New types of (arene)ruthenium alkynyl complexes

Article abstract of DOI:10.1021/om000834q

The reaction of [{RuCl(cym)}₂(μ-Cl)₂] (cym = η⁶-4-methylisopropylbenzene) with 1,10-phenanthroline and NaBAr′₄ (Ar′ = 3,5-bis(trifluoromethyl)phenyl), followed by addition of excess sodium acetylide, yielded the

Full text of DOI:10.1021/om000834q

Organometallics 2001, 20, 2775-2781
2775
New Typ es of (Ar en e)r u th en iu m Alk yn yl Com p lexes†
Carmen Mene´ndez, Dolores Morales, J ulio Pe´rez,* and V´ıctor Riera
Departamento de Quı´mica Orga´nica e Inorga´nica / IUQOEM, Facultad de Quı´mica,
Universidad de Oviedo-CSIC, 33071 Oviedo, Spain
Daniel Miguel
Departamento de Quı´mica Inorga´nica, Facultad de Ciencias, Universidad de Valladolid,
47071 Valladolid, Spain
Received September 27, 2000
The reaction of [{RuCl(cym)}2(µ-Cl)2] (cym ) η6-4-methylisopropylbenzene) with 1,10-
phenanthroline and NaBAr′4 (Ar′ ) 3,5-bis(trifluoromethyl)phenyl), followed by addition of
excess sodium acetylide, yielded the complex [Ru(CCH)(cym)(phen)]BAr′4 (1), the first cationic
(arene)ruthenium alkynyl. Similar [Ru(CCPh)(cym)(phen)]BAr′4 (2) and [Ru(CCSiMe3)(cym)-
(phen)]BAr′4 (3) complexes were prepared in an analogous manner from the corresponding
lithium acetylides and in situ generated ruthenium triflate precursors. Protonation of 1 with
HOTf afforded the acyl complex [Ru(C(O)CH 3)(cym)(phen)]BAr′4 (4), presumably by reaction
of an initially formed dicationic vinylidene with adventitious water. The reaction of [RuCl2-
(cym)(PMe3)] with excess LiCCPh afforded the complex [Ru(CCPh)2(cym)(PMe3)] (5), the first
(arene)ruthenium bis(acetylide) complex. All new compounds were characterized by IR and
NMR, and the crystal structures of 1, 4, and 5 were determined by X-ray diffraction.
In tr od u ction
[RuCl(CC(H)Ph)(η6-C6Me6)(PMe3)]+, which, in turn, re-
acted with methanol to afford methoxycarbenes [RuCl-
(C(OMe)CH2Ph)(η6-C6Me6)(PMe3)]+.6 [(η6-arene)RuCl2-
(PR3)] precursors were employed for the direct activation
of 1-alkynes in alcohols to yield alcoxycarbenes.6 The
(arene)ruthenium complexes showed a higher efficiency
than the isoelectronic [(η5-C5H5)RuCl(PMe3)2] com-
pounds, a fact that is attributed mainly to the higher
electrophilicity of the (arene)ruthenium vinylidene
Alkynyl complexes have attracted an ongoing inter-
est,1 in part due to their role as precursors of vinylidene
complexes, in turn highly reactive species,2 and due to
the usefulness of alkynyl complexes as building blocks
in the synthesis of polymetallic compounds.3
Ruthenium alkynyl and vinylidene complexes have
attracted much attention due to their interesting reac-
tivity.4,5 Ruthenium(II) alkynyls with ancillary η5-
cyclopentadienyl or related (pentamethylcyclopenta-
dienyl or indenyl) ligands have been extensively studied.
In contrast, much less is known about (arene)ruthenium
(II) alkynyls, although some of these compounds have
revealed an interesting reactivity. Le Bozec and Dixneuf
found that protonation of the alkynyl [RuCl(CCPh)(η6-
C6Me6)(PMe3)] yielded cationic vinylidene complexes
(4) Some recent leading references on ruthenium alkynyl chemis-
try: (a) Whittall, I. R.; Humphrey, M. G.; Persoons, A.; Honbrechts,
S. Organometallics 1996, 15, 1935. (b) Blenkiron, P.; Carty, A. J .; Peng,
S.; Lee, G.; Su, C.; Shin, C.; Chi, Y. Organometallics 1997, 16, 519. (c)
Kawata, Y.; Sato, M.; Organometallics 1997, 16, 1093. (d) J ones, N.
D.; Wolf, M. O. Organometallics 1997, 16, 1352. (e) Sato, M.; Kawata,
Y.; Shintate, H.; Habata, Y.; Akabori, S.; Unoura, K. Organometallics
1997, 16, 1693. (f) Koridze, A. A.; Zdanovich, V. I.; Sheloumov, A. M.;
Lagunova, V. Y.; Petrouskii, P. V.; Peregudov, A. S.; Dolgushin, F. M.;
Yanousky, A. Y. Organometallics 1997, 16, 2285. (g) Yang, S.; Chan,
M. C.; Chenng, K.; Che, C.; Peng, S. Organometallics 1997, 16, 2819.
(h) Yi, C. S.; Liu, N.; Rheingold, A. L.; Liable-Sands, L. M.; Guzei, I.
A. Organometallics 1997, 16, 3729. (i) McGrady, J . E.; Lovell, T.;
Stranger, R.; Humphrey, M. G. Organometallics 1997, 16, 4004. (j) Wu,
I. Y.; Lin, J . T.; Luo, J .; Sun, S. S.; Li, C. S.; Lin K. J .; Tsai, C.; Hsu,
C. C.; Lin, J . L. Organometallics 1997, 16, 2038. (k) Yi, C. S.; Liu, N.;
Rheingold, A. L.; Liable-Sands, L. M. Organometallics 1997, 16, 3910.
(l) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Lo´pez-Gonza´lez, M. C.;
Borge, J .; Garc´ıa-Granda, S. Organometallics 1997, 16, 4453. (m) Wu,
I.; Lin, J . T.; Luo, J .; Li, C.; Tsai, C.; Wen, Y.; Hsu, C.; Yeh, F.; Liou,
S. Organometallics 1998, 17, 2188. (n) Chan, C.; Lin, Y.; Lee, G.;
Huang, S.; Wang, Y. Organometallics 1998, 17, 2534. (o) Yi, C. S.; Liu,
N. Organometallics 1998, 17, 3158. (p) Cadierno, V.; Gamasa, M. P.;
Gimeno, J .; Moreto´, J . M.; Ricart, S.; Roig, A.; Molins, E. Organome-
tallics 1998, 17, 697. (q) de los R´ıos, I.; J ime´nez Tenorio, M.; Puerta,
M. C.; Valerga, P. Organometallics 1998, 17, 3356. (r) Touchard, D.;
Haquette, P.; Daridor, A.; Romero, A.; Dixneuf, P. H. Organometallics
1998, 17, 3844. (s) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Pe´rez-
Carren˜o, E.; Ienco, A. Organometallics 1998, 17, 5216. (t) Bustelo, E.;
J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga, P. Organometallics 1999,
18, 4563. (u) Zhu, Y.; Millet, D. B.; Wolf, M. O.; Rettig, R. J .
