;
N, 1.19. Found: C, 67.40; H, 4.82; N, 1.24. ΛM ) 118 Ω-1 cm2
mol-1 (acetone).
[Ru{dCdCHCd(NEt2)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2]-
[X]2 (7). To a solution of [Ru{dCdCdC(NEt2)[C(Me)dCPh2]}-
(η5-C9H7)(PPh3)2][PF6] in dichloromethane was added, at room
temperature, a slight excess of HBF4‚OEt2. The solvent was
removed under vacuum, and the solid residue was washed with
diethyl ether (3 × 20 mL) and dried in vacuo to give an orange
solid. Yield: 96%. 31P{1H} NMR (CDCl3): δ 31.44 and 31.95
2
(d, JPP ) 20.3 Hz). 1H NMR (CDCl3): δ 0.91 (m, 6H,
N(CH2CH3)2), 1.88 (s, 3H, CH3), 3.35 and 3.66 (m, 4H, N(CH2-
CH3)2), 5.17 (s, 1H, dCdCH), 5.52 (d, 1H, 3JHH ) 6.5 Hz, H-4,
3
H-5, H-6, or H-7), 5.64 (d, 1H, JHH ) 8.3 Hz, H-4, H-5, H-6,
[Ru{CtCC[dCdCdC(Me)2][C(Me)dCPh2]}(η5-C9H7)-
(PPh3)2] (10). Orange solid. Yield: 83% (0.85 g). IR (KBr,
cm-1): ν(CtC) 2062, ν(CdCdCdC) 2008. 31P{1H} NMR
or H-7), 5.68 and 5.74 (br, 1H each, H-1 and H-3), 6.42 (br,
1H, H-2), 6.66-7.57 (m, 42H, Ph, H-4, H-5, H-6, or H-7). 13C-
{1H} NMR (CDCl3): δ 11.52 and 12.65 (s, N(CH2CH3)2), 21.59
(s, dCCH3), 48.23 and 49.68 (s, N(CH2CH3)2), 84.53 and 86.09
1
(C6D6): δ 52.14 s. H NMR (C6D6): δ 1.75 (s, 6H, dC(CH3)2),
2.59 (s, 3H, dCCH3), 4.75 (d, 2H, 3JHH ) 2.4 Hz, H-1 and H-3),
2
(d, JCP ) 6.5 Hz, C-1 and C-3), 97.60 (s, C-2), 110.49 (s, Câ),
3
5.45 (t, 1H, JHH ) 2.4 Hz, H-2), 6.50 and 6.80 (m, 2H each,
119.00 and 121.01 (s, C-3a and C-7a), 123.35, 124.79 and
127.25 (s, C-4, C-5, C-6, or C-7), 127.81-146.02 (m, Ph, dCPh2,
dCCH3, C-4, C-5, C-6, or C-7), 171.84 (s, CγdN), 334.81 (t, 2JCP
) 14.7 Hz, RudCR).
H-4, H-5, H-6, and H-7), 7.07-7.70 (m, 40H, Ph). 13C{1H} NMR
(C6D6): δ 21.97, 24.16, and 24.75 (s, dCCH3 and dC(CH3)2),
2
75.28 (t, JCP ) 3.8 Hz, C-1 and C-3), 95.48 (s, C-2), 106.74
and 107.45 (s, CγdCdCdC), 109.61 (s, C-3a and C-7a), 114.64
(s, Câ), 121.03 (t, JCP ) 24.6 Hz, Ru-CR), 123.41 and 126.26
[Ru{dCdCdC(CtCR)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2]-
[BF4] (R ) Ph (8), SiMe3 (9)). A solution of [Ru{dCdCd
C(NEt2)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (1.19 g, 1 mmol)
in 50 mL of tetrahydrofuran was slowly added over the
corresponding alkynyllithium (5 mmol) (generated in situ by
addition of Li-n-Bu to a solution of the alkyne in 20 mL of
tetrahydrofuran, at -20 °C), at -20 °C. The reaction mixture
was warmed to room temperature and stirred for a further 30
min. The solvent was then removed under vacuum, the solid
residue was extracted with ca. 40 mL of diethyl ether, and
the orange solution was filtered off. This solution was cooled
at -20 °C, and HBF4‚Et2O was added dropwise. Immediately,
an insoluble blue-violet solid precipitated, but the addition was
continued until no further solid was formed. The solution was
then decanted and the solid washed with diethyl ether (3 ×
20 mL) and dried in vacuo. The solid was transferred to a silica
gel chromatography column. Elution with a dichloromethane/
MeOH (10/1) mixture gave a blue-violet band from which
complexes 8 and 9 were isolated after solvent removal. Data
for 8 are as follows. Yield: 90% (1.04 g). IR (KBr, cm-1): ν-
(CtC) 2167, ν(CdCdC) 1918, ν(BF4-) 1064. 31P{1H} NMR
(CDCl3): δ 47.75 s. 1H NMR (CDCl3): δ 2.39 (s, 3H, dCCH3),
2
(s, C-4, C-5, C-6, and C-7), 125.94-145.32 (m, Ph and Cγ),
136.85 (s, dCCH3), 147.15 (s, dCPh2), 158.58 (s, CγdCdCd
C(CH3)2). Anal. Calcd for C68H56P2Ru: C, 78.82; H, 5.45.
