Efficient one-pot synthesis of α,β-unsaturated carbyne complexes fac-[RuX3{≡CC(H)=CR2}(dppf)] (X = Cl, Br; R = aryl, alkyl; dppf = 1,1′-bis(diphenylphosphino)ferrocene)

Article abstract of DOI:10.1021/om050204u

Alkenyl-carbyne complexes fac-[RuX₃{≡CC(H)=CR ₂}(dppf)] (X = Cl, Br; R = Ph, ⁱPr or CR₂ = C₁₃H₈) (2a-c, 3a-c) have been prepared by reaction of the bis(allyl)-ruthenium(II) derivative [Ru(η

Full text of DOI:10.1021/om050204u

Organometallics 2005, 24, 3111-3117
3111
Efficient One-Pot Synthesis of r,â-Unsaturated Carbyne
Complexes fac-[RuX3{tCC(H)dCR2}(dppf)] (X ) Cl, Br; R
) Aryl, Alkyl; dppf )
1,1′-Bis(diphenylphosphino)ferrocene)
Victorio Cadierno,* Josefina D´ıez, Sergio E. Garc´ıa-Garrido, and Jose´ Gimeno*
Departamento de Quı´mica Orga´nica e Inorga´nica, Instituto Universitario de Quı´mica
Organometa´lica “Enrique Moles” (Unidad Asociada al CSIC), Facultad de Qu´ımica,
Universidad de Oviedo, E-33071 Oviedo, Spain
Received March 18, 2005
i
Alkenyl-carbyne complexes fac-[RuX3{tCC(H)dCR2}(dppf)] (X ) Cl, Br; R ) Ph, Pr or
CR2 ) C13H8) (2a-c, 3a-c) have been prepared by reaction of the bis(allyl)-ruthenium(II)
derivative [Ru(η3-2-C3H4Me)2(dppf)] (1) with the appropriate propargylic alcohol HCtCCR2-
(OH) in the presence of 3.5 equiv of the corresponding hydrogen halide HX. The structure
of compounds fac-[RuCl3{tCC(H)dCR2}(dppf)] (R ) Ph (2a) and iPr (2c)) has been confirmed
by X-ray crystallography. Structural parameters within the alkenyl-carbyne chain in 2a,c
suggest an important contribution of the zwitterionic vinylidene canonical form fac-[RuCl3-
{dCdC(H)-CR2}(dppf)]. Formation of complexes 2,3a-c involves the 1,3-addition of HX to
the corresponding dinuclear allenylidene intermediates [{RuX(µ-X)(dCdCdCR2)(dppf)}2].
Such allenylidene complexes, i.e., [{RuX(µ-X)(dCdCdCR2)(dppf)}2] (X ) Cl, Br; R ) Ph or
CR2 ) C13H8) (4a,b, 5a,b), have been prepared and characterized by treatment of fac-[RuX3-
{tCC(H)dCR2}(dppf)] (X ) Cl, Br; R ) Ph or CR2 ) C13H8) (2a,b, 3a,b) with 1 equiv of
AgSbF6, via halide abstraction and concomitant deprotonation of the alkenyl-carbyne chain.
Chart 1
Introduction
After Fischer and co-workers reported in 1973 the
preparation and structural characterization of the first
examples of transition metal carbyne complexes, namely,
[MX(tCR)(CO)4] (M ) Cr, Mo, W; X ) Cl, Br, I; R )
Me, Ph),1 the chemistry of this class of compounds has
been largely developed not only because of their unusual
type of bonding but also due to their growing applica-
tions in organic synthesis.2 Among the most useful
synthetic routes for the preparation of carbyne com-
plexes,2 the addition of electrophiles to the nucleophilic
Câ of coordinated vinylidene and allenylidene ligands
is now well established (see Chart 1).3,4 In particular,
when allenylidene complexes are used as starting
materials, R,â-unsaturated alkenyl-carbynes [M]tC-
C(E)dCR2 are readily generated.
In contrast to the high number of osmium-carbyne
complexes reported to date,5 those of ruthenium are
much less numerous6 despite some of them having
proven to be active catalysts in olefin metathesis.6b,e,i,m
In particular, ruthenium alkenyl-carbynes are very
scarce. Thus, until now, the only examples described in
the literature are (see Chart 2) [RuCl{tCC(H)dCPh2}-
{κ2(P,O)-Cy2P(CH2)2OMe}{κ1(P)-Cy2P(CH2)2OMe}]-
[BF4, PF6] (A),6f [Ru{tCC(H)dC(R)Ph}(η5-C5Me5)(dippe)]-
* Towhomcorrespondenceshouldbeaddressed.E-mail: jgh@uniovi.es
(J.G.); vcm@uniovi.es (V.C.).
(1) Fischer, E. O.; Kreis, G.; Kreiter, C. G.; Mu¨ller, J.; Huttner, G.;
Lorenz, H. Angew. Chem., Int. Ed. Engl. 1973, 12, 564.
(2) For general reviews on the chemistry of transition metal carbyne
complexes see: (a) Kim H. P.; Angelici, R. J. Adv. Organomet. Chem.
1987, 27, 51. (b) Fischer, H.; Hofmann, P.; Kreissl, F. R.; Schrock, R.
R.; Schubert, U.; Weiss, K. In Carbyne Complexes; VCH: Weinheim,
Germany, 1988. (c) Mayr, A.; Hoffmeister, H. Adv. Organomet. Chem.
1991, 32, 227. (d) Engel, P. F.; Pfeffer, M. Chem. Rev. 1995, 95, 2281.
(e) Schrock, R. R. J. Chem. Soc., Dalton Trans. 2001, 2541, and
references therein.
(4) For reviews on the chemistry of transition metal allenylidene
complexes see: (a) Le Bozec, H.; Dixneuf, P. H. Russ. Chem. Bull. 1997,
44, 801. (b) Werner, H. Chem. Commun. 1997, 903. (c) Bruce, M. I.
Chem. Rev. 1998, 98, 2797. (d) Touchard, D.; Dixneuf, P. H. Coord.
Chem. Rev. 1998, 178-180, 409. (e) Cadierno, V.; Gamasa, M. P.;
Gimeno, J. Eur. J. Inorg. Chem. 2001, 571. (f) Werner, H.; Ilg, K.; Lass,
R.; Wolf, J. J. Organomet. Chem. 2002, 661, 137. (g) Winter, R. F.;
Za´lisˇ, S. Coord. Chem. Rev. 2004, 248, 1565. (h) Rigaut, S.; Touchard,
D.; Dixneuf, P. H. Coord. Chem. Rev. 2004, 248, 1585. (i) Fischer, H.;
Szesni, N. Coord. Chem. Rev. 2004, 248, 1659.
(3) For reviews on the chemistry of transition metal vinylidene
complexes see: (a) Bruce, M. I. Chem. Rev. 1991, 91, 197. (b) Werner,
H. J. Organomet. Chem. 1994, 475, 45. (c) Bruneau, C.; Dixneuf, P. H.
Acc. Chem. Res. 1999, 32, 311. (d) Puerta, M. C.; Valerga, P. Coord.
Chem. Rev. 1999, 193-195, 977. (e) Selegue, J. P. Coord. Chem. Rev.