Organometallics 1999, 18, 1930. (v) Choi, M.; Chan, M. C.; Zhang, S.;
Cheung, K.; Che, C.; Wang, K. Organometallics 1999, 18, 2074. (w)
Carmona, D.; Vega, C.; Lahoz, F. J .; Atencio, R.; Oro, L. A.; Lamata,
M. P.; Viguri, F.; San J ose´, E. Organometallics 2000, 19, 2273.
† Dedicated to Professor R. Uso´n on the occasion of his 75th birthday.
* Correspondence author. E-mail: japm@sauron.quimica.uniovi.es.
(1) Manna, J .; J ohn, K. D.; Hopkins, M. D. Adv. Organomet. Chem.
1995, 38, 79.
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Rev. 1998, 98, 2797. (c) Bruneau, C.; Dixneuf, P. H. Acc. Chem. Res.
1999, 32, 311.
(3) (a) Lemke, F. R.; Szalda, D. J .; Bullock, R. M. J . Am. Chem. Soc.
1991, 113, 8466. (b) Espinet, P.; Fornie´s, J .; Mart´ınez, F.; Sote´s, M.;
Lalinde, E.; Moreno, M. T.; Ruiz, A.; Welch, A. J . J . Organomet. Chem.
1991, 403, 253. (c) Lang, H.; Ko¨hler, K.; Blau, S. Coord. Chem. Rev.
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1996, 2587. (e) Ara, I.; Berenguer, J . R.; Eguiza´bal, E.; Fornie´s, J .;
Lalinde, E., Mart´ın, A.; Mart´ınez, F. Organometallics 1998, 17, 4578.
(f) Falvello, L. R.; Fornie´s, J .; Mart´ın, A.; Go´mez, J .; Lalinde, E.;
Moreno, M. T.; Sacrista´n, J . Inorg. Chem. 1999, 38, 3116. (g) Charmant,
J . P. H.; Falvello, L. R.; Fornie´s, J .; Go´mez, J .; Lalinde, E.; Moreno,
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10.1021/om000834q CCC: $20.00 © 2001 American Chemical Society
Publication on Web 05/19/2001

2776 Organometallics, Vol. 20, No. 13, 2001
Mene´ndez et al.
Sch em e 1
intermediates.6 The only known (arene)ruthenium alky-
nyls were neutral complexes with a single alkynyl
ligand.6,7 Here we report the synthesis and character-
ization of two new types of (arene)ruthenium alkynyl
complexes: cationic alkynyls and one neutral bis-
(alkynyl) complex.
F igu r e 1. Thermal ellipsoid (drawn at the 30% probability
level) plot of 1.
Resu lts a n d Discu ssion
Syn th esis, Ch a r a cter iza tion , a n d Rea ctivity of
Ca t ion ic Alk yn yls [R u (CCR )(Cym )(p h en )]BAr ′4.
The complex [{RuCl(cym)}2(µ-Cl)2]8 reacts with 1,10-
phenanthroline (phen) and the salt NaBAr′4 (Ar′ ) 3,5-
bis(trifluoromethyl)phenyl)9 in THF. The solution of the
complex [RuCl(cym)(phen)]BAr′4 obtained in this way
reacts with excess sodium acetylide to yield, after
workup, the alkynyl complex [Ru(CCH)(cym)(phen)]-
BAr′4 (1) (Scheme 1).
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for Com p lex 1
Ru(1)-C(1)
Ru(1)-N(2)
Ru(1)-N(1)
Ru(1)-C(13)
Ru(1)-C(12)
2.022(9)
2.084(6)
2.090(6)
2.178(8)
2.189(7)
Ru(1)-C(15)
Ru(1)-C(14)
Ru(1)-C(16)
Ru(1)-C(11)
C(1)-C(2)
2.194(8)
2.232(8)
2.254(7)
2.263(7)
1.151(12)
C(2)-C(1)-Ru(1)
C(1)-Ru(1)-N(1)
175.7(10)
84.2(3)
C(1)-Ru(1)-N(2)
N(2)-Ru(1)-N(1)
83.8(3)
77.7(3)
The IR spectrum of 1 displays one band at 1974 cm-1
,
assigned to the stretching of the alkynyl triple bond.10
The ethynyl hydrogen occurs at 1.37 ppm in the 1H
NMR spectrum of 1.11 The 13C NMR shows low-intensity
signals at 99.9 and 88.9 ppm, attributable to the carbons
of the ethynyl group.3a Integration of the 1H NMR
spectrum further supports the [Ru(CCH)(cym)(phen)]-
BAr′4 composition for 1. This was confirmed by the
results of an X-ray determination carried out on a single
crystal of 1. The structure of the cation, shown in Figure
1, consists of a ruthenium atom coordinated to a
η6-cymene ligand, the two nitrogens of a 1,10-phenan-
throline ligand, and one carbon of the ethynyl group.
Selected distances and angles are given in Table 1.
These data establish for 1 a structure in the solid state
consistent with the spectroscopic data in solution, but,
given the low level of accuracy of the X-ray data, further
discussion of distances and angles is avoided.
The synthetic procedure outlined above involves the
preparation of the nonisolated intermediate [RuCl(cym)-
(phen)]BAr′4.12 In this first step, the coordination of the
phenanthroline ligand to the ruthenium center takes
place with cleavage of the doubly chloride-bridged
structure of the dimeric precursor. One chloride is
abstracted out of each ruthenium and precipitates as
sodium chloride. The high solubility of BAr′4 salts in
solvents of moderate polarity allows the use of mild
conditions for the synthesis.13,14 This first part can be
(5) Some recent leading references on ruthenium vinylidene chem-
istry: (a) Ting, P.; Lin, Y.; Lee, G.; Cheng, M.; Wang, Y. J . Am. Chem.
Soc. 1996, 118, 6433. (b) Merlic, C. A.; Pauly, M. E. J . Am. Chem. Soc.
1996, 118, 11319. (c) Bianchini, C.; Innocenti, P.; Peruzzini, M.;
Romerosa, A.; Zanobini, F. Organometallics 1996, 15, 272. (d) Guari,
Y.; Sabo-Etienne, S.; Chaudret, B. Organometallics 1996, 15, 3471.
(e) Braun, T.; Meuer, P.; Werner, H. Organometallics 1996, 15, 4075.
(f) Adams, H.; Gill, L. J .; Morris, M. J . Organometallics 1996, 15, 4182.
(g) Slugovc, C.; Mereiter, K.; Zobetz, E.; Schmid, R.; Kirchner, K.
Organometallics 1996, 15, 5275. (h) de los R´ıos, I.; J ime´nez Tenorio,
M.; Puerta, M. C.; Valerga, P. J . Am. Chem. Soc. 1997, 118, 66529. (i)
Oliva´n, M.; Eisenstein, O.; Caulton, K. G. Organometallics 1997, 16,
2227. (j) Yang, S.; Chan, M. C.; Cheung, K.; Che, C.; Peng, S.
