Synthesis and reactivity of indenyl ruthenium(II) complexes containing the labile ligand 1,5-cyclooctadiene (COD): Catalytic activity of [Ru(η5-C9H7)Cl(COD)]

Article abstract of DOI:10.1021/om010205w

The treatment of [RuCl₂(COD)]_n with KC₉H₇ in THF leads to the formation of [Ru(η⁵-C₉H₇)Cl(COD)] (1) (80% yield) in a one-pot synthesis. Complex 1 is also formed by the reaction of [RuCl₂(COD)]_n with NaC₉H₇ in THF followed by treatment of the intermediate complex [Ru(η⁵-C₉H₇)(η²- η³-C₈H₁₁)] (2) with HCl. Substitution of labile COD ligand by bulky phosphines PR₃ (R = Cy, ⁱPr₃) can be achieved at room temperature in THF to give 16-electron species [Ru(η⁵-C₉H₇) Cl(PR₃)], which react with CO (1 atm) to afford complexes [Ru(η⁵-C₉H₇)Cl(CO)(PR₃)] (R = Cy (3a), ⁱPr (3b)). Chelate complexes [Ru(η⁵-C₉H₇)Cl{(κ²-P,N)-o- Ph₂PC₆H₄C(H)=N^tBu}] (4) and [Ru(η⁴-C₉H₇){κ¹-(P)- Ph₂PCH₂C(O)^tBu} {κ²-(P,O)Ph₂PCH=C(O)^tBu}] (5) have been similarly prepared by reaction with the bidentate ligands. [Ru(η⁵-C₉H₇)CU(NBD)] (NBD = norbornadiene) (6) has been prepared through an exchange reaction of 1 with NBD and characterized by X-ray diffraction. Neutral complexes [Ru(η⁵-C₉H₇)X-(COD)] (X = FBF₃ (7), N₃ (8)) were prepared from complex 1 by metathesis reactions of the chloride ligand by AgBF₄ and NaN₃ respectively. The treatment of 7 in CH₂Cl₂ with an excess of pyridine and acetonitrile gives cationic complexes [Ru(η⁵-C₉H₇)(COD)L][BF₄] in good yield (L = py (9), CH₃CN (10)). The structure of complex 9 has been determined by X-ray diffraction. Complex 1 catalyzes [2+2] and [4+2] cycloaddition reactions of norbornene and 1,5-cyclooctadiene with alkynes to give exotricyclic [4.2.1.0] coupling products and exotricyclo [4.2.2.0]dec-7-enes, respectively. These processes take place with high efficiency and selectivity. Complex 1 is also active in the catalytic hydration of terminal alkynes to afford ketones in high yield and selectivity.

Full text of DOI:10.1021/om010205w

3762
Organometallics 2001, 20, 3762-3771
Syn th esis a n d Rea ctivity of In d en yl Ru th en iu m (II)
Com p lexes Con ta in in g th e La bile Liga n d
1,5-Cycloocta d ien e (COD): Ca ta lytic Activity of
[Ru (η5-C9H7)Cl(COD)]
Patricia Alvarez,† J ose´ Gimeno,*,† Elena Lastra,† Santiago Garc´ıa-Granda,‡
J uan Francisco Van der Maelen,‡ and Mauro Bassetti§
Departamento de Quı´mica Orga´nica e Inorga´nica, Facultad de Quı´mica,
Universidad de Oviedo, Instituto de Qu´ımica Universitaria “Enrique Moles” (Unidad Asociada
al CSIC), 33006 Oviedo, Spain, Departamento de Qu´ımica Fı´sica y Analı´tica,
Facultad de Quı´mica, Universidad de Oviedo, 33006 Oviedo, Spain,
and Centro CNR di Studio sui Meccanismi di Reazione, c/ o Dipartimento di Chimica,
Universita´ “La Sapienza”, 00185 Roma, Italy
Received March 15, 2001
The treatment of [RuCl2(COD)]n with KC9H7 in THF leads to the formation of [Ru(η5-
C9H7)Cl(COD)] (1) (80% yield) in a one-pot synthesis. Complex 1 is also formed by the reaction
of [RuCl2(COD)]n with NaC9H7 in THF followed by treatment of the intermediate complex
[Ru(η5-C9H7)(η2-η3-C8H11)] (2) with HCl. Substitution of the labile COD ligand by bulky
i
phosphines PR3 (R ) Cy, Pr3) can be achieved at room temperature in THF to give 16-
electron species [Ru(η5-C9H7)Cl(PR3)], which react with CO (1 atm) to afford complexes
[Ru(η5-C9H7)Cl(CO)(PR3)] (R ) Cy (3a ), iPr (3b)). Chelate complexes [Ru(η5-C9H7)Cl{(κ2-P,N)-