Found: C, 78.63; H, 5.54.
[Ru{CtCC[dCdCdCHPh][C(Me)dCPh2]}(η5-C9H7)-
(PPh3)2] (11). Red solid. Yield: 89% (0.96 g). IR (KBr, cm-1):
ν(CtC) 2059, (CdCdCdC) 1987. 31P{1H} NMR (C6D6): δ 51.46
1
and 51.62 s. H NMR (C6D6): δ 2.50 and 2.64 (s, 3H each, d
CCH3), 4.76 (br, 2H, 2H-1 and 2H-3), 5.40 (m, 2H, 2H-2), 5.97
and 6.03 (s, 1H each, dCH), 6.43-6.51 (m, 4H, H-4, H-5, H-6,
or H-7), 6.80-6.83 (m, 4H, H-4, H-5, H-6, or H-7), 6.95-7.21
(m, 90H, Ph). 13C{1H} NMR (C6D6): δ 22.02 and 22.13 (s, d
CCH3), 75.37 (m, 2C-1 and 2C-3), 95.33 and 95.95 (s, C-2),
101.48 (s, 2dCH), 109.57 and 109.79 (s, 2C-3a and 2C-7a),
113.57 and 113.89 (s, Câ), 118.42 and 118.99 (s, CγdCdCdC),
123.22, 123.37, 126.27, and 126.33 (s, 2C-4, 2C-5, 2C-6, and
2C-7), 126.72-138.71 (m, Ph, Ru-CR), 136.53 and 137.01 (s,
dCCH3), 139.56 (s, 2dCPh2), 140.06-145.25 (m, Cipso and Cγ),
155.39 and 155.80 (s, Cipso). Anal. Calcd for C72H56P2Ru: C,
79.76; H, 5.21. Found: C, 79.67; H, 5.14.
[Ru{CtCC(dCH2)C(Me)dCPh2]}(η5-C9H7)(PPh3)2] (12).
Yellow solid. Yield: 76% (0.74 g). IR (KBr, cm-1): ν(CtC) 2055.
31P{1H} NMR (C6D6): δ 53.02 s. 1H NMR (C6D6): δ 2.43 (s,
3H, dCCH3), 4.68 (s br, 2H, H-1 and H-3), 4.94 and 5.05 (d,
3
3
5.08 (t, 1H, JHH ) 2.8 Hz, H-2), 5.41 (d, 2H, JHH ) 2.8 Hz,
H-1 and H-3), 6.52 (m, 2H, H-4, H-5, H-6, or H-7), 6.85-7.45
(m, 47H, Ph, H-4, H-5, H-6, or H-7). 13C{1H} NMR (CDCl3): δ
26.89 (s, dCCH3), 89.25 (s, C-1 and C-3), 99.23 (s, tC), 100.72
(s, C-2), 102.21 (s, tC), 115.61 (s, C-3a and C-7a), 127.09-
146.76 (m, Ph, dCCH3), dCPh2, C-4, C-5, C-6, and C-7), 156.86
2
1H each, JHH ) 2.6 Hz, dCH), 5.39 (s br, 1H, H-2), 6.38 and
6.70 (m, 2H each, H-4, H-5, H-6, and H-7), 6.92-7.21 (m, 40H,
Ph). 13C{1H} NMR (C6D6): δ 21.80 (s, dCCH3), 74.91 (s br,
C-1 and C-3), 95.10 (s, C-2), 109.34 (s, C-3a and C-7a), 112.07
2
(s, Cγ), 222.68 (s, Câ), 281.78 (t, JCP ) 18.7 Hz, RudCR). MS
(FAB): m/z 1071 [M+], 741 [M+ - R], 479 [M+ - R - PPh3],
363 [M+ - R - PPh3 - C9H8] (R ) [CdCdC(CtCPh){C(Me)d
CPh2}]). ΛM ) 118 Ω-1 cm2 mol-1 (acetone). Data for 9 are as
follows. Yield: 94% (1.08 g). IR (KBr, cm-1): ν(CtC) 2131,
ν(CdCdC) 1922, ν(BF4-) 1058. 31P{1H} NMR (CD2Cl2): δ 48.22
2
(t, JCP ) 24.5 Hz, Ru-CR), 114.90 (s, Câ), 115.94 (s, dCH2),
123.29 and 126.09 (s, C-4, C-5, C-6, and C-7), 125.92-144.62
(m, Ph, dCMe, CdCH2 and dCPh2); Anal. Calcd for C64H52P2-
Ru: C, 78.11; H, 5.32. Found: C, 78.44; H, 4.94.