Organometallics 1997, 16, 2819. (k) Touchard, D.; Haquette, P.;
Guesmi, S.; Le Pichon, L.; Daridor, A.; Toupet, L.; Dixneuf, P. H.
Organometallics 1997, 16, 3640. (l) Kawata, Y.; Sato, M. Organome-
tallics 1997, 16, 1093. (m) Bruce, M. I., Hinterding, P.; Low, P. J .;
Skelton, B. W.; White, A. H. J . Chem. Soc., Dalton Trans. 1998, 467.
(n) Bruce, M. I.; Hall, B. C.; Zaitseva, N. N.; Skelton, B. W. White, A.
H. J . Chem. Soc., Dalton Trans. 1998, 1793, and references therein.
(o) Oliva´n, M.; Clot, E.; Eisenstein, O.; Caulton, K. C. Organometallics
1998, 17, 3091. (p) Chang, C.; Lin, Y.; Lee, G.; Wang, Y. Organome-
tallics 1999, 18, 3445. (q) Cadierno, V.; Gamasa, M. P.; Gimeno, J .,
Pe´rez-Carren˜o, E.; Garc´ıa-Granda, S. Organometallics 1999, 18, 2821.
(r) J ime´nez Tenorio, M. A.; J ime´nez Tenorio, M.; Puerta, M. C.;
Valerga, P. Organometallics 2000, 19, 1333. (s) Leung, W.; Lau, K.;
Zhang, Q.; Wong, W.; Tang, B. Organometallics 2000, 19, 2084. (t)
Saoud, M.; Romerosa, A.; Peruzzini, M. Organometallics 2000, 19,
4005.
(6) Le Bozec, H.; Ouzzine, K.; Dixneuf, P. H. Organometallics 1991,
10, 2768.
(7) (a) Consiglio, G.; Morandini, F.; Sironi, A. J . Organomet. Chem.
1986, 306, C45. (b) Carmona, D.; Vega, C.; Lahoz, F. J .; Atencio, R.;
Oro, L. A.; Lamata, M. P.; Viguri, F.; San J ose´, E. Organometallics
2000, 19, 2273.
(8) (a) Winkhaus, G.; Singer, H. J . Organomet. Chem. 1967, 7, 487.
(b) Zelonka, R. A.; Baird, M. C. Can. J . Chem. 1972, 50, 3063. (c)
Bennett, M. A.; Smith A. K. J . Chem. Soc., Dalton Trans. 1974, 233.
(d) Bennett, M. A.; Huang, T. N.; Matheson, T. W.; Smith, A. K. Inorg.
Synth. 1981, 21, 74.
(11) For the compound mentioned above the RuCCH resonance
signal appears at 1.39 ppm.
(12) Pe´rez, J .; Brookhart, M.; Templeton, J . L. Unpublished results.
(13) The preparation of [RuCl(η6-arene)(L-L)]X (L-L
)
1,10-
phenanthroline, 2,2′-bipyridine,
X ) PF6, BF4, AsF6) complexes
(9) Brookhart, M.; Grant, B.; Volpe, A. F., J r. Organometallics 1992,
11, 3920.
required high temperatures and/or polar solvents: (a) Robertson, D.
R.; Robertson, I. W.; Stephenson, T. A. J . Organomet. Chem. 1980,
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metallics 1993, 12, 610.
(10) The complex [Ru(CCH)(η5-C5H5)(PMe3)2] exhibits a C-C ab-
sorption band at 1921 cm-1; see ref 3a.

(Arene)ruthenium Alkynyl Complexes
Organometallics, Vol. 20, No. 13, 2001 2777
Sch em e 2
carried out without exclusion of air. In a second step, a
metathetical reaction between the ruthenium chloro-
complex and sodium acetylide affords the ethynyl
complex 1. A long reaction time (12 h) is needed due to
the low solubility of sodium acetylide.
The reaction of a metal halocomplex and an alkaline-
metal acetylide is perhaps the most general synthetic
scheme for the preparation of alkynyl complexes.15
However, it has been rarely employed for the direct
preparation of ethynyls. Rather, most ethynyls have
been synthesized by deprotection of trimethylsilylacetyl-
ide precursors15c,16 or by deprotonation of a cationic
vinylidene complex.3a,17
Ethynyl derivatives are relatively rare. Among the
plethora of known ruthenium alkynyls, the only crys-
tallographically characterized ethynyl complexes are, to
our knowledge, the octahedral compounds trans-
[Ru(CCH)Cl(dppm)2]17b and all-trans-[Ru(CCH)2(CO)2-
(PEt3)2].18 Complex 1 is the first (arene)ruthenium
ethynyl compound.
We aimed to extend the synthesis of alkynyls of the
type [Ru(CCR)(cym)(phen)]BAr′4 to derivatives with R
groups other than H. For this purpose, we chose the
lithium acetylides LiCCR (R ) Ph, SiMe3), conveniently
generated in situ by the reaction of the corresponding
acetylenes with n-BuLi. However, the lithium acetylides
were not reactive toward solutions of [RuCl(cym)(phen)]-
BAr′4. To increase the reactivity of the ruthenium
complex, we sought to substitute the chloride ligand by
the more labile triflate. Thus, a solution of [RuCl(cym)-
(phen)]BAr′4 was allowed to react in the absence of light
with an equimolar amount of AgOTf. The resulting
[Ru(OTf)(cym)(phen)]BAr′4 complex was not isolated.
Instead, the filtered solutions of the triflatocomplex were
transferred onto the solution of the appropriate lithium
acetylide reagent. By this way we were able to prepare
the complexes [Ru(CCPh)(cym)(phen)]BAr′4 (2) and [Ru-
(CCSiMe3)(cym)(phen)]BAr′4 (3) (Scheme 2). In the
synthesis of 2, we found that addition of some methanol
to the reaction mixture was needed. Similar use of
methanol as cosolvent in the preparation of [RuCl(η6-
C6Me6)(CCPh)(PMe3)] was reported by Dixneuf.6
the acetylenic C-C stretching band at 2111 cm-1 19
and
,
the two acetylenic carbons give rise to 13C NMR signals
at 111.2 and 105.9 ppm.6 For complex 3, the IR stretch-
ing of the acetylenic C-C bond20 occurs at 2039 cm-1
,
and, in the 13C NMR, the acetylenic carbons of 3 appear
as weak signals at 111.4 and 108.5 ppm.
The solubility of complexes 1-3 in solvents of moder-
ate polarity, such as dichloromethane, is very high, due
to the presence of the BAr′4 counteranion,14 facilitating
the acquisition of 13C NMR spectra with a good signal-
to-noise ratio. This is particularly relevant for alkynyl
complexes, for which the most informative signals, those
of acetylenic carbons, are of intrinsic low intensity.