o-Ph2PC6H4C(H)dNtBu}] (4) and [Ru(η4-C9H7){κ1-(P)-Ph2PCH2C(O)tBu}{κ2-(P,O)Ph2PCHd
C(O)tBu}] (5) have been similarly prepared by reaction with the bidentate ligands. [Ru(η5-
C9H7)Cl(NBD)] (NBD ) norbornadiene) (6) has been prepared through an exchange reaction
of 1 with NBD and characterized by X-ray diffraction. Neutral complexes [Ru(η5-C9H7)X-
(COD)] (X ) FBF3 (7), N3 (8)) were prepared from complex 1 by metathesis reactions of the
chloride ligand by AgBF4 and NaN3 respectively. The treatment of 7 in CH2Cl2 with an excess
of pyridine and acetonitrile gives cationic complexes [Ru(η5-C9H7)(COD)L][BF4] in good yield
(L ) py (9), CH3CN (10)). The structure of complex 9 has been determined by X-ray
diffraction. Complex 1 catalyzes [2+2] and [4+2] cycloaddition reactions of norbornene and
1,5-cyclooctadiene with alkynes to give exotricyclic [4.2.1.0] coupling products and exotricyclo
[4.2.2.0]dec-7-enes, respectively. These processes take place with high efficiency and
selectivity. Complex 1 is also active in the catalytic hydration of terminal alkynes to afford
ketones in high yield and selectivity.
In tr od u ction
sors of a wide series of derivatives, which have promoted
the development of a chemistry rich both in stoichio-
metric and catalytic transformations.3
The most genuine role in coordination chemistry of
carbocyclic η4-dienes such as 1,5-cyclooctadiene (COD),
2,5-norbornadiene (NBD), and tetrafluorobenzobar-
ralene (5,6,7,8-tetrafluoro-1,4-dihydro-1,4-ethenonaph-
thalene) relies on their ability to act as labile ligands.
This reactivity has been widely applied in numerous
ligand exchange processes.1 As the chemistry of orga-
noruthenium(II) derivatives is concerned, the ready
accessibility of the complexes [RuCl2(COD)]x and [RuCl2-
The growing interest during the past few years in the
synthesis and reactivity of ruthenium(II) complexes has
provided a variety of substrates. Among them, a series
of stable semisandwich η5-ring derivatives of the type
[Ru(η5-ring)X(η4-diene)] (X ) halide, H; ring ) Cp,
Cp*)4a-e and the analogous hydridotris(pyrazolyl)borate
and hydridotris(3,5-dimethyl)pyrazolyl)borate complexes
[RuTp(COD)X]4f have attracted preferential attention.
The lability of these η4-coordinated ligands, which are
able to undergo exchange reactions, is now well known.
In general these reactions occur under very mild condi-
2
(NBD)]x has allowed them to be used as useful precur-
† Departamento de Qu´ımica Orga´nica e Inorga´nica, Universidad de
Oviedo.
‡ Departamento de Qu´ımica F´ısica y Anal´ıtica, Universidad de
Oviedo.
§ Universita´ “La Sapienza”.
(3) (a) Naota, T.; Takaya, H.; Murahashi, S. I. Chem. Rev. 1998,
98, 2599-2660. (b) Trost, B. M. Chem. Ver. 1996, 129, 1313-1322. (c)
Wilkinson G.; Gillard, F. G.; McCleverty, E. W. Comprehensive
Coordination Chemistry; Pergamon: New York, 1987; Vol. 4, p 363.
(d) Seddon, E. A.; Seddon, K. The Chemistry of Ruthenium; Elsevier:
New York, 1984; p 729. (e) Wilkinson, G.; Stone, F. G.; Abel, E. W.
Comprehensive Coordination Chemistry; Pergamon: New York, 1995;
Vol. 4, p 748.
(1) (a) Abel, E. W.; Stone, F. G.; Wilkinson, G. Comprehensive
Organometallic Chemistry; Pergamon: New York, 1982; Vol. 5, p 602.
(b) Esteruelas, M. A.; Oro, L. A. Coord. Chem. Rev. 1999, 193-195,
557.
(2) (a) Herbert, D. K. Inorganic Synthesis; J ohn Wiley & Sons: New
York, 1989; Vol. 26, p 69. (b) Herbert, D. K. Inorganic Synthesis; J ohn
Wiley & Sons: New York, 1989; Vol. 26, p 250.