1
s. H NMR (CD2Cl2): δ -0.05 (s, 9H, Si(CH3)3), 2.33 (s, 3H,
[Ru{CtCC(dCHPr)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2](13).
Orange solid. Yield: 87% (0.89 g). IR (KBr, cm-1): ν(CtC)
2052. 31P{1H} NMR (C6D6): δ 53.09 s. 1H NMR (C6D6): δ 0.64
dCCH3), 5.05 (t, 1H, 3JHH ) 2.6 Hz, H-2), 5.47 (d, 2H, 3JHH
)
2.6 Hz, H-1 and H-3), 6.60 (m, 2H, H-4, H-5, H-6, or H-7),
7.04-7.46 (m, 42H, Ph, H-4, H-5, H-6, or H-7). 13C{1H} NMR
(CD2Cl2): δ -0.13 (s, Si(CH3)3), 23.78 (s, dCCH3), 86.61 (s,
C-1 and C-3), 97.51 (s, C-2), 101.99 and 110.84 (s, CtC), 112.51
(s, C-3a and C-7a), 123.96 (s, C-4, C-5, C-6, and C-7), 128.66-
143.87 (m, Ph, dCCH3 and dCPh2), 152.95 (s, Cγ), 221.88 (s,
3
(t, 3H, JHH ) 7.4 Hz, CH3), 1.14 (m, 2H, CH2), 1.84 (s, 3H,
3
dCCH3), 2.23 (m, 2H, CH2), 4.51 (d, JHH ) 2.4 Hz, H-1 and
H-3), 4.95 (t, 3JHH ) 7.1 Hz, dCH), 5.14 (t, 3JHH ) 2.4 Hz, H-2),
6.43 and 6.80 (m, 2H each, H-4, H-5, H-6, and H-7), 7.06-
7.36 (m, 40H, Ph). 13C{1H} NMR (C6D6): δ14.32 (s, CH3), 21.90

6308 Organometallics, Vol. 23, No. 26, 2004
Conejero et al.
(s, dCCH3), 22.99 (s, CH2), 32.86 (s, dCCH2), 74.78 (s, C-1 and
C-3), 95.76 (s, C-2), 109.99 (s, C-3a and C-7a), 113.00 (t, JCP
mixture (10/1) gave the title compound after solvent removal
as a violet solid. Yield: 82% (0.90 g). IR (KBr, cm-1): ν(Cd
CdC) 1934, ν(PF6-) 837. 31P{1H} NMR (CD2Cl2): δ 46.97 s.
1H NMR (CD2Cl2): δ 5.34 (d, 2H, 3JHH ) 2.9 Hz, H-1 and H-3),
2
) 23.8 Hz, Ru-CR), 113.12 (s, Câ), 123.68 and 126.14 (s, C-4,
C-5, C-6, and C-7), 132.55 (s, dCH), 125.70-144.90 (m, Ph,
dCMe, dCPh2, CdC). Anal. Calcd for C67H58P2Ru: C, 78.42;
H, 5.69. Found: C, 78.62; H, 5.46.
3
5.46 (t, 1H, JHH ) 2.9 Hz, H-2), 6.37 (m, 2H, H-4, H-5, H-6,
or H-7), 6.45 (d, 1H, 3JHH ) 12.1 Hz, dCH), 6.82-7.65 (m, 42H,
Ph, H-4, H-5, H-6, or H-7), 8.48 (d, 1H, 3JHH ) 12.1 Hz, dCd
CdCH). 13C{1H} NMR (CD2Cl2): δ 85.45 (s, C-1 and C-3), 97.50
(s, C-2), 112.47 (s, C-3a and C-7a), 123.65-141.63 (m, Ph, C-4,
C-5, C-6, and C-7), 138.79 (s, dCH), 146.60 (s, Cγ), 160.67 (s,
dCPh2), 215.69 (s, Câ), 292.66 (t, 2JCP ) 18.9 Hz, RudCR). Anal.
Calcd for C62H49F6P3Ru: C, 67.57; H, 4.48. Found: C, 67.39;
H, 4.21. ΛM ) 125 Ω-1 cm2 mol-1 (acetone).