Complex 1 reacted with a stoichiometric amount of
trifluoromethylsulfonic acid to yield the acyl complex
[Ru(C(O)CH3)(cym)(phen)]BAr′4 (4). The characteriza-
tion of complex 4 is based on its spectroscopic data. The
strong IR absorption at 1631 cm-1 is consistent with
the presence of the acyl ligand, and the chemical shifts
1
in the H NMR (1.85 ppm) and 13C NMR (252.7 ppm
for the carbonylic carbon and 42.2 ppm for the methyl
carbon) spectra are very close to those found for other
Ru(II) acetyl complexes.21 19F NMR of 4 showed only
the signal of the BAr′4 anion, indicating that no incor-
poration of triflate was taking place.
An X-ray determination carried out on a single crystal
of 4 (Figure 2, Table 2) confirmed the [Ru(C(O)CH3)-
(cym)(phen)]BAr′4 formulation. However, again the low
accuracy of the results and, in particular, the presence
of disorder affecting the acetyl group (see Experimental
Section) would render meaningless a discussion of the
metrical parameters.
The reaction of alkynyl complexes with electrophiles
typically affords vinylidenes.2a,b Obtention of an acyl as
the product of the protonation of alkynyl complexes has
been found in several instances2a,22 and takes place by
the reaction of a highly reactive vinylidene intermediate
with traces of water present in the reaction mixture.
For (arene)ruthenium complexes, the related reaction
of the cationic vinylidene [RuCl(CC(H)Ph)(η6-C6Me6)-
(PMe3)]+ with methanol to yield a methoxycarbene has
been reported.6 (Arene)ruthenium vinylidenes were
The 19F NMR spectra of complexes 2 and 3 showed
only the signal of the BAr′4 anion (-62.79 ppm).
Therefore, BAr′4/OTf exchange did not take place under
the reaction conditions when the chloride ligand was
substituted by triflate. The presence of the alkynyl
ligands in compounds 2 and 3 was clearly indicated by
their spectroscopic features. The IR spectrum of 2 shows
(14) (a) Strauss, S. H. Chem. Rev. 1993, 93, 927. (b) Burk, M. J .;
Feng, S.; Gross, M. F.; Tumas, W. J . Am. Chem. Soc. 1995, 117, 8277.
(c) Schuster, D. M.; White, P. S.; Templeton, J . L. Organometallics
2000, 19, 1540.
(15) (a) Nast, R. Coord. Chem. Rev. 1982, 47, 89. (b) Wong, A.; Kang,
P. C. W.; Tagge, C. D.; Leon, D. R. Organometallics 1990, 9, 1992. (c)
Ramsden, J . A.; Weng, W.; Gladysz, J . A. Organometallics 1992, 11,
3635. (d) Albertin, G.; Antoniutti, S.; Bordignon, E.; Cazzaro, F.; Ianelli,
S.; Pelizzi, G. Organometallics 1995, 15, 4114. (e) Bruce, M. I.; Ke,
M.; Low, P. I. J . Chem. Soc., Chem. Commun. 1996, 2405.
(16) Sakurai, A.; Akita, M.; Moro-oka, Y. Organometallics 1999, 18,
3241.
(17) (a) Senn, D. R.; Wong, A.; Patton A. T.; Marsi, M.; Strouse, C.
E.; Gladysz, J . A. J . Am. Chem. Soc. 1988, 110, 6096. (b) Haquette,
P.; Pirio, N.; Touchard, D.; Toupet, L.; Dixneuf, P. H. Organometallics
1993, 12, 3132. (c) Le Narvor, N.; Toupet, L.; Lapinte, C. J . Am. Chem.
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(18) Sun, Y.; Taylor, N. J .; Carty, A. J . J . Organomet. Chem. 1992,
423, C43.
(19) Tables with IR νCC data of many phenylethynyl complexes are
included in ref 1.
(20) A collection of IR data for trimethylsylylacetylide derivatives
is included in the Supporting Information of: J ohn, K. D.; Stoner, T.
C.; Hopkins, M. D. Organometallics 1997, 16, 4948.
(21) (a) McCooney, K. M.; Probitts, E. J .; Mawby, R. J . J . Chem.
Soc., Dalton Trans. 1987, 1713. (b) Bellachioma, G.; Cardaci, G.;
Gramlich, V.; Macchioni, A.; Valentini, M.; Zuccaccia, C. Organome-
tallics 1998, 17, 5025.
(22) Hill, F. A. In Comprehensive Organometallic Chemistry II; Abel,
E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford,
UK, 1995; Vol. 7, p 351.

2778 Organometallics, Vol. 20, No. 13, 2001
Mene´ndez et al.
Sch em e 4
the reaction is catalytic in triflic acid. However, at-
tempts to carry out the reaction with less than stoichio-
metric amounts of triflic acid led to decreased yields.
In our opinion, this reflects the need of a strongly acidic
medium to achieve the initial protonation of the cationic
alkynyl.
F igu r e 2. Thermal ellipsoid (drawn at the 30% probability
level) plot of 4.
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for Com p lex 4
Since the reaction of (arene)ruthenium vinylidenes
with alcohols is known to afford alcoxycarbenes,5,23 we
added HOTf to a solution of 1 in a mixture CH2Cl2/
MeOH, expecting that the trapping of the initially
formed vinylidene by MeOH would give a cationic
methoxycarbene. No reaction took place. We believe that
the presence of methanol reduces the acidity of the
medium to a level that is not enough for the protonation
of 1 to take place.
Ru(1)-C(1)
Ru(1)-N(1)
Ru(1)-C(26)
Ru(1)-C(21)
Ru(1)-C(24)
C(1)-C(2)
2.084(11)
2.088(8)
2.207(10)
2.256(9)
2.321(8)
1.312(17)
Ru(1)-N(2)
Ru(1)-C(23)
Ru(1)-C(22)
Ru(1)-C(25)
C(1)-O(1)
2.088(8)
2.203(9)
2.209(9)
2.308(9)
1.252(15)
C(1)-Ru(1)-N(2)
N(2)-Ru(1)-N(1)
O(1)-C(1)-Ru(1)
85.5(4)
78.2(3)
124.6(9)
C(1)-Ru(1)-N(1)
O(1)-C(1)-C(2)
C(2)-C(1)-Ru(1)
81.4(3)
120.0(12)
112.8(9)
Syn t h esis a n d Ch a r a ct er iza t ion of t h e Bis-
(a lk yn yl) [Ru (CCP h )2(cym )(P Me3)] (5). The complex
[RuCl2(cym)(PMe3)]24 reacted with excess lithium phen-
ylacetylide to yield, after workup, the complex [Ru-
(CCPh)2(cym)(PMe3)] (5) (Scheme 4).
Sch em e 3
1
Integration of the H NMR spectrum of 5 indicated
the presence of two phenylacetylide groups in the
molecule. An additional indication of the [Ru(CCPh)2-
(cym)(PMe3)] formulation for 5 is provided by the
presence of a single doublet for the isopropyl CH3
groups. A complex [RuX(CCPh)(cym)(PMe3)] would be
chiral, and, therefore, two doublets for the diastereotopic
CH3 groups would be seen. The 13C NMR spectrum of 5
showed weak signals a 115.3 and 113.5 ppm for the
acetylenic carbons of the two equivalent alkynyl ligands.