10.1021/om010205w CCC: $20.00 © 2001 American Chemical Society
Publication on Web 07/21/2001

Indenyl Ruthenium(II) Complexes
Organometallics, Vol. 20, No. 17, 2001 3763
tions especially in Cp and Cp* derivatives.5a-d Despite
this appealing behavior, which leads to the generation
of free coordination sites under mild conditions, there
have been only a few reports on the catalytic activity of
these complexes, most of them containing COD as the
diene ligand.6 Catalytic transformations include (i)
[2+2], [4+2], and [2+2+2] cycloadditions,7 (ii) coupling
reactions of alkynes with allyl alcohols,8 propargyl
alcohols,9 and carboxylic acids5c,10 (iii) Alder-ene type
reactions,11 (iv) cycloisomerization of enynes,12 (v) ally-
lation of thiols,13 (vi) oligomerization of alkynes,5c and
(vii) ketone reductions to alcohols via hydrogen transfer
and hydrogenation reactions.14
It could be anticipated that the analogous semisand-
wich indenyl derivatives of the type [Ru(η5-C9H7)X(η4-
diene)] should show an increased catalytic activity on
the basis of the enhanced reactivity expected for the
indenyl derivatives (indenyl effect).15 However, as far
as we know, no reaction catalyzed by these types of
derivatives has been reported to date.16
We have recently reported that [Ru(η5-C9H7)Cl-
(PPh3)2] shows a dissociative indenyl effect giving rise
to rate constants for the exchange of PPh3 which are 1
Sch em e 1
order of magnitude greater than for the cyclopentadienyl
complex.17 These results have prompted us to study the
reactivity of the known complex [Ru(η5-C9H7)Cl(COD)]18
with the aim of exploring its catalytic activity. Here we
report (a) the synthesis of novel neutral indenyl der-
ivatives [Ru(η5-C9H7)Cl(NBD))], [Ru(η5-C9H7)Cl(CO)-
(PR3)] (PR3 ) PCy3, PiPr3), [Ru(η5-C9H7)Cl{κ2-(P,N)-(o-
Ph2P-C6H4-CHdNtBu}], and [Ru(η5-C9H7){κ1-(P)Ph2-
PCH2C(O)tBu}{κ2-(P,O)-Ph2PCHdC(O)tBu}], which have
been obtained via exchange reactions of COD in [Ru-
(η5-C9H7)Cl(COD)] under mild reaction conditions; (b)
chloride metathesis reactions of [Ru(η5-C9H7)Cl(COD)]
with anionic and neutral ligands leading to the forma-
tion of either neutral [Ru(η5-C9H7)(FBF3)(COD)], [Ru-
(η5-C9H7)(N3)(COD)] or cationic [Ru(η5-C9H7)(COD)(py)]-
[BF4], [Ru(η5-C9H7)(COD)(NCMe)][BF4] complexes; (c)
the first studies on the catalytic activity of the complex
[Ru(η5-C9H7)Cl(COD)] in C-C coupling reactions and
the hydration of alkynes. An improved one-pot synthetic
approach of the complex [Ru(η5-C9H7)Cl(COD)] is also
reported.
(4) (a) Albers, M. O.; Robinson, D. J .; Shaver, A.; Singleton, E.
Organometallics 1986, 5, 2199-2205. (b) Fagan, P. J .; Mahoney, W.
S.; Calabrese, J . C.; Williams, I. D. Organometallics 1990, 9, 1843-
1852. (c) Oshima, N.; Suzuki, H.; Moro-oka, Y. Chem. Lett. 1984, 1161-
1164. (d) Tilley, T. D.; Grubbs, R. H.; Bercaw, J . E. Organometallics
1984, 3, 274-278. (e) Conroy-Lewis, F. M.; Simpson, S. J . J . Orga-
nomet. Chem. 1987, 322, 221-228. (f) Slugvoc, C.; Schmid, R.; Kirchner,
K. Coord. Chem. Rev. 1999, 185-186, 109-126.
(5) For leading references on phosphine exchange reactions see: (a)
Reference 4e. (b) Albers, M. O.; Francesca, S.; Crosby, A.; Liles, D. C.;
Robinson, D. J .; Shaver, A.; Singleton, E. Organometallics 1987, 6,
2014. (c) Gemel, C.; Trimmel, G.; Slugvoc, C.; Kremel, S.; Mereiter,
K.; Schmid, R.; Kirchner, K. Organometallics 1996, 15, 3998-4004.
(d) Shen, J .; Stevens, E. D.; Nolan, S. P. Organometallics 1998, 17,
3000-3005, and references therein. (e) Gemel, C.; Kickelbick, G.;
Schmid, R.; Kirchner, K. J . Chem. Soc., Dalton Trans. 1997, 2113-
2117.