[Ru{CtCC(dCHCHdCH2)[C(Me)dCPh2]}(η5-C9H7)-
(PPh3)2] (14). Orange solid. Yield: 74% (0.74 g). IR (KBr,
cm-1): ν(CtC) 2041. 31P{1H} NMR (C6D6): δ 53.30 s. 1H NMR
3
(C6D6): δ 2.24 (s, 3H, dCCH3), 4.68 (d, 2H, JHH ) 2.6 Hz,
3
2
H-1 and H-3), 4.88 (dd, 1H, JHH ) 10.3 Hz, JHH ) 1.9 Hz,
3
2
dCHaHb), 5.00 (dd, 1H, JHH ) 17.1 Hz, JHH ) 1.9 Hz,
CHaCHb), 5.32 (t, 1H, 3JHH ) 2.6 Hz, H-2), 6.11 (d, 1H, 3JHH
)
[Ru{dCdCdC(NEt2)[(CMedCH)C(Me)dCPh2]}(η5-C9H7)-
(PPh3)2][PF6] (18). This complex was prepared as described
for 3 and 4 by starting from the allenylidene derivative 16
(0.077 mL, 1 mmol) and the ynamine MeCtCNEt2 (83 mL, 2
mmol) as an orange powder. Yield: 0.49 g (80%). IR (KBr,
cm-1): ν(CdCdC) 1992, ν(CdN) 1536, ν(PF6-) 840. 31P{1H}
NMR (CDCl3): δ 49.40 (s). 1H NMR (CDCl3): δ 1.08 and 1.21
(t, 3H each, 3JHH ) 6.8 Hz, CH2CH3), 1.51 and 1.86 (s, 3H each,
10.8 Hz, dCH), 6.51 and 6.77 (m, 2H each, H-4, H-5, H-6, and
H-7), 6.93-7.50 (m, 41H, Ph and dCH). 13C{1H} NMR (C6D6):
δ 22.09 (s, dCCH3), 75.11 (m, C-1 and C-3), 95.43 (s, C-2),
110.01 (s, C-3a and C-7a), 113.43 (s, dCH2), 114.33 (s, Câ),
2
120.94 (t, JCP ) 23.8 Hz, Ru-CR), 123.82 and 126.50 (s, C-4,
C-5, C-6, and C-7), 126.19-139.33 (m, Ph), 132.99 and 138.06
(s, dCH), 133.41 (s, dCCH3), 137.18 (s, Cγ), 139.73 (s, dCPh2),
144.42 and 144.81 (s, Cipso). Anal. Calcd for C66H54P2Ru: C,
78.47; H, 5.39. Found: C, 78.32; H, 5.25.
3
dCCH3), 3.08 and 3.76 (q, 2H each, JHH ) 6.8 Hz, CH2CH3),
[Ru{CtCCH(NEt2)[C(Me)dCPh2]})(η5-C9H7)(PPh3)2] (15).
LiBHEt3 (1 M in tetrahydrofuran; 0.090 mL, 0.08 mmol) was
added to a solution of 3 (0.090 g, 0.08 mmol) in [D8]-
tetrahydrofuran at 0 °C, in a NMR tube. Total conversion of
complex 3 took place instantaneously. 31P{1H} NMR ([D8]-
4.83 (br, 2H, H-1 and H-3), 5.26 (br, 1H, H-2), 5.88 (s, 1H,
dCH), 6.05 (m, 2H, H-4, H-5, H-6, or H-7), 6.90-7.35 (m, 42H,
Ph, H-4, H-5, H-6, or H-7). 13C{1H} NMR (CDCl3): δ 12.90
and 13.78 (s, CH2CH3), 17.33 and 20.60 (s, dCCH3), 45.91 and
47.02 (s, CH2CH3), 76.39 (s, C-1 and C-3), 95.46 (s, C-2), 110.51
(s, C-3a and C-7a), 121.07 (s, Câ), 123.05 (s, C-4, C-5, C-6, or
C-7), 126.98-143.33 (m, Ph, dCCH3, dCPh2, C-4, C-5, C-6, or
2
1
tetrahydrofuran): δ 52.43 and 52.73 (d, JPP ) 34.0 Hz). H
NMR ([D8]tetrahydrofuran): δ 0.80 (m, 6H, CH2CH3), 1.99 (s,
2
3
C-7), 132.41 (s, dCH), 156.21 (s, CγN), 202.21 (t, JCP ) 21.2
3H, dCCH3), 2.65 and 2.72 (q, 2H each, JHH ) 6.8 Hz, CH2-
Hz, RudCR). Anal. Calcd for C70H64F6NP3Ru: C, 68.51; H, 5.26;
N, 1.14. Found: C, 68.14; H, 5.14; N, 1.19. ΛM ) 121 Ω-1 cm2
mol-1 (acetone). MS (FAB): m/z 1082 [M+], 820 [M+ - PPh3],
479 [M+ - PPh3 - R] (R ) [CdCdC(NEt2){CMedCHC(Me)d
CPh2}]).