The signal at 113.5 ppm showed a 35 Hz coupling with
phosphorus (no resolved coupling is seen in the slightly
broadened signal at 115.3 ppm) and is therefore as-
signed to the carbon atom directly bound to ruthenium.
The IR spectrum of the bis(acetylide) 5 displays a single
band at 2089 cm-1. In (arene)ruthenium(II) complexes
such as 5, the angles between the monodentate ligands
must be considerably less than 180°. Hence, two C-C
stretching bands in the IR spectrum are expected for
the two independent, active vibration modes of a bis-
(acetylide) complex like 5. In octahedral dicarbonyl
complexes, the presence of one or two C-O stretching
bands is a safe diagnostic of the trans or cis mutual
disposition of the carbonyl ligands.25 A single C-C band,
found to be more reactive than Cp derivatives, and only
the (arene)ruthenium vinylidene mentioned above could
be spectroscopically detected. This enhanced reactivity
has been attributed to an increase in the electrophilic
character of the vinylidene group as a result of a
decrease in the electronic density at the metal center.
The protonation of a cationic alkynyl such as 1 would
give a dicationic vinylidene complex. This species should
possess a high electrophilic character, and, hence, it is
not surprising that it reacts instantaneously (the acyl
4 was the only ruthenium species observed by 1H NMR
when the reaction of 1 with HOTf was carried out in
CD2Cl2 in a NMR tube) with traces of water (Scheme
3). The overall reaction leading to the obtention of 4
involves the formal addition of the elements of OH- from
water. The remaining H+ of H2O plus the OTf anion
(which would be one of the counterions in the dicationic
vinylidene intermediate) would regenerate HOTf. Thus,
(23) (a) Pilette, D.; Ouzzine, K.; Le Bozec, H.; Dixneuf, P. H.
Organometallics 1992, 11, 809. (b) Devanne, D.; Dixneuf, P. H. J .
Organomet. Chem. 1990, 390, 371.
(24) Bennett, M. A.; Smith, K. A. J . Chem. Soc., Dalton Trans. 1974,
233.
(25) Crabtree, R. H. The Organometallic Chemistry of the Transition
Metals, 2nd ed; J ohn Wiley & Sons: New York, 1994; p 259.

(Arene)ruthenium Alkynyl Complexes
Organometallics, Vol. 20, No. 13, 2001 2779
distances are in the typical range of transition metal
alkynyls.1 The angle between the two metal-bonded
alkynyl carbon atoms and ruthenium, 91.3(5)°, is only
slightly greater than the Cl-Ru-Cl angles (88.1° and
88.18(3)°) found in [RuCl2(PR3)(arene)] complexes29 and
is almost identical to the C-Ru-C angle found in the
octahedral cis-bis(alkynyl) [Ru(CCPh)2L], L ) P(CH2-
CH2PPh2)3 (90.7(5)°).28a
The synthesis of bis(acetylide) transition metal com-
plexes that can be used as metalloligands with a tweezer
geometry toward a second metal center has attracted
the attention of several research groups.3c,g,k,25,30-33 Most
of these bis(acetylide) complexes are based on group 4
metallocene fragments3c,30,32 or are square-planar pal-
ladium or platinum compounds.3d,g,30e,31a,b As far as we
know, the only ruthenium complex that was used as
tweezer metalloligand is the octahedral compound cis-
[Ru(Ph2PCH2PPh2)2(CCFc)2] (Fc ) ferrocenyl), which
acts as a chelate toward CuI with a C-Ru-C angle of
82.6(3)°.34 Complex 5 is the first pseudotetrahedral
piano-stool ruthenium bis(alkynyl) complex, and the fact
that the angle between the alkynyl groups is similar to
those found in tweezer-like bimetallic complexes35 is
encouraging with regard to the use of 5 as a metallo-
ligand.
F igu r e 3. Thermal ellipsoid (drawn at the 30% probability
level) plot of 5.
Ta ble 3. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for Com p lex 5
Ru(1)-C(3)
Ru(1)-C(12)
Ru(1)-C(11)
Ru(1)-P(1)
Ru(1)-C(15)
C(2)-C(21)
C(4)-C(31)
2.003(9)
2.242(7)
2.245(8)
2.267(2)
2.276(8)
1.474(10)
1.447(11)
Ru(1)-C(1)
Ru(1)-C(13)
Ru(1)-C(16)
Ru(1)-C(14)
C(1)-C(2)
2.026(6)
2.243(7)
2.260(8)
2.268(8)
1.168(7)
1.139(9)
C(3)-C(4)
C(3)-Ru(1)-C(1)
C(1)-Ru(1)-P(1)
C(1)-C(2)-C(21)
C(3)-C(4)-C(31)
91.5(3)
85.3(2)
174.5(10)
178.7(12)
C(3)-Ru(1)-P(1)
C(2)-C(1)-Ru(1)
C(4)-C(3)-Ru(1)
81.5(3)
168.0(9)
168.6(9)
Exp er im en ta l Section
however, is observed for several cis-bis(acetylides),1,26
as for complex 5. To our knowledge, no explanation has
been given for this apparent inconsistency, and we have
to assume that the two stretching modes in bis(acetyl-
ide) complexes fall in a narrow wavenumber range and,
due to the intrinsic width of the IR bands, the two bands
often overlap.
Gen er a l P r oced u r es. All manipulations were carried out
under nitrogen using standard Schlenk techniques or in a
drybox. Solvents were distilled from freshly wired Na (hex-
anes), Na/benzophenone (Et2O and THF), NaOMe (MeOH),
and CaH2 (CH2Cl2). CD2Cl2 and CDCl3 were degassed by three
freeze-pump-thaw cycles, dried over molecular sieves (MS4A),
and stored in the dark. Elemental analyses were obtained
using a Perkin-Elmer 240-B microanalyzer. The IR and NMR
spectra were recorded on Perkin-Elmer FT 1720-X and Bruker
AC-200 or AC-300 spectrometers, respectively. [{RuCl(cym)}2-
The reaction of [RuCl2(η6-C6Me6)(PMe3)] with an
excess of LiCCPh in hexane/MeOH to give the alkynyl
complex [RuCl(CCPh)(η6-C6Me6)(PMe3)] was reported by
Le Bozec and Dixneuf.6 We have found that the employ-
ment of THF (instead of hexane/MeOH mixtures) is
needed to obtain the bis(alkynyl) product 5. The reaction
of [RuCl(CCPh)(cym)(PMe3)] with additional LiCCPh in
THF yields [Ru(CCPh)2(cym)(PMe3)], 5, although this
stepwise synthesis of 5 does not offer any advantage.