2004, 248, 1543. (f) Cadierno, V.; Gamasa, M. P.; Gimeno, J. Coord.
Chem. Rev. 2004, 248, 1627. (g) Werner, H. Coord. Chem. Rev. 2004,
248, 1692. (h) Katayama, H.; Ozawa, F. Coord. Chem. Rev. 2004, 248,
1703.
10.1021/om050204u CCC: $30.25 © 2005 American Chemical Society
Publication on Web 05/18/2005

3112 Organometallics, Vol. 24, No. 13, 2005
Cadierno et al.
Chart 2
[B(ArF)4]2 (dippe ) 1,2-bis(diisopropylphosphino)ethane;
R ) H, Ph; ArF ) 3,5-C6H3(CF3)2) (B),6g trans-[RuCl-
{tCC(H)dC(R)Me}(dppe)2][BF4]2 (dppe ) bis(diphenyl-
phosphino)ethane; R ) Me, Ph) (C),6k trans-[Cl(dppe)2-
Ru{tCC(H)dC(Me)-p-C6H4-C(Me)dC(H)Ct}RuCl(dppe)2]-
[BF4]4 (D),6k [RuCl{tCC(H)dCPh2}(η6-p-cymene)(PCy3)]-
[CF3SO3]2 (E),6m,7 and mer,trans-[RuCl3{tCC(H)dCMe2}-
(PPh3)2] (F).6h
carbyne ruthenium complexes fac-[RuX3{tCC(H)dCR2}-
(dppf)] (G) (dppf ) 1,1′-bis(diphenylphosphino)fer-
rocene)8 (see Chart 3), which avoids the use of isolated
Chart 3
With the exception of complex F, which has been
obtained by reacting [RuHCl(PPh3)3] with an excess of
3-chloro-3-methyl-1-butyne (HCtCC(Cl)Me2),6h the rest
of alkenyl-carbynes A-E have been generated by pro-
tonation of the corresponding allenylidene derivatives.
This synthetic methodology requires that these starting
materials have to be available.
In the present paper we report a straightforward and
efficient synthetic approach to novel neutral alkenyl-
(5) For recent examples see: (a) Castarlenas, R.; Esteruelas, M. A.;
Gutie´rrez-Puebla, E.; On˜ate, E. Organometallics 2001, 20, 1545. (b)
Wen, T. B.; Zhou, Z. Y.; Jia, G. Angew. Chem., Int. Ed. 2001, 40, 1951.
(c) Castarlenas, R.; Esteruelas, M. A.; On˜ate, E. Organometallics 2001,
20, 3283. (d) Baya, M.; Esteruelas, M. A.; On˜ate, E. Organometallics
2001, 20, 4875. (e) Baya, M.; Esteruelas, M. A. Organometallics 2002,
21, 2332. (f) Barrio, P.; Esteruelas, M. A.; On˜ate, E. Organometallics
2002, 21, 2491. (g) Baya, M.; Esteruelas, M. A.; On˜ate, E. Organome-
tallics 2002, 21, 5681. (h) Wen, T. B.; Ng, S. M.; Hung, W. Y.; Zhou, Z.
Y.; Lo, M. F.; Shek, L.-Y.; Williams, I. D.; Lin, Z.; Jia, G. J. Am. Chem.
Soc. 2003, 125, 884. (i) Esteruelas, M. A.; Gonza´lez, A. I.; Lo´pez, A.
M.; On˜ate, E. Organometallics 2003, 22, 414. (j) Barrio, P.; Esteruelas,
M. A.; On˜ate, E. Organometallics 2003, 22, 2472. (k) Wen, T. B.; Zhou,
Z. Y.; Lo, M. F.; Williams, I. D.; Jia, G. Organometallics 2003, 22, 5217.
(l) Barrio, P.; Esteruelas, M. A.; On˜ate, E. J. Am. Chem. Soc. 2004,
126, 1946. (m) Esteruelas, M. A.; Lo´pez, A. M.; On˜ate, E.; Royo, E.
Organometallics 2004, 23, 3021. (n) Esteruelas, M. A.; Gonza´lez, A.
I.; Lo´pez, A. M.; On˜ate, E. Organometallics 2004, 23, 4858. (o) Asensio,
A.; Buil, M. L.; Esteruelas, M. A.; On˜ate, E. Organometallics 2004,
23, 5787. (p) Wen, T. B.; Hung, W. Y.; Zhou, Z. Y.; Lo, M. F.; Williams,
I. D.; Jia, G. Eur. J. Inorg. Chem. 2004, 2837.
(6) (a) Baker, L. J.; Clark, G. R.; Rickard, C. E. F.; Roper, W. R.;
Woodgate, S. D.; Wright, L. J. J. Organomet. Chem. 1998, 551, 247.
(b) Stu¨er, W.; Wolf, J.; Werner, H.; Schwab, P.; Schulz, M. Angew.
Chem., Int. Ed. 1998, 37, 3421. (c) Gonza´lez-Herrero, P.; Weberndo¨rfer,
B.; Ilg, K.; Wolf, J.; Werner, H. Angew. Chem., Int. Ed. 2000, 39, 3266.
(d) Coalter, J. N., Bollinger, J. C.; Eisenstein, O.; Caulton, K. G. New
J. Chem. 2000, 24, 925. (e) Gonza´lez-Herrero, P.; Weberndo¨rfer, B.;
Ilg, K.; Wolf, J.; Werner, H. Organometallics 2001, 20, 3672. (f) Jung,
S.; Brandt, C. D.; Werner, H. New J. Chem. 2001, 25, 1101. (g) Bustelo,
E.; Jime´nez-Tenorio, M.; Mereiter, K.; Puerta, M. C.; Valerga, P.
Organometallics 2002, 21, 1903. (h) Amoroso, D.; Snelgrove, J. L.;
Conrad, J. C.; Drouin, S. D.; Yap, G. P. A.; Fogg, D. E. Adv. Synth.
Catal. 2002, 344, 757. (i) Jung, S.; Ilg, K.; Brandt, C. D.; Wolf, J.;
Werner, H. J. Chem. Soc., Dalton Trans. 2002, 318. (j) Conrad, J. C.;
Amoroso, D.; Czechura, P.; Yap, G. P. A.; Fogg, D. E. Organometallics
2003, 22, 3634. (k) Rigaut, S.; Touchard, D.; Dixneuf, P. H. Organo-
metallics 2003, 22, 3980. (l) Beach, N. J.; Jenkins, H. A.; Spivak, G. J.
Organometallics 2003, 22, 5179. (m) Castarlenas, R.; Dixneuf, P. H.
Angew. Chem., Int. Ed. 2003, 42, 4524. (n) Jung, S.; Ilg, K.; Brandt,
C. D.; Wolf, J.; Werner, H. Eur. J. Inorg. Chem. 2004, 469.
allenylidenes as starting materials. They have been
prepared in a one-pot manner by reacting the bis(allyl)-
ruthenium(II) complex [Ru(η3-2-C3H4Me)2(dppf)] (1)9
with propargylic alcohols in the presence of HCl or HBr.