CH3), 4.40 and 4.47 (br, 1H each, H-1 and H-3), 4.42 (s, 1H,
3
3
CH), 5.13 (t, 1H, JHH ) JHH′ ) 2.4 Hz, H-2), 6.29 and 6.68
(m, 2H each, H-4, H-5, H-6, and H-7), 6.84-7.37 (m, 40H, Ph).
13C{1H} NMR ([D8]tetrahydrofuran): δ 10.82 (s, CH2CH3),
16.82 (s, dCCH3), 42.09 (s, CH2CH3), 58.79 (s, CγH), 73.22 and
73.36 (s, C-1 and C-3), 93.60 (t, JCP ) JCP ) 22.7 Hz, Ru-
CR), 94.83 (s, C-2), 109.11, 109.64, and 110.24 (s, C-3a, C-7a,
and Câ), 122.74 and 123.27 (s, C-4, C-5, C-6, or C-7), 125.10-
138.89 (m, Ph, C-4, C-5, C-6, or C-7), 142.89 and 143.94 (s,
dCCH3 and dCPh2).
2
2
[Ru{dCdCdC(NEt2)[(C(SiMe3)dCH)C(Me)dCPh2]}(η5-
C9H7)(PPh3)2][PF6] (19). A solution of [Ru{dCdCdC(H)-
[C(Me)dCPh2]}(η5-C9H7)(PPh3)2][PF6] (16; 1.17 g, 1 mmol) in
50 mL of tetrahydrofuran was slowly added to a solution of
Me3SiCtCNEt2 (0.34 g, 2 mmol) in 10 mL of tetrahydrofuran
at room temperature. The solution became immediately or-
ange, and the reaction mixture was stirred for a further 1 h.
The solvent was then removed under vacuum and the residue
washed with diethyl ether (2 × 30 mL). The solid residue was
purified by chromatography column on silica gel with diethyl
ether/dichloromethane (4/1) as eluant, giving an orange band.
Evaporation of the solvents yielded complex 19 as an orange
solid. Yield: 0.77 g (60%). IR (KBr, cm-1): ν(CdCdC) 1987,
ν(CdN) 1533, ν(PF6-) 839. 31P{1H} NMR (CDCl3): δ 47.60 and
48.32 (d, 2JPP ) 26.1 Hz). 1H NMR (CDCl3): δ 0.41 (s, 9H, Si-
(CH3)3), 0.84 and 0.92 (t, 3H each, 3JHH ) 7.1 Hz, N(CH2CH3)2),
2.13 (s, 3H, dCCH3), 3.02 and 3.19 (m, 1H each, NCH2CH3),
3.02-3.44 (m, 2H, NCH2CH3), 4.76 and 4.86 (br, 1H each, H-1
[Ru{dCdCdC(H)[C(Me)dCPh2]}(η5-C9H7)(PPh3)2]-
[PF6] (16). A solution of 15 (0.5 mmol) in tetrahydrofuran (5
mL) was transferred to a silica gel column (20 cm). Elution
with a hexane/diethyl ether mixture (3/1) produced a change
of color from orange to violet. Once the transformation of color
finished, the elution with a mixture of dichloromethane/MeOH
(10/1) gave a violet band. Evaporation of the solvents yields
complex 16 as a violet powder. Yield: 0.53 g, 86%. IR (KBr,
cm-1): ν(CdCdC) 1932, ν(PF6-) 839. 31P{1H} NMR (CDCl3):
δ 46.99 (s). 1H NMR (CDCl3): δ 2.30 (s, 3H, dCCH3), 5.31 (br,
2H, H-1 and H-3), 5.39 (br, 1H, H-2), 6.33 (m, 2H, H-4, H-5,
H-6, or H-7), 7.14-7.57 (m, 42H, Ph, H-4, H-5, H-6, or H-7),
8.34 (s, 1H, dCdCdCH). 13C{1H} NMR (CDCl3): δ 19.13 (s,
dCCH3), 84.92 (s, C-1 and C-3), 96.81 (s, C-2), 111.65 (s, C-3a
and C-7a), 123.25 (s, C-4, C-5, C-6, or C-7), 126.47-142.35 (m,
Ph, dCCH3, C-4, C-5, C-6, or C-7), 150.61 (s, Cγ), 161.70 (s,
dCPh2), 208.84 (s, Câ), 295.05 (t, 2JCP ) 19.7 Hz, RudCR). Anal.