In chlorinated solvents, 5 undergoes a slow (12 h in
CDCl3, 60 h in CD2Cl2) transformation to [RuCl2(cym)-
(PMe3)]. 31P NMR monitoring of this decomposition in
CD2Cl2 showed the presence of [RuCl(CCPh)(cym)-
(PMe3)]27 as an intermediate. In contrast, 5 is indefi-
nitely stable in THF or toluene solutions.
9
(µ-Cl)2]8 and NaBAr′4 were prepared according to literature
procedures. All other chemicals were used as received from
commercial sources. 13C NMR signals of the BAr′4 anion are
almost identical in all complexes and are given only for 1.
Syn th esis of [Ru (CCH)(cym )(p h en )]BAr ′4 (1). A mixture
of [{RuCl(cym)}2(µ-Cl)2] (0.026 mmol, 0.016 g), 1,10-phenan-
throline (0.055 mmol, 0.010 g), and NaBAr′4 (0.055 mmol, 0.048
g) was dissolved in THF and stirred for 2 h. The resulting
orange solution of [RuCl(cym)(phen)]BAr′4 was transferred via
(29) (a) Bennett, M. A.; Robertson, G. B.; Smith, A. K. J . Organomet.
Chem. 1972, 43, C41. (b) Elsegood, M. R. J .; Tocher, D. A. Polyhedron
1995, 14, 3147.
(30) (a) Lang, H.; Herres, M.; Zsolnai, L.; Imhof, W. J . Organomet.
Chem. 1991, 409, C7. (b) Lang, H.; Frosch, W.; Wu, I. Y.; Blau, S.;
Nuber, B. Inorg. Chem. 1996, 35, 6266. (c) Delgado, E.; Herna´ndez,
E.; Mansilla, N.; Moreno, M. T.; Sabat, M. J . Chem. Soc., Dalton Trans.
1999, 533. (d) Back, S.; Rheinwald, G.; Lang, H. J . Organomet. Chem.
2000, 601, 93. (e) Frosch, W.; del Villar, A.; Lang, H. J . Organomet.
Chem. 2000, 602, 91.
(31) (a) Ara, I.; Berenguer, J . R.; Fornie´s, J .; Lalinde, E. Inorg. Chim.
Acta 1997, 264, 199. (b) Ara, I.; Berenger, J . R.; Eguiza´bal, E.; Fornie´s,
J .; Lalinde, E.; Mart´ınez, F. Organometallics 1999, 18, 4344. (c)
Falvello, L. R.; Fornie´s, J .; Go´mez, J .; Lalinde, E.; Mart´ın, A.; Moreno,
M. T.; Sacrista´n Chem. Eur. J . 1999, 5, 474. (d) Adams, C. J .; J ames,
S. L.; Liu, X.; Raithby, P. R.; Yellowlees, L. J . J . Chem. Soc., Dalton
Trans. 2000, 63.
(32) (a) Lang, H.; Zsolnai, L. J . Organomet. Chem. 1991, 406, C5.
(b) Back, S.; Pritzkow, H.; Lang, H. Organometallics 1998, 17, 41. (c)
Back, S.; Rheinwald, G.; Lang, H. Organometallics 1999, 18, 4119.
(33) Lang, H.; George, D. S. A.; Rheinwald, G. Coord. Chem. Rev.
2000, 206-207, 101.
(34) Zhu, Y.; Clot, O.; Wolf, M. O.; Yap, G. P. A. J . Am. Chem. Soc.
1998, 120, 1812.
(35) For typical angles see refs 28a, 31c, and 32b,c.
The molecular structure of complex 5 was determined
by single-crystal X-ray diffraction (Figure 3, Table 3).
The geometry of 5 can be described as a three-legged
piano stool. The Ru-Calkynyl distances, 2.003(9) and
2.026(6) Å, are similar to those found in other ruthen-
ium alkynyl complexes.18,28 Triple bond carbon-carbon
(26) J ames, S. L.; Younus, M.; Raithby, P. R.; Lewis, J . J . Orga-
nomet. Chem. 1997, 543, 233.
(27) Spectroscopic data for [RuCl(CCPh)(cym)(PMe3)]: IR ν(CC)
(CH2Cl2): 2095 cm-1
.
1H NMR (CDCl3): 7.30 (m, 5H, Ph), 5.76
(apparent triplet J ) 5.87 Hz), 5.16, 5.08 (d (5.87), 4H, C6H4), 2.85
(sep, 1H, CH(Pri)), 2.15 (s, 3H, CH3-C6H4), 1.65 (d(10.75), 9H, PCH3),
1.28 (apparent triplet J ) 6.65, 6H, CH3(Pri)). 31P{1H} NMR (CDCl3):
δ 10.24.
(28) (a) Bianchini, C.; Frediani, P.; Masi, D.; Peruzzini, M.; Zanobini
F. Organometallics 1994, 13, 4616. (b) Pedersen, A.; Tilset, M.; Folting,
K.; Caulton, K. G. Organometallics 1995, 14, 875.

2780 Organometallics, Vol. 20, No. 13, 2001
Mene´ndez et al.
mixture was allowed to reach room temperature and stirred
for 12 h. The workup was as described for 1, affording 3 as a
brown microcrystalline solid. Yield: 0.055 g, 82%. Anal. Calcd
for C59H43BF24N2RuSi: C, 51.46; H, 3.12; N, 2.03. Found: C,
51.61; H, 3.25; N, 1.75. IR ν(CC) (CH2Cl2): 2039 cm-1. 1H NMR
(CDCl3): 9.07 (dd (5.1 and 1.2), 2H, H2), 8.43 (dd (8.3 and 1.3),
2H, H4), 7.91 (s, 2H, H5), 7.84 (dd (8.45 and 5.37), 2H, H3),
7.70 (m, 8H, Ho), 7.49 (m, 4H, Hp), 5.68, 5.66, 5.48, 5.46 (q
AB, 4H, C6H4), 2.81 (sep, 1H, CH(Pri)), 2.13 (s, 3H, CH3-C6H4),
1.11 (d (6.9), 6H, CH3(Pri)), -0.37 (s, 9H, SiCH3). 13C{1H} NMR
(CDCl3): 154.1 (s, C2), 146.0 (s, C7), 137.6 (s, C4), 130.5 (s, C5),
127.4 (s, C6), 126.2 (s, C3), 118.9 (s, C-Pri), 111.4 (s, RuCC),
108.5 (s, RuCC), 105.9 (s, C-CH3), 87.5 (s, CA), 86.9 (s, CB),
31.5 (s, CH(Pri)), 22.2 (s, CH3 of Pri), 18.4 (s, CH3-C6H4), 0.7
(s, SiCH3).
F igu r e 4. Atom-labeling schemes for phenanthroline,
BAr′4, and cym.
cannula onto sodium acetylide (0.15 mmol, 0.008 g). The best
results were obtained when the commercial sodium acetylide
was washed with hexanes (3 × 10 mL) and briefly dried in
vacuo, leaving a loose solid that was weighted in a drybox.