The process involves the initial formation of dinuclear
allenylidene species [{RuX(µ-X)(dCdCdCR2)(dppf)}2]
(H), via HX-promoted releasing of the η3-allyl units from
1,10 which react in situ with HX to give the alkenyl-
carbyne derivatives G. The synthesis of these dinuclear
metallacumulenes by treatment of fac-[RuX3{tCC(H)d
CR2}(dppf)] (G) with AgSbF6 is also reported.
(7) P. H. Dixneuf and co-workers have recently demonstrated that
the dicationic alkenyl-carbyne [RuCl{tCC(H)dCPh2}(η6-p-cymene)-
(PCy3)][CF3SO3]2 (E) is a key intermediate in the intramolecular
transformation of the diphenylallenylidene complex [RuCl(dCdCd
CPh2)(η6-p-cymene)(PCy3)][CF3SO3] into the indenylidene derivative
[RuCl(3-phenylinden-1-ylidene)(η6-p-cymene)(PCy3)][CF3SO3], the lat-
ter showing an extremely high catalytic activity in ROMP. See ref 6m
and (a) Bassetti, M.; Centola, F.; Se´meril, D.; Bruneau, C.; Dixneuf,
P. H. Organometallics 2003, 22, 4459. We note that related ruthenium
indenylidene complexes of type [RuCl2(L)(L′)(3-phenylinden-1-ylidene)]
(L ) L′ ) PCy3, PPh3; L ) N-heterocyclic carbene, L′ ) PCy3, PPh3),
resulting from the corresponding diphenylallenylidenes, have been
widely used as robust and efficient catalysts for olefin RCM and ROMP
reactions. See for example: (b) Dragutan, V.; Dragutan, I.; Verpoort,
F. Platinum Met. Rev. 2005, 49, 33, and references therein.
(8) For reviews on the coordination chemistry of dppf and related
ferrocenyl-phosphine ligands see: (a) Gan, K. S.; Hor, T. S. A. In
Ferrocenes: Homogeneous Catalysis, Organic Synthesis and Material
Science; Togni, A., Hayashi, T., Eds.; VCH: Weinheim, 1995; p 3. (b)
Bandoli, G.; Dolmella, A. Coord. Chem. Rev. 2000, 209, 161. (c) Colacot,
T. J. Platinum Met. Rev. 2001, 45, 22.
(9) Smith, D. C., Jr.; Cadoret, J.; Jafarpour, L.; Stevens, E. D.; Nolan,
S. P. Can. J. Chem. 2001, 79, 626.

Synthesis of R,â-Unsaturated Carbyne Complexes
Organometallics, Vol. 24, No. 13, 2005 3113
Scheme 1
Results and Discussion
Synthesis and Characterization of the Alkenyl-
Carbyne Complexes fac-[RuX3{tCC(H)dCR2}-
i
(dppf)] (X ) Cl, Br; R ) Ph, Pr or CR2 ) C13H8)
(2a-c, 3a-c). Dehydration of propargylic alcohols HCt
CC(OH)R2 upon coordination to an unsaturated metal
center is probably the most general synthetic approach
to allenylidene complexes [M]dCdCdCR2.4,11 We have
recently reported that the treatment of the readily
available bis(allyl)-ruthenium(II) derivative [Ru(η3-2-
C3H4Me)2(dppf)] (1)9 with 2 equiv of hydrogen halides
HX (X ) Cl, Br) effectively delivers the unsaturated
ruthenium(II) fragments [RuX2(dppf)], via releasing of
2-methylpropene, which can be readily trapped in the
presence of isocyanides, affording complexes trans,cis,-
cis-[RuX2(CNR)2(dppf)].10d On the basis of these results
we wondered about the possibility of using the highly
reactive species [RuX2(dppf)] as suitable starting ma-
terials for the preparation of five-coordinate allenylidene-
ruthenium(II) complexes [RuX2(dCdCdCR2)(dppf)] by
trapping them with propargylic alcohols.12,13
However, we have found that the treatment of dichlo-
romethane or acetone solutions of complex [Ru(η3-2-
C3H4Me)2(dppf)] (1) with 1,1-diphenyl-2-propyn-1-ol,
9-ethynyl-9-fluorenol, or 3-isopropyl-4-methyl-1-pentyn-
3-ol, in the presence of 2 equiv of HX, leads instead to
complicated reaction mixtures containing the desired
allenylidene derivatives and the alkenyl-carbyne com-
plexes fac-[RuX3{tCC(H)dCR2}(dppf)] (2a-c, 3a-c)
along with several unidentified species. The presence
in these mixtures of both alkenyl-carbyne and alle-
nylidene species strongly suggests that a rapid 1,3-
addition of a HX molecule to the allenylidene interme-
diates [RuX2(dCdCdCR2)(dppf)] has occurred. This has
been assessed by performing the reactions with a slight
excess of HX (3.5 equiv), which leads to the selective
formation of the alkenyl-carbynes fac-[RuX3{tCC(H)d
CR2}(dppf)] (2a-c, 3a-c) (see Scheme 1).
typical ν(CdC) absorption band in the range 1540-1574
cm-1, (ii) (31P{1H} NMR) the appearance of a singlet
signal at 19.15-22.27 ppm, in accord with the proposed
fac stereochemistry and the chemical equivalence of the
phosphorus nuclei of the dppf ligand, (iii) (1H NMR) a
singlet (2b,c and 3c) or triplet (2a and 3a,b; 4JHP ) 3.7-
4.0 Hz) resonance at 3.59-4.33 ppm assigned to the
olefinic dCH hydrogen, and (iv) (13C{1H} NMR) char-
acteristic low-field resonances for the carbynic RutCR
and olefinic CâdCγ carbon nuclei which appear in the
ranges 292.45-298.52, 130.13-138.95, and 151.19-
175.75 ppm, respectively.14 These chemical shifts com-
pare well with those previously observed in the related
alkenyl-carbyne complexes A-F (see Chart 2). We note
also that the RutCR carbon resonance appears in all
cases as a triplet due to the coupling with the two
equivalent phosphorus nuclei of the dppf ligand. The
2
relatively low values of the JCP coupling constant
(15.8-16.9 Hz) clearly reveal that the alkenyl-carbyne
chain is located in a cis disposition with respect to both
phosphorus atoms of the diphosphine.