Calcd for C63H51F6P3Ru: C. 67.80; H, 4.60. Found: C, 67.64;
H, 4.75. ΛM ) 127 Ω-1 cm2 mol-1 (acetone). MS (FAB): m/z
971 [M+], 741 [M+ - R], 479 [M+ - R - PPh3] (R ) [CdCd
CH{C(Me)dCPh2}]).
3
3
and H-3), 5.38 (t, 1H, JHH ) JHH′ ) 2.6 Hz, H-2), 5.74 and
3
5.90 (d, 1H each, JHH ) 7.1 Hz, H-4, H-5, H-6, or H-7), 6.61
(s, 1H, dCH), 6.66-7.39 (m, 42H, Ph, H-4, H-5, H-6, or H-7).
13C{1H} NMR (CDCl3): δ 0.67 (s, Si(CH3)3), 12.37 and 13.23
(s, N(CH2CH3)2), 21.70 (s, dCCH3), 45.19 and 45.65 (s, N(CH2-
2
2
CH3)2), 74.71 (d, JCP ) 6.5 Hz, C-1 or C-3), 75.66 (d, JCP
)
5.5 Hz, C-1 or C-3), 96.13 (s, C-2), 110.90 and 111.27 (s, C-3a
and C-7a), 121.27 (s, Câ), 123.05 and 123.25 (s, C-4, C-5, C-6,
or C-7), 127.28-137.18 (m, Ph, C-4, C-5, C-6, or C-7), 130.79
(s, dCCH3), 141.10, 141.80, 141.94, and 144.46 (s, Cipso, dCPh2
and dCSiMe3), 145.30 (s, dCH), 159.14 (s, CγN), 201.50 (dd,
[Ru{dCdCdC(H)(CHdCPh2)}(η5-C9H7)(PPh3)2][PF6] (17).
LiBHEt3 (1 M; 1.2 mL, 1.2 mmol) was added, at -20 °C, to a
solution of [Ru{dCdCdC(NEt2)(CHdCPh2)}(η5-C9H7)(PPh3)2]-
[PF6] (6; 1.17 g, 1 mmol) in 50 mL of tetrahydrofuran. The
mixture was warmed to room temperature, and the solvent
was concentrated to ca. 5 mL. The orange solution was
transferred to a silica gel chromatography column (20 cm
high). Elution with a hexane/diethyl ether (3/1) mixture led
to a color change from orange to violet. Once the orange color
totally disappeared, elution with a dichloromethane/MeOH
2
2JCP ) 21.7 Hz, JCP′ ) 19.9 Hz, RudCR). Anal. Calcd for
C72H70F6NP3SiRu: C. 67.28; H, 5.49; N, 1.08. Found: C, 66.91;
H, 5.52; N, 0.99. ΛM ) 122 Ω-1 cm2 mol-1 (acetone).
[Ru{CtCCH(NEt2)[(CMedCH)C(Me)dCPh2]}(η5-C9H7)-
(PPh3)2] (20). This complex was prepared in a NMR tube as
described for 16 by starting from the allenylidene complex 18
(0.080 g, 0.07 mmol) and LiBHEt3 (1 M in tetrahydrofuran;

Indenylruthenium(II) Aminoallenylidenes
Organometallics, Vol. 23, No. 26, 2004 6309
Table 3. Crystal Data and Structure Refinement
0.080 mL, 0.07 mmol). Total conversion of complex 18 took
place instantaneously. 31P{1H} NMR ([D8]tetrahydrofuran): δ
52.18and52.95(d,2JPP )31.7Hz).1HNMR([D8]tetrahydrofuran):
Details for 3‚EtOH
chem formula
fw
C66H58F6NP3Ru‚EtOH
3
δ 0.83 (t, 6H, JHH ) 7.0 Hz, CH2CH3), 1.47 and 1.66 (s, 3H
1225.69
3
each, dCCH3), 2.36 (q, 4H, JHH ) 7.0 Hz, CH2CH3), 3.99 (s,
T (K)
200(2)
1H, CH), 4.39 and 4.45 (br, 1H each, H-1 and H-3), 5.15 (br,
1H, H-2), 6.14 and 6.61 (m, 2H each, H-4, H-5, H-6, and H-7),
6.74 (s, 1H, dCH), 7.01-7.28 (m, 40H, Ph). 13C{1H} NMR ([D8]-
tetrahydrofuran): δ 13.35 and 13.38 (s, CH2CH3), 16.02 and
21.36 (s, dCCH3), 42.75 and 43.84 (s, CH2CH3), 62.57 (s, CγH),
wavelength (Å)
cryst system
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
1.54184
triclinic
P1h
13.0687(6)
13.7345(6)
18.4915(7)
110.983(2)
104.348(2)
90.063(3)
2
73.58 and 73.86 (s, C-1 and C-3), 94.57 (s, C-2), 95.87 (t, JCP
) 2JCP′ ) 24.8 Hz, Ru-CR), 107.19, 108.53, and 109.34 (s, C-3a,
C-7a, and Câ), 122.34, 122.93, 124.93, and 125.95 (s, C-4, C-5,
C-6, and C-7), 125.39-143.92 (m, Ph, dCH, dCCH3, dCPh2).