The resulting slurry was stirred for 12 h. After filtration
(diatomaceous earth), the solvent was removed in vacuo. The
residue was extracted with CH2Cl2 (3 × 10 mL), and the
solution was filtered a second time. This second filtration in
CH2Cl2 was found to remove traces of pyrophoric sodium
acetylide. The solution was concentrated by in vacuo evapora-
tion to a volume of 5 mL. Slow diffusion of hexane into this
solution at -20 °C produced orange crystals of 1. A single
crystal obtained in this way was used for the X-ray analysis.
Yield: 0.042 g, 61%. Anal. Calcd for C56H35BF24N2Ru: C, 51.57;
H, 2.68; N, 2.15. Found: C, 51.31; H, 2.50; N, 2.10. IR ν(CC)
(CH2Cl2): 1974 cm-1. 1H NMR (CD2Cl2): 9.17 (dd (5.0 and 1.0),
2H, H2), 8.56 (dd (8.2 and 1.1), 2H, H4), 8.02 (s, 2H, H5), 7.88
(dd (8.45 and 5.37), 2H, H3), 7.76 (m, 8H, Ho), 7.57 (m, 4H,
Hp), 5.57, 5.73, 5.58, 5.56 (q AB, 4H, C6H4), 2.78 (sep, 1H,
CH(Pri)), 2.25 (s, 3H, CH3-C6H4), 1.37 (s, 1H, CCH), 1.09 (d
(6.9), 6H, CH3(Pri)). 13C{1H} NMR (CD2Cl2): 162.1 (q (49.9),
Ci), 154.8 (s, C2), 146.4 (s, C7), 138.2 (s, C4), 135.1 (s, br, Co),
Syn th esis of [Ru (C(O)CH3)(cym )(p h en )]BAr ′4 (4). To a
solution of [Ru(CCH)(cym)(phen)]BAr′4 (0.04 mmol, 0.050 g)
in 10 mL of CH2Cl2 was added CF3SO3H (0.03 mmol, 3 µL).
The color immediately changed from brown to orange. The
solution was stirred for 10 min and filtered through diatoma-
ceous earth, the solvent was eliminated in vacuo, and the
residue was washed with hexane (3 × 10 mL). Slow diffusion
of hexane in a concentrated solution of 4 in CH2Cl2 at -20 °C
afforded orange crystals, one of which was used for the X-ray
analysis. Yield: 0.065 g, 88%. Anal. Calcd for C56H37BF24N2-
ORu: C, 50.84; H, 2.80; N, 2.12. Found: C, 50.78; H, 2.65; N,
2.10. IR ν(CO) (CH2Cl2): 1631 cm-1 1H NMR (CDCl3): 9.27
.
(dd (5.0 and 1.0), 2H, H2), 8.39 (dd (8.2 and 1.1), 2H, H4), 7.86
(s, 2H, H5), 7.79 (dd (8.45 and 5.37), 2H, H3), 7.73 (m, 8H, Ho),
7.59 (m, 4H, Hp), 5.62, 5.59, 5.32, 5.29 (q AB, 4H, C6H4), 2.52
(sep, 1H, CH(Pri)), 2.17 (s, 3H, CH3-C6H4), 1.85 (s, 3H, C(O)-
CH3), 0.88 (d (6.9), 6H, CH3(Pri)). 13C{1H} NMR (CDCl3): 252.7
(s, CO), 154.8 (s, C2), 145.0 (s, C7), 137.1 (s, C4), 130.1 (s, C5),
127.5 (s, C6), 112.6 (s, C3), 115.0 (s, C-Pri), 106.6 (s, C-CH3),
76.9 (s, CA), 76.5 (s, CB), 42.2 (s, C(O)CH3), 31.2 (s, CH(Pri)),
22.4 (s, CH3 of Pri), 18.5 (s, CH3-C6H4).
2
4
131.2 (s, C5), 129.1 (qq, J CF ) 31, J CF ) 3, Cm), 128.1 (s, C6),
127.9 (s, C3), 126.1 (q(272), CF), 119.9 (s, C-Pri), 117.8 (s, Cp),
105.9 (s, C-CH3), 99.9 (s, RuCC), 88.9 (s, RuCC), 88.9 (s, CA),
87.1 (s, CB), 31.8 (s, CH(Pri)), 22.4 (s, CH3 of Pri), 19.0 (s, CH3-
C6H4).
Syn th esis of [Ru (CCP h )(cym )(p h en )]BAr ′4 (2). To a
solution of [RuCl(cym)(phen)]BAr′4, prepared as described for
1, 0.05 mmol in THF (20 mL), was added AgOTf (0.055 mmol,
0.014 g), and the mixture was stirred for 2 h in the absence of
light at room temperature. The color of the resulting solution
was yellow, and a white solid (AgCl) precipitated. The solution
of [Ru(OTf)(cym)(phen)]BAr′4 obtained in this way was trans-
ferred through a cannula tipped with filter paper to a solution
of LiCCPh, freshly prepared from HCCPh (0.09 mmol, 9.8 µL)
and n-BuLi (0.09 mmol, 56 µL, 1.6 M solution in hexanes) in
10 mL of THF at -78 °C. MeOH (2 mL) was added, and the
mixture was stirred at room temperature for 12 h. The color
of the solution changed from yellow to brown. The solvent was
evaporated under reduced pressure, and the residue was
extracted with CH2Cl2 and filtered. A yellow solution was
obtained, which was concentrated in vacuo to a volume of 5
mL. Addition of hexane (20 mL) gave 2 as a yellow micro-
crystalline solid, which was dried under reduced pressure.
Yield: 0.040 g, 63%. Anal. Calcd for C62H39BF24N2Ru: C, 53.96;
H, 2.84; N, 2.03. Found: C, 53.80; H, 2.72; N, 1.85. IR ν(CC)
(CH2Cl2): 2111 cm-1. 1H NMR (CDCl3): 9.22 (dd (5.1 and 1.2),
2H, H2), 8.59 (dd (8.24 and 1.2), 2H), 8.05 (s, 2H, H5), 7.93 (dd
(8.24 and 5.50), 2H, H3), 7.75 (m, 8H, Ho), 7.57 (m, 4H, Hp),
6.90 (m, 5H, Ph), 5.81, 5.78, 5.63, 5.61 (q AB, 4H, C6H4), 2.85
(sep, 1H, CH(Pri)), 2.28 (s, 3H, CH3-C6H4), 1.16 (d (7), 6H, CH3-
(Pri)). 13C{1H} NMR (CDCl3): 154.1 (s, C2), 145.9 (s, C7), 137.7
(s, C4), 130.9 (s, Ph), 130.5 (s, C5), 128.4 (s, C6), 127.6 (s, C3),
127.5 (s, Ph), 125.5 (s, Ph), 121.6 (s, C-Pri), 111.2 (s, RuCC),
105.9 (s, RuCC), 102.4 (s, C-CH3), 87.5 (s, CA), 86.7 (s, CB),
31.5 (s, CH(Pri)), 22.2 (s, CH3 of Pri), 18.5 (s, CH3-C6H4).