The proposed stereochemistry for complexes 2a-c
and 3a-c has been unequivocally confirmed by X-ray
diffraction studies on fac-[RuCl3{tCC(H)dCPh2}(dppf)]
(2a) and fac-[RuCl3{tCC(H)dCiPr2}(dppf)] (2c). ORTEP
plots are shown in Figure 1; selected bond distances and
angles are listed in Table 1. In both molecules the
ruthenium atom is in a slightly distorted octahedral
environment with the three chloride ligands disposed
in a mutually fac arrangement. The carbyne unit is
located trans to one of the chloride ligands and is bound
to ruthenium in a nearly linear fashion (Ru-C(35)-
C(36) ) 171.1(5)° (2a) and 175.86(18)° (2c)). Bond
lengths within the metalla-carbyne unit are very similar
in both structures: Ru-C(35) of 1.731(6) Å (2a) vs
1.717(2) Å (2c); C(35)-C(36) of 1.390(8) Å (2a) vs 1.398-
(3) Å (2c); C(36)-C(37) of 1.343(9) Å (2a) vs 1.356(3) Å
(2c). These values can be compared to those previously
reported for the related alkenyl-carbyne complexes [Ru-
{tCC(H)dCPh2}(η5-C5Me5)(dippe)][B(ArF)4]2 and mer,-
trans-[RuCl3{tCC(H)dCMe2}(PPh3)2] (B and F in Chart
2).6g,h It is interesting to note that in both cases the
C(35)-C(36) and C(36)-C(37) bond lengths are quite
similar (ca. (0.05 Å) despite the fact that the former
corresponds to a single C-C bond and the latter to a
CdC bond. This seems to indicate an important contri-
Compounds 2a-c and 3a-c, which are only slightly
soluble in polar organic solvents, have been isolated as
air-stable orange solids in 92-97% yield. They have
been characterized by elemental analyses and IR and
NMR (1H, 31P{1H}, and 13C{1H}) spectroscopy (details
are given in the Experimental Section). Key spectro-
scopic features are as follows: (i) (IR) the presence of a
(10) It is well-known that η3-allyl groups act as labile ligands,
generating free coordination sites in acidic media. See for example:
(a) Braterman, P. S. In Reactions of Coordinated Ligands: Braterman,
P. S., Ed.; Plenum Press: New York, 1986; Vol. 1, p 103. (b)
Ratovelomanana-Vidal, V.; Geneˆt, J. P. J. Organomet. Chem. 1998,
567, 163, and references therein. (c) Cadierno, V.; Crochet, P.; D´ıez,
J.; Garc´ıa-Garrido, S. E., Gimeno, J. Organometallics 2003, 22, 5226.
(d) Cadierno, V.; Crochet, P.; D´ıez, J.; Garc´ıa-Garrido, S. E.; Gimeno,
J. Organometallics 2004, 23, 4836.
(11) Selegue, J. P. Organometallics 1982, 1, 217.
(12) A related synthetic methodology has been successfully applied
for the preparation of the five-coordinate vinylidene complexes
[RuCl2{dCdC(H)R}(PiPr3)2] (R ) Ph, tBu) by reacting [Ru(η3-2-C3H4-
Me)2(COD)] (COD ) 1,5-cyclooctadiene) with PiPr3 (2 equiv), HCl (2
equiv), and the corresponding terminal alkyne HCtCR (R ) Ph, tBu).
Katayama, H.; Ozawa, F. Organometallics 1998, 17, 5190.
(13) To the best of our knowledge, only three examples of 16-electron
allenylidene-ruthenium(II) complexes have been reported, i.e., [RuCl2-
(dCdCdCPh2)(PCy3)(L)] (L ) PCy3, 1,3-bis(2,4,6-trimethylphenyl)-
imidazol-2-ylidene) and [RuCl(dCdCdCPh2)(PCy3)(DMSO)2][CF3SO3]
(DMSO ) dimethyl sulfoxide). (a) Schanz, H.-J.; Jafarpour, L.; Stevens,
E. D.; Nolan, S. P. Organometallics 1999, 18, 5187. (b) Abdallaoui, I.
A.; Se´meril, D.; Dixneuf, P. H. J. Mol. Catal. A: Chem. 2002, 182-
183, 577.
(14) No signal could be experimentally observed for the RutC
carbon nuclei in complexes 2c and 3c despite trials with long
acquisition periods due to their low solubility in common deuterated
solvents.

3114 Organometallics, Vol. 24, No. 13, 2005
Cadierno et al.
Figure 1. ORTEP-type views of the structure of fac-[RuCl3{tCC(H)dCPh2}(dppf)] (2a; on the left) and fac-[RuCl3{tCC(H)dCi-
Pr2}(dppf)] (2c; on the right) showing the crystallographic labeling scheme. Hydrogen atoms have been omitted for clarity
(except that on C(36)). Thermal ellipsoids are drawn at the 20% (2a) or 30% (2c) probability level.
Table 1. Selected Bond Distances (Å) and Angles (deg) for Complexes 2a and 2ca
2a
2c
Bond Distances
Ru-P(1)
2.4157(19)
2.3977(18)
2.4836(18)
2.4432(17)
2.3919(18)
1.731(6)
Ru-P(1)
2.4185(5)
2.3824(5)
2.5130(5)
2.3966(5)
2.4442(5)
1.717(2)
Ru-P(2)
Ru-P(2)
Ru-Cl(1)
Ru-Cl(2)
Ru-Cl(3)
Ru-C(35)
C(35)-C(36)
C(36)-C(37)
Fe-C*
Ru-Cl(1)
Ru-Cl(2)
Ru-Cl(3)
Ru-C(35)
C(35)-C(36)
C(36)-C(37)
Fe-C*
1.390(8)
1.398(3)
1.343(9)
1.6381(10)
1.6441(10)
1.356(3)
1.6419(3)
1.6418(3)
Fe-C**
Fe-C**
Bond Angles
P(1)-Ru-P(2)
P(1)-Ru-Cl(1)
P(1)-Ru-Cl(2)
P(1)-Ru-Cl(3)
P(2)-Ru-Cl(1)
P(2)-Ru-Cl(2)
P(2)-Ru-Cl(3)
Cl(1)-Ru-Cl(2)
Cl(1)-Ru-Cl(3)
Cl(2)-Ru-Cl(3)
P(1)-Ru-C(35)
P(2)-Ru-C(35)
Cl(1)-Ru-C(35)
Cl(2)-Ru-C(35)
Cl(3)-Ru-C(35)
Ru-C(35)-C(36)
C(35)-C(36)-C(37)
C*-Fe-C**
103.07(6)
80.94(6)
86.48(6)
164.61(6)
97.71(6)
168.73(6)
85.15(6)
89.62(6)
85.11(6)
86.97(6)
91.1(2)
85.92(19)
171.8(2)
87.96(19)
102.6(2)
171.1(5)
130.2(6)
179.53(7)
P(1)-Ru-P(2)
P(1)-Ru-Cl(1)
P(1)-Ru-Cl(2)
P(1)-Ru-Cl(3)
P(2)-Ru-Cl(1)
P(2)-Ru-Cl(2)
P(2)-Ru-Cl(3)
Cl(1)-Ru-Cl(2)
Cl(1)-Ru-Cl(3)
Cl(2)-Ru-Cl(3)
P(1)-Ru-C(35)
P(2)-Ru-C(35)
Cl(1)-Ru-C(35)
Cl(2)-Ru-C(35)
Cl(3)-Ru-C(35)
Ru-C(35)-C(36)
C(35)-C(36)-C(37)
C*-Fe-C**
102.492(18)
97.189(18)
85.349(17)
168.800(18)
80.298(17)
164.953(19)
87.553(18)
86.032(17)
89.307(18)
86.013(17)
85.58(7)
90.79(7)
171.04(7)
102.71(7)
89.38(7)
175.86(18)
122.8(2)
178.67(2)
a C* and C** denote the centroids of the cyclopentadienyl rings C(1), C(2), C(3), C(4), C(5) and C(6), C(7), C(8), C(9), C(10), respectively.