Resu lts a n d Discu ssion
Syn th esis of [Ru (η5-C9H7)Cl(COD)] (1). Although
the starting material [Ru(η5-C9H7)Cl(COD)] (1) has been
previously prepared (40% yield),18 we have used a
modified synthetic approach which allows a one-pot
synthesis of 1 (80% yield) by the reaction of [RuCl2-
(COD)]n with KC9H7 in THF at room temperature
(Scheme 1). 1H NMR data are in accordance with those
published.18 Unreported 13C{1H} spectral and mass data
(FAB) are collected in the Experimental Section. How-
ever, the reaction of [RuCl2(COD)]n with NaC9H7 in THF
proceeds in a different way, leading instead to the
formation of [Ru(η5-C9H7)(η2-η3-C8H11)] (2) (90% yield).
Complex 2 is isolated as an air-sensitive dark orange
oil by evaporation of the reaction mixture to dryness
followed by extraction of the solid residue with CH2Cl2
and subsequent purification by column chromatography
(Scheme 1).
Elemental analysis as well as NMR and mass spec-
trometry data support this formulation in which the
original COD ligand has undergone a deprotonation (see
Experimental Section for details). 1H and 13C{1H} NMR
spectra including DEPT experiments are consistent with
a η2-η3 coordination mode of C8H11. Significantly, the
1H NMR spectrum shows signals in the range δ 1.03-
2.58 ppm assigned to the six unequivalent CH2 protons,
olefinic CH signals at δ 4.28 and 4.80, and allylic
resonances at δ 1.89, 3.22, and 3.88 ppm. Furthermore,
(6) Butenscho¨n, H. Angew. Chem., Int. Ed. Engl. 1994, 33, 636-
638.
(7) (a) Mitsudo, T.; Naruse, H.; Kondo, T.; Ozaki, Y.; Watanabe, Y.
Angew. Chem., Int. Ed. Engl. 1994, 33, 580. (b) Trost, B. M.; Imi, K.;
Indolese, A. F. J . Am. Chem. Soc. 1993, 115, 8831-8832. (c) Yamamoto,
Y.; Ogawa, R.; Itoh, K. Chem. Commun. 2000, 549-550. (d) Yamamoto,
Y.; Kitahara, H.; Ogawa, R.; Itoh, K. J . Org. Chem. 1998, 63, 9610-
9611. (e) Yamamoto, Y.; Kitahara, H.; Hattori, R.; Itoh, K. Organo-
metallics 1998, 17, 1910. (f) J ordan, R. W.; Tam, W. Org. Lett. 2000,
19, 3031.
(8) (a) Trost, B. M.; Martinez, J . A.; Kulawiec, R. J .; Indolese, A. F.
J . Am. Chem. Soc. 1993, 115, 10402. (b) Derien, S.; J an, D.; Dixneuf,
P. H. Tetrahedron 1996, 52, 5511. (c) Derien, S.; Ropartz, L.; Le Paih,
J .; Dixneuf, P. H. J . Org. Chem. 1999, 64, 3524-3531.
(9) Derien, S.; Gomez Vicente, B.; Dixneuf, P. H. Chem. Commun.
1997, 1405.
(10) Le Paih, J .; Derien, S.; Dixneuf, P. H. Chem. Commun. 1999,
1437-1438.
(11) (a) Trost, B. M.; Indolese, A. F. J . Am. Chem. Soc. 1993, 115,
4361-4362. (b) Trost, B. M.; Indolese, A. F.; Mu¨ller, T. J . J .; Treptow,
B. J . J . Am. Chem. Soc. 1995, 117, 615. (c) Trost, B. M.; Mu¨ller, T. J .
J .; Martinez, J . J . Am. Chem. Soc. 1995, 117, 1888. (d) Trost, B. M.;
Mu¨ller, T. J . J . J . Am. Chem. Soc. 1994, 116, 4985.
(12) Le Paih, J .; Cuervo Rodriguez, D.; Derien, S.; Dixneuf, P. H.
Synlett 2000, 95-97.
(13) Kondo, T.; Morisaki, Y.; Uenoyama, S.; Wada, K.; Mitsudo, T.
J . Am. Chem. Soc. 1999, 121, 8657-8658.
(14) Vicente, C.; Shul’pin, G. B.; Moreno, B.; Sabo-Etienne, S.;
Chaudret, B. J . Mol. Catal. A Chem. 1995, 98, L5-L8.
(15) Cadierno, V.; Diez, J .; Gamasa, M. P.; Gimeno, J .; Lastra, E.