Syn th esis of [Ru (CCSiMe3)(cym )(p h en )]BAr ′4 (3). A
solution of LiCCSiMe3, prepared from HCCSiMe3 (0.049 mmol,
7 µL) in 10 mL of THF and n-BuLi (0.05 mmol, 30 µL, 1.6 M
solution in hexanes) at -78 °C, was transferred onto a solution
of [Ru(OTf)(cym)(phen)]BAr′4 (0.05 mmol), prepared as de-
scribed above, in 20 mL of THF at -78 °C. The reaction
Syn th esis of [Ru (CCP h )2(cym )(P Me3)] (5). [{RuCl(cym)}2-
(µ-Cl)2] (0.16 mmol, 0.10 g) and PMe3 (0.32 mmol, 28 µL) in
10 mL of THF were allowed to react for 30 min. The resulting
solution of [RuCl2(cym)(PMe3)] was transferred onto a solution
of LiCCPh, freshly prepared from HCCPh (0.65 mmol, 72 µL)
and n-BuLi (0.65 mmol, 406 µL, 1.6 M solution in hexanes) in
10 mL of THF at -78 °C. The solution was stirred for 12 h.
The solvent was evaporated in a vacuum, and the residue was
extracted with CH2Cl2 and filtered through diatomaceous
earth. Recrystallization with hexane gave a brown microcrys-
talline solid. A crystal suitable for an X-ray determination was
obtained by slow diffusion of hexane into a solution of 5 in
Et2O at -20 °C. Compound 5 is moisture sensitive. It slowly
decomposes in CDCl3 (12 h) and in CD2Cl2 (60 h) to yield
[RuCl2(cym)(PMe3)] as the major product. Yield: 0.097 g, 59%.
Anal. Calcd for C29H33PRu: C, 69.11; H, 6.55. Found: C, 69.05;
H, 6.49. IR ν(CC) (CH2Cl2): 2089 cm-1. 1H NMR (CDCl3): 7.30
(m, 10H, Ph), 5.57, 5.55, 5.53, 5.51 (q AB, 4H, C6H4), 2.86 (sep,
1H, CH(Pri)), 2.23 (s, 3H, CH3-C6H4), 1.65 (d(11.2), 9H, PCH3),
1.29 (d (6.9), 6H, CH3(Pri)). 13C{1H} NMR (CD2Cl2): 131.3 (s,
Co and Cm, Ph), 129.9 (s, Ci, Ph), 124.2 (s, Cp, Ph), 115.3 (s,
RuCC), 113.5 (d(35.0), RuCC), 104.4 (s, C-Pri), 102.7 (s, C-CH3),
94.3 (s, CA), 91.4 (s, CB), 32.1 (s, CH(Pri)), 24.3 (s, CH3 of Pri),
19.6(d(36.2), PCH3), 19.2 (s, CH3-C6H4). 31P{1H} NMR (CD2-
Cl2): δ 15.06.
X-r a y Cr ysta l Str u ctu r e Deter m in a tion of Com p lexes
1, 4, a n d 5. In each case, a suitable crystal was attached to a
glass fiber and transferred to a Bruker AXS SMART 1000
diffractometer with graphite-monochromatized Mo KR X-
radiation and a CCD area detector. A hemisphere of the
reciprocal space was collected up to 2θ ) 48.6°. Raw frame
data were integrated with the SAINT36 program. The structure
(36) SAINT+.SAX area detector integration program, Version 6.02;
Bruker AXS, Inc.: Madison, WI, 1999.

(Arene)ruthenium Alkynyl Complexes
Organometallics, Vol. 20, No. 13, 2001 2781
Ta ble 4. Cr ysta l Da ta a n d Refin em en t Deta ils for Com p lexes 1, 4, a n d 5
1
4
5
formula
fw
cryst syst
space group
a, Å
C
61H39BF24N2Ru
C56H39BF24N2ORu
1323.77
triclinic
P1h
13.267(2)
13.868(2)
16.370(3)
74.013(4)
87.625(5)
75.313(5)
2799.5(9)
2
C19H33PRu
513.59
monoclinic
C2/c
25.243(7)
11.725(3)
18.631(5)
90
106.644(5)
90
5284(2)
8
1367.82
triclinic
P1h
13.083(7)
13.917(7)
16.421(8)
73.54(1)
85.12(1)
74.64(1)
2765(2)
2
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
T, K
293
1.64
1368
293
1.57
1324
295
1.29
2128
F
calc, g cm-3
F(000)
λ (Mo KR), Å
0.71073
0.37 × 0.25 × 0.2, yellow
0.409
1 e θ e 21
SADABS
1.000, 0.847
12694
5741
5741/0/760
1.053
0.71073
0.2 × 0.2 × 0.2, yellow
1.570
1 e θ e 21
SADABS
1.000, 0.7845
12874
5841
5841/0/771
1.056
0.71073
cryst size, mm; color
0.13 × 0.12 × 0.1, yellow
µ, mm-1
scan range, deg
abs corr
corr factors (min., max.)
no. of reflns measured
no. of indep reflns
no. of data/restraints/params
goodness-of-fit on F2
no of reflns obsd, I g 2σ(I)
R1 (obsd reflns)
wR2 (all data)
0.667
1 e θ e 21
SADABS
1.000, 0.7904
11144
2762
2762/0/286
0.783
1397
0.0406
0.0703
4975
0.0669
0.1862
4891
0.0771
0.2291
was solved by direct methods with SHELXTL.37 An empirical
absorption correction was applied with the program SAD-
ABS.38 All non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were set in calculated positions and refined
as riding atoms with a common thermal parameter. All
calculations were made with SHELXTL. In the structure of 4
several peaks were found in the region of the acetyl group,
suggesting the existence of several disordered positions which
arise from rotation of the acetyl group around the Ru-C(1)
Additional material is available from the Cambridge Crys-
tallographic Data Center, including atomic coordinates, ther-
mal parameters, and a full list of bond lengths and angles.
Ack n ow led gm en t. We thank Luc´ıa Riera and Eva
Hevia for checking several experiments, Ministerio de
Ciencia y Tecnolog´ıa (Projects MCT-00-BQU-0220 and
PB97-0470-C02-01) for financial support, and FICYT
(Asturias, Spain) for a postdoctoral scholarship (to
D.M.).
bond. Unfortunately, it was not possible to construct
a
satisfactory model for this situation, and only the main
orientation has been included. Moreover, the final model must
be considered as an average which contains disordered O(1)
and C(2) interchanging positions.
Su p p or tin g In for m a tion Ava ila ble: Tables giving posi-
tional and thermal parameters, bond distances, and bond
angles for 1, 4, and 5. This material is available free of charge
via the Internet at http://pubs.acs.org.
(37) Sheldrick, G. M. SHELXTL, An integrated system for solving,
refining and displaying crystal structures from diffraction data, Version
5.1; Bruker AXS, Inc.: Madison, WI, 1998.
(38) Sheldrick, G. M. SADABS, Empirical Absorption Correction
Program; University of Go¨ttingen, 1997.
OM000834Q