bution of the vinylidene-type canonical form B to the
structure of alkenyl-carbynes 2a-c and 3a-c (see
Figure 2).15 A high contribution of a vinylidene-type
canonical form has been previously proposed by Valerga
and co-workers for the alkenyl-carbyne complex [Ru{t
CC(H)dCPh2}(η5-C5Me5)(dippe)][B(ArF)4]2.6g
Synthesis and Characterization of Dinuclear
Allenylidene Complexes [{RuX(µ-X)(dCdCdCR2)-
(dppf)}2] (X ) Cl, Br; R ) Ph or CR2 ) C13H8) (4a,b,
5a,b). Although all attempts to isolate allenylidene
intermediates [RuX2(dCdCdCR2)(dppf)] by reacting
[Ru(η3-2-C3H4Me)2(dppf)] (1) with 1-alkyn-3-ols in the
presence of 2 equiv of HX failed, these metallacumulenic
species have been obtained using the alkenyl-carbyne
complexes fac-[RuX3{tCC(H)dCR2}(dppf)] as starting
materials. Thus, we have found that the treatment of
dichloromethane solutions of complexes 2a,b and 3a,b
with 1 equiv of AgSbF4 generates the dinuclear alle-
nylidene compounds [{RuX(µ-X)(dCdCdCR2)(dppf)}2]
Figure 2. Canonical forms of alkenyl-carbynes 2a-c and
3a-c.
(15) This fact should be also reflected in a longer Ru-C(35) bond
length in comparison to simple (no R,â-unsaturated) ruthenium-
carbynes [Ru]tCR. Nevertheless, the values reported in the literature
for this type of complex fall in a broad range (from 1.66 to 1.88 Å; see
ref 6), preventing precise conclusions.

Synthesis of R,â-Unsaturated Carbyne Complexes
Organometallics, Vol. 24, No. 13, 2005 3115
Scheme 2
vs the corresponding 16-electron allenylidenes [RuX2-
(dCdCdCR2)(dppf)] is a thermodynamically favored
process. Moreover, the involvement of these dinuclear
allenylidenes as the actual intermediate species in the
generation of alkenyl-carbynes fac-[RuX3{tCC(H)d
CR2}(dppf)] (2a-c, 3a-c) from the reactions of [Ru(η3-
2-C3H4Me)2(dppf)] (1) with propargylic alcohols and 2
equiv of HX has been assessed by comparison of the 31P-
{1H} NMR spectra of 4a,b and 5a,b with those obtained
from the corresponding reaction mixtures. In agreement
with this, the treatment of dichloromethane solutions
of allenylidenes 4a,b and 5a,b with hydrogen halides
HX (X ) Cl, Br) regenerates the alkenyl-carbynes 2a,b
and 3a,b quantitatively.
(4a,b, 5a,b) via halide abstraction and concomitant
deprotonation of the alkenyl-carbyne chain (see Scheme
2).16,17
Complexes 4a,b and 5a,b, isolated as violet air-stable
solids in 93-98% yield, have been characterized by
Conclusions
1
standard analytical and spectroscopic (IR and H, 31P-
In this paper we have described an efficient, straight-
forward, and stereoselective synthetic route for the
preparation of novel alkenyl-carbyne ruthenium com-
plexes fac-[RuX3{tCC(H)dCR2}(dppf)] (2a-c, 3a-c).
This synthetic methodology involves the use of the
readily available bis(allyl)-ruthenium(II) derivative [Ru-
(η3-2-C3H4Me)2(dppf)] (1) as starting material. Thus,
complex 1 reacts with propargylic alcohols in the pres-
ence of an excess of hydrogen halides HX (X ) Cl, Br),
leading to the R,â-unsaturated carbynes in a one-pot
manner. To the best of our knowledge, only the neutral
alkenyl-carbyne mer,trans-[RuCl3{tCC(H)dCMe2}-
(PPh3)2] (F; see Chart 2), serendipitously obtained by
reacting [RuHCl(PPh3)3] with an excess of 3-chloro-3-
methyl-1-butyne (HCtCC(Cl)Me2), has been previously
reported.6h We note also that, in comparison with the
classical two-step methodology, namely, preparation and
isolation of an allenylidene precursor and its subsequent
protonation, the synthetic route reported here is much
more simple and efficient. It is proposed that formation
of alkenyl-carbynes 2a-c and 3a-c proceeds via 1,3-
addition of HX to dinuclear allenylidene intermediates
[{RuX(µ-X)(dCdCdCR2)(dppf)}2]. Remarkably, these
metallacumulenic species can be also easily prepared
from fac-[RuX3{tCC(H)dCR2}(dppf)] through abstrac-
tion of one halide ligand and concomitant deprotonation
of the alkenyl-carbyne chain. Although the chemistry
of allenylidene-ruthenium(II) complexes has been the
subject of special attention during the last years due to
the wealth of their applications in stoichiometric and
catalytic reactions,4a,c-e,g,h the allenylidene derivatives
described here [{RuX(µ-X)(dCdCdCR2)(dppf)}2] belong
to the limited series of dinuclear complexes containing
halide-bridged ligands.18
{1H}, and 13C{1H} NMR) techniques (details are given
in the Experimental Section). Moreover, their dinuclear
nature has been confirmed by FAB-MS, which shows
the presence of peaks corresponding to the loss of one
halide ligand from the parent ion ([M+ - X]).18 The
spectroscopic data obtained for 4a,b and 5a,b are in
agreement with the presence of two equivalent alle-
nylidene chains. Thus, the IR spectra (KBr) exhibit a
broad and strong ν(CdCdC) absorption band (asym-
metric stretching vibration) at ca. 1930 cm-1, and the
13C{1H} NMR spectra display the characteristic low-
2
field doublet of doublet (2JCP ) JCP′ ) 13.8-18.9 Hz)
resonance for the carbenic RudCR atom at 300.30-
316.28 ppm. The 2JCP values observed clearly reveal that
the allenylidene groups are located in a cis disposition
with respect to both phosphorus nuclei of the dppf
ligands. The spectra also show two singlet signals in
the ranges δC 218.03-228.35 and 153.66-159.74 ppm
corresponding to the â- and γ-carbon nuclei, respec-
tively, as expected for their sp and sp2 character. All
these data are comparable to those previously reported
in the literature for other allenylidene-ruthenium(II)
complexes.4,13,18 We also note that, in accord with the
proposed structure, the 31P{1H} NMR spectra display
a typical AB pattern (δP 43.03-49.08 ppm; 2JPP ) 25.3-
28.3 Hz) indicating that (i) both dppf ligands are
equivalent and (ii) phosphorus atoms within each dppf
ligand are inequivalent.19
Apparently, the formation of the coordinatively satu-
rated dinuclear species [{RuX(µ-X)(dCdCdCR2)(dppf)}2]
(16) It is known that the hydrogen atom on the â-carbon of alkenyl-
carbyne complexes is highly acidic, being easily deprotonated even with
weak bases such as diethyl ether or acetone. See refs 6f,g.
(17) (a) Allenylidene complexes 4a,b and 5a,b are also generated
in the reaction of carbyne complexes 2a,b and 3a,b with Et3N.