[Ru{dCdCdC(H)[(CMedCH)C(Me)dCPh2]}(η5-C9H7)-
(PPh3)2][PF6] (21). This complex was prepared as described
for 16 starting from complex 20 (0.5 mmol) to give a violet
powder. Yield: 0.48 g (83%). IR (KBr, cm-1): ν(CdCdC) 1938,
ν(PF6-) 839. 31P{1H} NMR (CDCl3): δ 48.06 (s). 1H NMR
(CDCl3): δ 2.00 and 2.25 (s, 3H each, dCCH3), 5.22 (t, 1H,
2987.5(2)
Z
2
F
calcd (g cm-3
)
1.363
µ (mm-1
F(000)
)
3.401
1267
cryst size (mm)
monochromator
θ range (deg)
index ranges
0.23 × 0.075 × 0.075
graphite
2.65-69.88
-15 e h e 15
-16 e k e 15
0 e l e 22
27 340
3
3JHH ) 2.6 Hz, H-2), 5.27 (d, 2H, JHH ) 2.6 Hz, 1H, H-1 and
H-3), 6.32 (m, 2H, H-4, H-5, H-6, or H-7), 6.92-7.44 (m, 43H,
Ph, dCH, H-4, H-5, H-6, or H-7), 8.17 (s, 1H, dCdCdCH).
13C{1H} NMR (CDCl3): δ 15.71 and 20.06 (s, dCCH3), 84.73
(s, C-1 and C-3), 96.68 (s, C-2), 111.31 (s, C-3a and C-7a),
123.08 (s, C-4, C-5, C-6, and C-7), 126.95-134.69 (m, Ph, d
CCH3), 142.41 and 142.71 (s, Cipso), 145.39 (s, dCCH3), 150.60
(s, dCPh2), 152.32 (s, Cγ), 158.49 (s, dCH), 203.50 (s, Câ),
290.93 (t, 2JCP ) 19.2 Hz, RudCR). Anal. Calcd for C66H55F6P3-
Ru: C, 68.56; H, 4.79. Found: C, 68.21; H, 4.88. ΛM ) 119
Ω-1 cm2 mol-1 (acetone). MS (FAB): m/z 1010 [M+], 741 [M+
- R], 479 [M+ -R - PPh3] (R ) [CdCdC(H){(CMedCH)C-
(Me)dCPh2}).
no. of rflns collected
no. of indep rflns
11 083 (R(int) ) 0.076)
712/3
0.892
R1 ) 0.0503, wR2 ) 0.1166
R1 ) 0.0778, wR2 ) 0.1275
0.961 and -0.649 e
no. of params/restraints
goodness of fit on F2
R (I > 2σ(I))a
R (all data)
largest diff peak and hole (e Å-3
)
2 2
a R1 ) ∑(|Fo| - |Fc|)/∑|Fo|; wR2 ) {∑[w(Fo2 - Fc2)2]/∑[w(Fo ) ]}1/2
.
The structure was solved by Patterson methods using the
program DIRDIF.20 A multiscan absorption correction was
applied using SORTAV21 (ratio of minimum to maximum
apparent transmission 077099). Full-matrix least-squares
refinement on F2 was carried out with SHELXL-97.22 All non-H
atoms were anisotropically refined except the F atoms and
[Ru{dCdCdC(NEt2)[(CMedCH)2C(Me)dCPh2]}(η5-
C9H7)(PPh3)2][PF6] (22). This complex was prepared as
described for 3 and 4 by starting from the allenylidene
derivative 21 (0.29 g, 0.25 mmol) and the ynamine MeCt
CNEt2 (0.039 mL, 0.5 mmol) to give an orange powder. Yield:
0.14 g (45%). IR (KBr, cm-1): ν(CdCdC) 1990, ν(CdN) 1533,
ν(PF6-) 840. 31P{1H} NMR (CDCl3): δ 49.59 (s). 1H NMR
(CDCl3): δ 1.26 and 1.31 (t, 3H each, 3JHH ) 7.4 Hz, CH2CH3),
1.49, 1.65, and 1.88 (s, 3H each, dCCH3), 3.54 and 3.88 (q, 2H
each, 3JHH ) 7.4 Hz, CH2CH3), 4.82 (d, 2H, 3JHH ) 2.6 Hz, H-1
-
C68, C69, and O1 atoms of the disordered PF6 and ethanol
solvent molecules, respectively, which were isotropically re-
fined. The H atoms were geometrically placed, and their
coordinates were refined riding on their parent atoms. The
final cycle of full-matrix least-squares refinement based on
11 083 reflections and 712 parameters converged to a final
value of R1 (F2 > 2σ(F2)) ) 0.0503. The function minimized
was [∑w(Fo2 - Fc2)/∑w(Fo2)]1/2, where w ) 1/[σ2(Fo2) + (0.0324P)2]
3
and H-3), 5.20 (t, 1H, JHH ) 2.6 Hz, H-2), 5.50 and 5.97 (s,
1H each, dCH), 6.12 (m, 2H, H-4, H-5, H-6, or H-7), 6.90-
7.50 (m, 42H, Ph, H-4, H-5, H-6, or H-7). 13C{1H} NMR
(CDCl3): δ 13.02 and 13.76 (s, CH2CH3), 16.78, 18.22, and