Coord. Chem. Rev. 1999, 193-195, 147-205.
(16) The complex [Ru(η5-C9H7)Cl(PPh3)2] has been used as catalyst
in (a) redox isomerization of allyl alcohols: Trost, B. M.; Kulawiec, R.
J . J . Am. Chem. Soc. 1993, 115, 2027. (b) Redox isomerization of
propargyl alcohols to enals: Trost, B. M.; Livingston, R. C. J . Am.
Chem. Soc. 1995, 117, 9586. (c) Transformations of R-diazo carbonyl
compounds in cis-enediones: Baratta, W.; Del Zotto, A.; Rigo, P. Chem.
Commun. 1997, 2163. (d) Tandem [2+2+2]/[4+2] cycloaddition of 1,6-
heptediyne with norbornene: see ref 7e.
(17) Gamasa, M. P.; Gimeno, J .; Gonzalez-Bernardo, C.; Martin-
Vaca, B. M.; Monti, M.; Bassetti, M. Organometallics 1996, 15, 302.
(18) Morandini, F.; Consiglio, G.; Sironi, A.; Moret, M. J . Organomet.
Chem. 1989, 370, 305.

3764 Organometallics, Vol. 20, No. 17, 2001
Alvarez et al.
Sch em e 2
Sch em e 3
the 1H-1H COSY spectrum of complex 2 shows an
interaction between the carbons C(6) and C(8). These
data are consistent with the formation of the unsatur-
ated η2-η3-cyclooctadienyl carbocycle. A similar η2-η3-
coordination of the C8H11 ring has been described in the
complex [Ru(MeCN)((R)-BINAP)(η2-η3-C8H11)][BF4].19a,b
The chemical characterization of complex 2 is con-
firmed by its protonation. As expected, the addition to
a solution of 2 in CH2Cl2 of 1.5 equiv of HCl (33% in
water) leads to the formation of complex 1 (75%) in
quantitative yield (Scheme 1).
readily react with CO to give the stable 18-electron
species. Complexes 3a ,b have been isolated as air stable
orange solids (75% and 80% yield, respectively) and
characterized by analysis and spectroscopic methods. IR
spectra (CH2Cl2) show the expected ν(CO) strong ab-
sorptions at 1935.5 (3a ) and 1936.6 (3b) cm-1. Proton,
carbon, and phosphorus resonances in the NMR spectra
are in accordance with this formulation (see the Ex-
perimental Section for details). In particular 31P{1H}
NMR spectra exhibit one singlet resonance at δ 56.75
(3a ) and 65.54 ppm (3b), the latter one appearing at a
similar value shown by the analogous complex [Ru-
(C5H5)Cl(CO)(PiPr3)]21 (δ 66.4 ppm).
Su bstitu tion Rea ction s in [Ru (η5-C9H7)Cl(COD)]
(1). (a ) Exch a n ge of COD. The lability of COD in
complex 1 has been assessed in a series of substitution
reactions including monodentate and bidentate ligands.
Thus, the exchange of COD in complex 1 by PPh3,
PMePh2, PMe2Ph, and dppm proceeds instantaneously
in refluxing THF to give quantitatively the known
phosphine derivatives [Ru(η5-C9H7)ClL2].17 It is note-
worthy that the analogous exchange reaction of the two
PPh3 in the complex [Ru(η5-C9H7)Cl(PPh3)2] by PMePh2,
PMe2Ph, or dppm proceeds under refluxing toluene in
preparative conditions. Significantly, the substitution
of COD by the bulky phosphines PCy3 and PiPr3 in
complex 1 takes place at room temperature, leading to
an instantaneous change of color from orange to purple.
The reaction is monitored by 31P{1H} NMR, showing one
single resonance at δ 45.7 (PCy3) and 53.0 ppm (PiPr3).
However, all attempts to isolate the phosphine complex
have failed. The partial evaporation of the resulting
THF solution followed by the addition of hydrocarbon
solvents or the slow crystallization led to decomposition
products. In contrast, the carbonyl complexes [Ru(η5-
Reaction of complex 1 with 1 equiv of the iminophos-
phine o-Ph2PC6H4C(H)dNtBu22 in THF yields the
chelate complex [Ru(η5-C9H7)(Cl){κ2-(P,N)-o-Ph2PC6H4C-
(H)dNtBu}] (4) (80% yield). Elemental analysis along
1
with IR, H, 13C{1H}, and 31P{1H} NMR spectroscopic
data are in accordance with the presence of the imino-
phosphine group as a chelating ligand (see Experimen-
tal Section) (Scheme 3). It is noteworthy that complex
4 remains unchanged in the presence of an excess of
the iminophosphine. The reluctance to incorporate one
further ligand seems to indicate the strong chelate effect
of the ligand and/or the steric hindrance arising from
the two relatively close bulky ligands.