Nevertheless, we were unable to isolate 4a,b and 5a,b in pure form
by this route since all attempts to separate the ammonium salts [Et3-
NH]X (X ) Cl, Br), formed as byproducts in these reactions, failed
(chromatographic workup leads to extensive decompositions). (b) One
of the referees directed our attention to the formulation of allenylidene
complexes 4a,b and 5a,b as cationic dimers containing three halide-
bridged ligands [Ru2(µ-X)3(dCdCdCR2)2(dppf)2][X]. Conductance mea-
surements at room temperature allow discarding this formulation. ΛM
values of acetone solutions (ca. 10-3 mol dm-3) of complexes 4a,b and
5a,b are in all cases <30 Ω-1 cm2 mol-1 (typical values for 1:1
electrolytes fall in the range 100-140 Ω-1 cm2 mol-1).
(18) The dinuclear allenylidene-ruthenium(II) complexes containing
halide-bridged ligands [{Ru(dCdCdCR2)(PPh3)2}2(µ-Cl)3][PF6] (R )
Ph, o-C6H4Cl, o-C6H4F) and [Na]4[{RuCl(µ-Cl)(dCdCdCPh2)(TPPMS)2}2]
(TPPMS ) Ph2P(o-C6H4SO3Na) are known: (a) Touchard, D.; Guesmi,
S.; Bouchaib, M.; Haquette, P.; Daridor, A.; Dixneuf, P. H. Organo-
metallics 1996, 15, 2579. (b) Saoud, M.; Romerosa, A.; Peruzzini, M.
Organometallics 2000, 19, 4005.
Experimental Section
Synthetic procedures 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 purifica-
tion with the exception of compound [Ru(η3-2-C3H4Me)2(dppf)]
(1), which was prepared by following the method reported in
the literature.9 Infrared spectra were recorded on a Perkin-
(19) We note that all these NMR spectroscopic data are comparable
to those recently reported by us for the dimeric species [{RuX(µ-X)-
(CO)(dppf)2}2] (X ) Cl, Br), which present the same arrangement of
the two metallic units. See ref 10c.

3116 Organometallics, Vol. 24, No. 13, 2005
Cadierno et al.
Elmer 1720-XFT spectrometer. FAB mass spectra were re-
corded using a VG-Autospec spectrometer operating in positive
mode; 3-nitrobenzyl alcohol (NBA) was used as the matrix.
The C and H analyses were carried out with a Perkin-Elmer
2400 microanalyzer. NMR spectra were recorded on a Bruker
DPX300 instrument at 300 MHz (1H), 121.5 MHz (31P), or 75.4
MHz (13C) using SiMe4 or 85% H3PO4 as standards. DEPT
experiments have been carried out for all the compounds
reported in this paper.
for FeRuC43H43Br3P2: C, 50.71; H, 4.26. Found: C, 50.96; H,
4.41. IR (KBr, cm-1): ν 1540 (CdC). 31P{1H} NMR (CD2Cl2):
1
δ 21.47 (s) ppm. H NMR (CD2Cl2): δ 1.12 and 1.23 (br, 6H
each, CH(CH3)3), 2.73 and 3.41 (m, 1H each, CH(CH3)3), 3.63
(s, 1H, dCH), 4.29, 4.60, 4.76, and 5.53 (br, 2H each, C5H4),
6.95-8.15 (m, 20H, Harom) ppm. 13C{1H} NMR (CD2Cl2): δ
20.71 and 22.15 (s, CH(CH3)3), 30.56 and 31.05 (s, CH(CH3)3),
71.57 (br, 2C, CH of C5H4), 73.60 and 76.02 (br, CH of C5H4),
77.27 (d, 1JCP ) 55.2 Hz, C of C5H4), 125.05-136.25 (m, Carom
and CHarom), 136.27 (s, dCâH), 151.19 (s, dCγ) ppm. RutC not
observed.
Synthesis of fac-[RuCl3{tCC(H)dCR2}(dppf)] (R ) Ph
i
(2a), CR2 ) C13H8 (2b), R ) Pr (2c)). To a solution of [Ru-
(η3-2-C3H4Me)2(dppf)] (1) (0.765 g; 1.0 mmol) in 120 mL of a
mixture of acetone/hexane (1:5) were added HCl (3.5 mL of a
1.0 M solution in diethyl ether; 3.5 mmol) and the correspond-
ing propargylic alcohol (2 mmol). The reaction mixture was
then stirred at room temperature for 24 h. The orange
precipitate formed during the reaction was collected by filtra-
tion, washed with hexane (10 × 10 mL), and dried in vacuo.
2a: yield 93% (0.886 g). Anal. Calcd for FeRuC49H39Cl3P2: C,
61.75; H, 4.12. Found: C, 62.11; H, 4.35. IR (KBr, cm-1): ν
1572 (CdC). 31P{1H} NMR (CD2Cl2): δ 21.29 (s) ppm. 1H NMR
(CD2Cl2): δ 4.14 (t, 1H, 4JHP ) 4.0 Hz, dCH), 4.62, 4.68, 4.73,
and 5.60 (br, 2H each, C5H4), 6.70-8.10 (m, 30H, Harom) ppm.
13C{1H} NMR (CD2Cl2): δ 73.29 (br, 2C, CH of C5H4), 75.53
and 76.76 (br, CH of C5H4), 77.41 (d, 1JCP ) 55.6 Hz, C of C5H4),
126.70-138.25 (m, Carom and CHarom), 136.83 (s, dCâH), 175.75
Synthesis of [{RuCl(µ-Cl)(dCdCdCR2)(dppf)}2] (R )
Ph (4a), CR2 ) C13H8 (4b)). AgSbF6 (0.176 g, 0.5 mmol) was
added, at room temperature, to a solution of complexes fac-
[RuCl3{tCC(H)dCR2}(dppf)] (2a,b; 0.5 mmol) in 20 mL of
dichloromethane. The reaction mixture was stirred, at room
temperature and in the absence of light, for 30 min. The AgCl
formed was then filtered off over Kieselguhr and the solvent
removed under reduced pressure to afford a violet solid, which
was washed with diethyl ether (3 × 50 mL) and vacuum-dried.
4a: yield 93% (0.426 g). Anal. Calcd for Fe2Ru2C98H76Cl4P4:
C, 64.21; H, 4.18. Found: C, 64.53; H, 4.23. IR (KBr, cm-1): ν
1934 (CdCdC). 31P{1H} NMR (CD2Cl2): δ 46.36 and 49.05 (d,
2JPP ) 28.3 Hz) ppm. 1H NMR (CD2Cl2): δ 4.10-4.30 (m, 16H,
C5H4), 7.20-7.70 (m, 60H, Harom) ppm. 13C{1H} NMR (CD2-
Cl2): δ 72.10, 72.20, 72.79, and 73.50 (d, 2JCP ) 4.6 Hz, CH of
C5H4), 75.94, 76.13, 76.34, and 76.45 (d, 3JCP ) 8.7 Hz, CH of
C5H4), 80.17 and 80.91 (d, 1JCP ) 45.0 Hz, C of C5H4), 127.25-
145.25 (m, Carom and CHarom), 159.00 (s, Cγ), 218.03 (s, Câ),
312.04 (dd, 2JCP ) 16.5 and 16.5 Hz, RudCR) ppm. MS (FAB):
m/z 1797 [M+ - Cl], 881 [1/2M+ - Cl]. 4b: yield 98% (0.448
g). Anal. Calcd for Fe2Ru2C98H72Cl4P4: C, 64.35; H, 3.97.