21.09 (s, dCCH3), 46.40 and 47.55 (s, CH2CH3), 76.70 (s, C-1
and C-3), 95.43 (s, C-2), 110.42 (s, C-3a and C-7a), 121.14 (s,
Câ), 123.15 (s, C-4, C-5, C-6, and C-7), 126.60-143.18 (m, Ph,
dCCH3, dCPh2, dCH), 157.11 (s, CγN), 202.61 (t, 2JCP ) 21.5
Hz, RudCR). Anal. Calcd for C73H68F6NP3Ru: C, 69.18; H, 5.41;
N, 1.10. Found: C, 69.34; H, 5.15; N, 1.06. ΛM ) 115 Ω-1 cm2
mol-1 (acetone).
with σ2(Fo ) from counting statistics and P ) (Max (Fo ,0) +
2Fc2)/3. Atomic scattering factors were taken from ref 23.
Geometrical calculations were made with PARST.24 The
crystallographic plots were made with PLATON.25
2
2
Acknowledgment. This work was supported by the
Ministerio de Ciencia y Tecnolog´ıa (MCT) (Project
BQU2000-0227). S.C. thanks the Ministerio de Educa-
cio´n y Cultura (MEC) of Spain for the award of a Ph.D.
grant.
X-ray Structure Determination of 3‚EtOH. Crystals
suitable for X-ray diffraction analysis were obtained by slow
diffusion of n-pentane into a saturated solution of the complex
in ethanol. Data collection, crystal, and refinement parameters
are collected in Table 3. Diffraction data were recorded at 200-
(2) K on a Nonius KappaCCD single-crystal diffractometer
using Cu KR radiation. The crystal-to-detector distance was
fixed at 29 mm, and a total of 1210 frames were collected using
the oscillation method, with 2° oscillation and 40 s exposure
time per frame. The data collection strategy was calculated
with the program Collect.18 Data reduction and cell refinement
were performed using the programs HKL Denzo and Scale-
pack.19 Unit cell dimensions were determined from 10 681
reflections. All data completeness was 98%.
(20) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
Garc´ıa-Granda, S.; Gould, R. O.; Smits, J. M. M.; Smykalla, C. The
DIRDIF Program System; Techical Report of the Crystallographic
Laboratory; University of Nijimegen, Nijimegen, The Netherlands,
1996.
(21) Blessing, R. H. Acta Crystallogr., Sect. A 1995, 51, 33.
(22) Sheldrick, G. M. SHELXL-97: Program for the Refinement of
Crystal Structures; University of Go¨ttingen, Go¨ttingen, Germany,
1997.
(23) International Tables for X-ray Crystallography; Kynoch
Press: Birmingham, U.K., 1974; Vol. IV (present distrubutor: Kluwer
Academic Publishers, Dordrecht, The Netherlands).
(24) Nardelli, M. Comput. Chem. 1983, 7, 95.
(25) Spek, A. L. PLATON, a Multipurpose Crystallographic Tool;
Utrecht University, Utrecht, The Netherlands, 2003.
(18) Collect, Nonius BV, Delft, The Netherlands, 1997-2000.
(19) Otwinowski, Z.; Minor, W. Methods Enzymol. 1997, 276, 307.

6310 Organometallics, Vol. 23, No. 26, 2004
Conejero et al.
Supporting Information Available: Text giving synthe-
sis details and characterization data for complex 23 and tables
and a CIF file giving crystallographic data for complex 3. This
material is available free of charge via the Internet at http://
pubs.acs.org. Crystallographic data have also been deposited
with the Cambridge Crystallographic Data Centre, CCDC Nos.
235820 (3) and 179713 (18). These data can be obtained free
of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or
from the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB21EZ, U.K.; fax (internat.) (+44)1223/336-
033; e-mail deposit@ccdc.cam.ac.uk).
OM049413P