This behavior contrasts with that found in the reac-
tion of complex 1 with the ketophosphine Ph2PCH2C-
(O)tBu.23a Monitoring the reaction by 31P{1H} NMR, a
mixture of substituted species (ca. 60/40%) is formed,
namely, [Ru(η5-C9H7)Cl{κ1-(P)-Ph2PCH2(CO)tBu}2] (δ
51.0 and 49.0; 2J PP ) 27.5) and [Ru(η5-C9H7){κ1-(P)-Ph2-
PCH2C(O)tBu}{κ2-(P,O)-Ph2PCH2C(O)tBu}][Cl] (broad
signals at δ 29.6 and 73.4). After working up the
reaction mixture followed by a column chromatography
(Al2O3), the neutral complex [Ru(η5-C9H7){κ1-(P)-Ph2-
PCH2C(O)tBu}{κ2-(P,O)-Ph2PCHdC(O)tBu}] (5) is iso-
lated (80% yield) as an air stable solid (Scheme 3).
i
C9H7)Cl(CO)(PR3)] (R ) Cy(3a ); Pr(3b)) are formed
after bubbling CO (1 atm) through the original THF
solution (Scheme 2). This seems to indicate that inter-
mediate 16-electron complexes [Ru(η5-C9H7)Cl(PR3)] are
generated which, although they could not be isolated,20
(19) (a) Wiles, J . A.; Lee, C. E.; McDonald, R.; Bergens, S. H.
Organometallics 1996, 15, 3782. (b) The analogous [Rh(η2-η3-C8H11)-
(C24H44)][BF4] has been recently described: Burrows, A. D.; Green, M.;
J effery, J . C.; Lynam, J . M.; Mahon, M. F. Angew. Chem., Int. Ed. 1999,
38, 3043.
(21) (a) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.;
On˜ate, E.; Oro, L. A. Organometallics 1996, 15, 3423. (b) Gimeno, J .
Unpublished results.
(22) Ghilardi, C. A.; Midollini, S.; Moneti, S.; Orlandini, A.; Scapacci,
G. J . Chem. Soc., Dalton Trans. 1992, 3371.
(23) (a) Demerseman, B.; Guilbert, B.; Renouard, C.; Gonzalez, M.;
Dixneuf, P. H. Organometallic 1993, 12, 3906. (b) Crochet, P.; Dem-
erseman, B.; Vallejo, M. I.; Gamasa, M. P.; Gimeno, J .; Borge, J .;
Garc´ıa-Granda, S. Organometallics 1997, 16, 5406.
(20) The analogous complex [Ru(η5-C5Me5)Cl(PiPr3)] has been iso-
lated as a stable solid. (a) J ohnson, T. J .; Folting, K.; Streib, W. E.;
Martin, J . D.; Huffman, J . C.; J ackson, S. A.; Eisenstein, O.; Caulton,
K. G. Inorg. Chem. 1995, 34, 488. (b) Campion, B. K.; Heyn, R. H.;
Tilley, T. D. J . Chem. Soc., Chem. Commun. 1992, 1201.

Indenyl Ruthenium(II) Complexes
Organometallics, Vol. 20, No. 17, 2001 3765
Sch em e 4
F igu r e 1. Structure of [Ru(η5-C9H7)Cl(NBD)]. Selected
bond distances (Å) are as follows: Ru-C*, 1.915 (4); Ru-
C(15), 2.189(4); Ru-C(16), 2.172(4); Ru-C(11), 2.156(4);
Ru-C(10), 2.164(4); Ru-Cl, 2.442(1). Selected bond angles
(deg) are as follows: C*-Ru-C(10), 116.26(17); C*-Ru-
C(15), 117.54(17); C*-Ru-C(11), 144.25(17); C*-Ru-
C(16), 145.59(17); Cl-Ru-C*, 113.30(13). 4 ) 0.141(4); FA
) 5.29(33); HA ) 6.99(35). a4 ) d(Ru-C(4),C(9)) - d(Ru-
C(1),C(3)). bFA (fold angle) ) angle between normals to
least-squares planes defined by C(1), C(2), C(3) and C(4),
C(5), C(6), C(7), C(8), C(9). cHA (hinge angle) ) angle
between normals to least-squares planes defined by C(1),
C(2), C(3) and C(1), C(3), C(4), C(9). C* ) centroid of C(1),
C(2), C(3), C(4), C(9).
with a hinge angle (HA) of 7.0(3)° and a fold angle (FA)
of 5.3(3)°. The characteristic slippage of the indenyl ring
is also observed with a slip-fold (∆) value of 0.141(4) Å.