Found: C, 64.72; H, 4.16. IR (KBr, cm-1): ν 1934 (CdCdC).
31P{1H} NMR (CD2Cl2): δ 43.17 and 49.08 (d, 2JPP ) 28.0 Hz)
2
(s, dCγ), 298.52 (t, JCP ) 15.8 Hz, RutCR) ppm. 2b: yield
96% (0.913 g). Anal. Calcd for FeRuC49H37Cl3P2: C, 61.88; H,
3.92. Found: C, 62.23; H, 4.23. IR (KBr, cm-1): ν 1570 (Cd
1
C). 31P{1H} NMR (CD2Cl2): δ 22.27 (s) ppm. H NMR (CD2-
Cl2): δ 4.33 (s, 1H, dCH), 4.62, 4.69, 4.76, and 5.61 (br, 2H
each, C5H4), 6.75-9.50 (m, 28H, Harom) ppm. 13C{1H} NMR
(CD2Cl2): δ 73.42 (br, 2C, CH of C5H4), 75.81 and 76.65 (br,
1
CH of C5H4), 76.83 (d, JCP ) 54.2 Hz, C of C5H4), 120.20-
1
ppm. H NMR (CD2Cl2): δ 4.22-4.54 (m, 16H, C5H4), 6.90-
142.50 (m, Carom and CHarom), 136.64 (s, dCâH), 165.13 (s, d
7.90 (m, 56H, Harom) ppm. 13C{1H} NMR (CD2Cl2): δ 71.53,
71.99, 73.44, and 73.87 (d, 2JCP ) 4.7 Hz, CH of C5H4), 75.64,
2
Cγ), 292.45 (t, JCP ) 16.9 Hz, RutCR) ppm. 2c: yield 97%
(0.858 g). Anal. Calcd for FeRuC43H43Cl3P2: C, 58.36; H, 4.90.
Found: C, 58.53; H, 5.08. IR (KBr, cm-1): ν 1573 (CdC). 31P-
{1H} NMR (CD2Cl2): δ 21.06 (s) ppm. 1H NMR (CD2Cl2): δ
1.09 and 1.20 (br, 6H each, CH(CH3)3), 2.82 and 3.38 (m, 1H
each, CH(CH3)3), 3.59 (s, 1H, dCH), 4.25, 4.57, 4.72, and 5.49
(br, 2H each, C5H4), 6.85-8.10 (m, 20H, Harom) ppm. 13C{1H}
NMR (CD2Cl2): δ 21.66 and 23.10 (s, CH(CH3)3), 31.51 and
32.00 (s, CH(CH3)3), 73.83 (br, 2C, CH of C5H4), 75.43 and
3
75.80, 76.11, and 76.64 (d, JCP ) 8.5 Hz, CH of C5H4), 78.78
1
and 80.38 (d, JCP ) 54.3 Hz, C of C5H4), 121.50-165.15 (m,
Carom and CHarom), 153.66 (s, Cγ), 227.37 (s, Câ), 300.30 (dd,
2JCP ) 13.8 and 13.8 Hz, RudCR) ppm. MS (FAB): m/z 1793
[M+ - Cl], 879 [1/2M+ - Cl].
Synthesis of [{RuBr(µ-Br)(dCdCdCR2)(dppf)}2] (R )
Ph (5a), CR2 ) C13H8 (5b)). Complexes 5a,b, isolated as violet
solids, were prepared as described for 4a,b starting from fac-
[RuBr3{tCC(H)dCR2}(dppf)] (3a,b; 0.5 mmol) and AgSbF6
(0.176 g, 0.5 mmol). 5a: yield 93% (0.467 g). Anal. Calcd for
Fe2Ru2C98H76Br4P4: C, 58.53; H, 3.81. Found: C, 58.31; H,
3.70. IR (KBr, cm-1): ν 1926 (CdCdC). 31P{1H} NMR (CD2-
Cl2): δ 44.59 and 48.79 (d, 2JPP ) 25.3 Hz) ppm. 1H NMR (CD2-
1
76.97 (br, CH of C5H4), 77.82 (d, JCP ) 51.7 Hz, C of C5H4),
126.00-136.10 (m, Carom and CHarom), 130.13 (s, dCâH), 152.14
(s, dCγ) ppm. RutC not observed.
Synthesis of fac-[RuBr3{tCC(H)dCR2}(dppf)] (R ) Ph
i
(3a), CR2 ) C13H8 (3b), R ) Pr (3c)). Complexes 3a-c,
isolated as orange solids, were prepared as described for 2a-c
starting from [Ru(η3-2-C3H4Me)2(dppf)] (1) (0.765 g, 1.0 mmol),
HBr (3.5 mL of a 1.0 M solution in diethyl ether; 3.5 mmol),
and the corresponding propargylic alcohol (2 mmol). 3a: yield
94% (1.021 g). Anal. Calcd for FeRuC49H39Br3P2: C, 54.17; H,
3.62. Found: C, 54.35; H, 3.94. IR (KBr, cm-1): ν 1574 (Cd
Cl2): δ 4.06-4.55 (m, 16H, C5H4), 6.85-7.95 (m, 60H, Harom
)
ppm. 13C{1H} NMR (CD2Cl2): δ 71.89, 72.31, 72.74, and 74.12
(d, 2JCP ) 5.1 Hz, CH of C5H4), 75.71, 76.22, 76.36, and 76.64
(d, 3JCP ) 7.5 Hz, CH of C5H4), 80.45 and 80.91 (d, 1JCP ) 54.2
Hz, C of C5H4), 122.00-165.50 (m, Carom and CHarom), 159.74
2
1
C). 31P{1H} NMR (CD2Cl2): δ 19.15 (s) ppm. H NMR (CD2-
(s, Cγ), 218.70 (s, Câ), 312.82 (dd, JCP ) 18.9 and 18.9 Hz,
RudCR) ppm. MS (FAB): m/z 1931 [M+ - Br], 925 [1/2M+
-
Cl2): δ 3.99 (t, 1H, 4JHP ) 3.7 Hz, dCH), 4.62, 4.69, 4.75, and
5.70 (br, 2H each, C5H4), 6.60-8.20 (m, 30H, Harom) ppm. 13C-
{1H} NMR (CD2Cl2): δ 74.25, 75.15, 77.08, and 77.40 (br, CH
Br]. 5b: yield 96% (0.482 g). Anal. Calcd for Fe2Ru2C98H72-
Br4P4: C, 58.65; H, 3.62. Found: C, 58.91; H, 3.85. IR (KBr,
cm-1): ν 1932 (CdCdC). 31P{1H} NMR (CD2Cl2): δ 43.03 and
1
of C5H4), 78.67 (d, JCP ) 52.2 Hz, C of C5H4), 125.40-141.90
2
48.49 (d, JPP ) 25.5 Hz) ppm. 1H NMR (CD2Cl2): δ 4.01-
(m, Carom and CHarom), 138.95 (s, dCâH), 175.34 (s, dCγ), 296.61
(t, 2JCP ) 16.4 Hz, RutCR) ppm. 3b: yield 92% (0.998 g). Anal.