All of these values can be compared with those previ-
ously reported by us.25 Norbornadiene is η4-bonded to
the ruthenium atom with an average Ru-C distance of
2.170(4) Å, which is typical for a π-olefin ruthenium
bond and is in the range shown by the analogous
complexes [Ru(η5-C5Me5)(NBD)(H2O)][BF4] (2.201(8) Å)26a
and [RuCl2(NBD)(PPh3)2] (2.205 Å).26b
(b) Syn th esis of [Ru (η5-C9H7)X(COD)] (X ) F BF 3,
N3) Com p lexes. Chloride metathesis reactions have
been carried out. Thus, [Ru(η5-C9H7)(FBF3)(COD)] (7)
has been prepared by reacting 1 with AgBF4 (1 equiv)
in CH2Cl2 (Scheme 4). This complex is isolated (70%
yield) as an air and water sensitive solid by evaporating
to dryness the filtered reaction solution and has been
characterized by elemental analysis and spectroscopic
techniques (see Experimental Section). Mass spectrom-
etry (FAB) shows the cation [M+] (411) and fragmenta-
tions [M+ - F] (392), [M+ - F2] (373), indicating the
Complex 5 was characterized by elemental analyses and
spectroscopic techniques. Thus, its IR spectrum shows
two absorptions at 1701 (νCdO) and 1495 (νC)C-O) cm-1
as expected for the presence of the ketone and the
1
enolate functionalities. H, 31P{1H}, and 13C{1H} NMR
are also in accordance with this formulation. In par-
ticular, its 31P{1H} NMR spectrum shows two doublet
resonances at δ 69.9 and 41.4 ppm (d, J PP ) 36.9 Hz)
assigned to the κ2 (P,O) enolate phosphorus atom and
the (κ-P) ketophosphine, respectively.23
-
coordination of the BF4 fragment to the metal center.
Moreover, conductivity measurements in CH2Cl2 show
that complex 7 behaves as a nonelectrolite. The 19F{1H}
NMR spectrum at room temperature shows signals that
are consistent with the presence of an equilibrium
The chelating enolate κ2-(P,O)-Ph2PCHdC(O)tBu com-
plex 5 results from the deprotonation of one of the acid
CH2 protons in either κ2-(P,O) and/or κ1-(P) ketophos-
phine ligands, which takes place under the chromatog-
raphy conditions. This type of transformation has been
described previously as one that proceeds readily in the
presence of a base.23
Complex 1 also undergoes a rapid exchange of COD
by norbornadiene (NBD) in refluxing THF to give the
analogous complex [Ru(η5-C9H7)Cl(NBD)] (6).24 Elemen-
tal analysis and 1H and 13C{1H} NMR spectroscopic
data are in agreement with the proposed formulation
(see Experimental Section). In addition, the structure
of complex 6 has been confirmed by an X-ray diffraction
study. An ORTEP-type view of the molecule is depicted
in Figure 1, and selected bond distances and angles are
listed in the caption.
-
between the coordinated and free BF4 anion in ac-
cordance with other reported data.27
Similarly, the treatment of complex 1 in THF/MeOH
(10:1) with NaN3 affords [Ru(η5-C9H7)(N3)(COD)] (85%
yield) (8) as an air stable solid. Complex 8 has been
1
characterized by elemental analyses, H and 13C{1H}
NMR spectroscopy, and IR spectroscopy. In particular,
the IR spectrum (Nujol) of 8 shows the expected νN3
absorption at 2029 cm-1. The rest of the data reveals
the presence of the ligands but providing that there are
no relevant features will not be further commented on
(see Experimental Section for details).
(25) The slight distortion toward an η3 binding mode in the solid
state of complex 6 appears to be maintained in solution, according to
the value of ∆δ(C-3a, 7a) ) -19.8(6) ppm obtained from the 13C{1H}
NMR spectrum (see Experimental Section). (a) Cadierno, V.; Gamasa,
M. P.; Gimeno, J .; Borge, J .; Garc´ıa-Granda, S. Organometallics 1997,
16, 3178. (b) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Gonza´lez-Cueva,
M.; Lastra, E.; Borge, J .; Garc´ıa-Granda, S.; Pe´rez-Carren˜o, E. Orga-
nometallics 1996, 15, 2137.