Calcd for FeRuC49H37Br3P2: C, 54.27; H, 3.44. Found: C,
54.56; H, 3.71. IR (KBr, cm-1): ν 1570 (CdC). 31P{1H} NMR
4.40 (m, 16H, C5H4), 6.55-7.95 (m, 56H, Harom) ppm. 13C{1H}
NMR (CD2Cl2): δ 72.02, 72.60, 73.44, and 74.90 (d, 2JCP ) 5.8
Hz, CH of C5H4), 75.84, 76.19, 76.36, and 77.02 (d, 3JCP ) 8.2
Hz, CH of C5H4), 79.63 and 80.52 (d, 1JCP ) 55.8 Hz, C of C5H4),
122.00-165.45 (m, Carom and CHarom), 154.37 (s, Cγ), 228.35
(s, Câ), 316.28 (dd, 2JCP ) 18.5 and 18.5 Hz, RudCR) ppm. MS
(FAB): m/z 1927 [M+ - Br], 923 [1/2M+ - Br].
1
(CD2Cl2): δ 20.40 (s) ppm. H NMR (CD2Cl2): δ 4.28 (t, 1H,
4JHP ) 3.9 Hz, dCH), 4.68, 4.71, 4.80, and 5.70 (br, 2H each,
C5H4), 6.10-9.70 (m, 28H, Harom) ppm. 13C{1H} NMR (CD2-
Cl2): δ 73.98, 74.49, 76.97, and 77.25 (br, CH of C5H4), 78.26
1
(d, JCP ) 53.3 Hz, C of C5H4), 120.20-143.00 (m, Carom and
X-ray Crystal Structure Determination of Complexes
2a and 2c. Crystals suitable for X-ray diffraction analysis were
obtained by slow diffusion of n-pentane into saturated solu-
2
CHarom), 136.01 (s, dCâH), 165.12 (s, dCγ), 296.15 (t, JCP
)
16.4 Hz, Ru≡CR) ppm. 3c: yield 93% (0.947 g). Anal. Calcd

Synthesis of R,â-Unsaturated Carbyne Complexes
Organometallics, Vol. 24, No. 13, 2005 3117
Table 2. Crystal Data and Structure Refinement Details for 2a and 2c
2a
2c
chemical formula
fw
C
49H39Cl3P2FeRu
C43H43Cl3P2FeRu‚C2H4Cl2
983.94
953.01
T (K)
223(2)
0.71073
100(2)
wavelength (Å)
cryst syst
space group
cryst size, mm
a, Å
1.54178
monoclinic
P21/c (No. 14)
0.25 × 0.20 × 0.15
11.512(3)
15.153(4)
27.063(6)
90
93.156(6)
90
4
4714.1(19)
1.343
0.897
1936
monoclinic
P21/c (No. 14)
0.22 × 0.13 × 0.12
16.6808(1)
13.6309(1)
18.8276(1)
90
b, Å
c, Å
R, deg
â, deg
98.265(1)
90
4
4236.45(5)
1.543
9.493
2008
γ, deg
Z
V, Å3
F
calcd, g cm-3
µ, mm-1
F(000)
θ range, deg
index ranges
1.51 to 30.59
-12 e h e 16
-21 e k e 21
-36 e l e 38
97.4%
2.68 to 70.62
-18 e h e 20
-16 e k e 15
-20 e l e 21
92.3%
completeness to θmax
no. of data collected
no. of unique data
no. of params/restraints
refinement method
goodness of fit on F2
weight function (a, b)
R1a [I > 2σ(I)]
39 831
20 532
11 423 (Rint ) 0.1654)
505/0
7503 (Rint ) 0.0308)
676/0
full-matrix least-squares on F2
0.849
1.036
0.0592, 0
0.0806
0.0338, 1.7542
0.0255
wR2a [I > 2σ(I)]
0.1471
0.0632
R1 (all data)
0.2146
0.0278
wR2 (all data)
0.1833
0.0645
largest diff peak and hole, e Å-3
0.755 and -1.343
0.556 and -0.551
a R1 ) ∑(|Fo| - |Fc|)/∑|Fo|; wR2 ) {∑[w(Fo - Fc )2]/∑[w(Fo2)2]}1/2
.
2
2
tions of complexes 2a and 2c in dichloromethane or 1,2-
dichloroethane, respectively. 2c was obtained as solvated
crystals that contained one 1,2-dichloroethane molecule per
molecular unit. The most relevant crystal and refinement data
are collected in Table 2. Diffraction data for 2a were recorded
on a Bruker Smart CCD diffractometer using Mo KR radiation.
Diffraction data for 2c were recorded on a Bruker Smart 6k
CCD area-detector three-circle diffractometer using Cu KR
radiation. In both cases, the data were collected using 0.3° wide
ω scans with a crystal-to-detector distance of 40 mm. The
diffraction frames were integrated using the SAINT package20
and corrected for absorption with SADABS.21
The software package WINGX was used for space group
determination, structure solution, and refinement.22 The struc-
tures were solved by Patterson interpretation and phase
expansion using DIRDIF.23 Isotropic least-squares refinement
on F2 using SHELXL97 was performed.24 During the final
stages, all non-hydrogen atoms for 2a and 2c were refined with
anisotropic displacement parameters. The H atoms for 2a were
geometrically located, and their coordinates were refined riding
on their parent atoms. The H atoms for 2c were located by
difference maps and refined isotropically. The function mini-
mized was [∑w(Fo - Fc2)/∑w(Fo )]1/2 where w ) 1/[σ2(Fo ) +
2
2
2
2
(aP)2 + bP] (a and b values are shown in Table 2) with σ(Fo )
2
from counting statistics and P ) (Max(Fo , 0) + 2Fc2)/3. Atomic
scattering factors were taken from the International Tables
for X-Ray Crystallography.25 Geometrical calculations were
made with PARST.26 The crystallographic plots were made
with PLATON.27
Acknowledgment. We are indebted to the Minis-
terio de Ciencia y Tecnolog´ıa (MCyT) of Spain (Project
BQU2003-00255) for financial support. S.E.G.G and
V.C. thank the MCyT for the award of a Ph.D. grant
and a “Ramo´n y Cajal” contract, respectively.
Supporting Information Available: Tables and a CIF
file giving crystallographic data for complexes 2a and 2c. This
material is available free of charge via the Internet at
http://pubs.acs.org.
(20) SAINT, version 6.02; Bruker Analytical X-ray Systems; Madi-
son, WI, 2000.
(21) Sheldrick, G. M. SADABS: Empirical Absorption Program;
University of Go¨ttingen: Go¨ttingen, Germany, 1996.
(22) Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837.
(23) 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 of the Crystallographic
Laboratory; University of Nijmegen: Nijmegen, The Netherlands,
1999.
OM050204U
(25) International Tables for X-Ray Crystallography; Kynoch
Press: Birmingham, U.K., 1974; Vol. IV (Present distributor: Kluwer
Academic Publishers: Dordrecht, The Netherlands).
(26) Nardelli, M. Comput. Chem. 1983, 7, 95.
(27) Spek, A. L. PLATON: A Multipurpose Crystallographic Tool;
University of Utrecht: Utrecht, The Netherlands, 2005.
(24) Sheldrick, G. M. SHELXL97: Program for the Refinement of
Crystal Structures; University of Go¨ttingen: Go¨ttingen, Germany,
1997.