The structure shows an approximately octahedral
geometry at ruthenium. Although the indenyl group is
bound to ruthenium in a typical η5 fashion, there is a
slight distortion of the five-carbon ring from planarity
(26) (a) Suzuki, H.; Kakigano, T.; Fukui, H.; Tanaka, M.; Moro-oka,
Y. J . Organomet. Chem. 1994, 473, 295. (b) Bergbreiter, D. E.; Bursten,
B. E.; Cotton, F. A. J . Organomet. Chem. 1981, 205, 407.
(27) Beck, W.; Su¨nkel, K. Chem. Rev. 1998, 88, 1405.
(24) When an excess of NBD is used, a ring-opening metathesis
polymerization of NBD takes place even at room temperature, indicat-
ing complex 1 is a ROMP catalyst. Unpublished results.

3766 Organometallics, Vol. 20, No. 17, 2001
Alvarez et al.
Sch em e 5
Ta ble 1. P r od u ct An a lysis of th e [2+2]
Cycloa d d ition Rea ction of Nor bor n en e w ith
Alk yn es, Ca ta lyzed by [Ru (η5-C9H7)Cl(COD)]
entry
alkyne
% conversion % selectivity % yielda
1
2
3
4
5
6
MeO2CCtCCO2Me
HOH2CCtCCH2OH
MeCtCPh
PhCtCPh
HCtC(CH2)5Me
HCtCCH2OH
100
90
95
95
80
90
99
77
97
97
40
16
99b (98)c
63b
93b (91)c
92b
32b
15b
a
b
Yield based on the alkyne. GC data. c Yield of the isolated
product obtained after complete transformation of the alkyne
under preparative reaction conditions (see Experimental Section).
F igu r e 2. Structure of the cation of [Ru(η5-C9H7)(py)-
(COD)]. Selected bond distances (Å) are as follows: Ru-
C*, 1.913(11); Ru-C(15), 2.185(11); Ru-C(22), 2.206(11);
Ru-C(18), 2.238(10); Ru-C(19), 2.240(11); Ru-N, 2.197-
(8); C(22)-C(15), 1.396(16); C(15)-C(16), 1.496(15); C(16)-
C(17), 1.544(17); C(17)-C(18), 1.490(16); C(18)-C(19),
1.387(15); C(19)-C(20), 1.530(17); C(20)-C(21), 1.483(18);
C(21)-C(22), 1.554(17). Selected bond angles (deg) are as
follows: C*-Ru-C(22), 113.28(45); C*-Ru-C(19), 114.37-
(46); C*-Ru-C(18), 143.12(43); C*-Ru-C(15), 135.13(44);
N-Ru-C*, 111.49(43); N-Ru-C(19), 115.1(4); N-Ru-
C(18), 80.8(4); N-Ru-C(15), 83.6(4); N-Ru-C(22), 120.6-
The COD ligand adopts a twist-boat or tub conforma-
tion showing an average Ru-C distance of 2.217(11) Å,
both features being similar to those found in other
ruthenium complexes.5c,26a The Ru-N distance is 2.197-
(8) Å.29 It is interesting to note that C9H7 appears to be
related more closely to C5Me5 and tris(pyrazolyl)borate
than to C5H5 in the series of the related complexes [Ru-
(η5-C9H7)X(COD)], [Ru(η5-C5Me5)X(COD)], and [Ru(T-
p)X(COD)] (Tp ) HB(pz)3), which afford similar cationic
acetonitrile complexes in contrast to [Ru(η5-C5H5)Cl-
(COD)].5c,26a,30
a
(4). 4 ) 0.156(11); FA ) 8.2(8); HA ) 7.1(9). 4 ) d(Ru-
b
C(13),C(8)) - d(Ru-C(14),C(7)). FA (fold angle) ) angle
Ca ta lytic Activity of [Ru (η5-C9H7)Cl(COD)]. (a )
[2+2] Cycloa d d ition s of Nor bor n en e w ith Alk yn es.
Internal alkynes are converted selectively into exo-
tricyclic [4.2.1.0] coupling products (Scheme 5 and Table
1) essentially in quantitative yields under both analyti-
cal and preparative conditions (entries 1 and 3). On the
other hand, cycloadditions of 1-heptyne and propargyl
alcohol (entries 5 and 6) proceed with lower yield and
selectivity. In fact, among other uncharacterized byprod-
ucts, the major components of the reaction mixture are
the products of trimerization of the alkyne, which
account for reduced selectivity of cycloaddition. There-
fore, the presence of the terminal alkyne functionality
drives the reaction toward trimerization, while the [2+2]
cycloaddition process of internal alkynes appears in-
sensitive to the nature of the substituents. As previously
reported,7a,f in the case of [Ru(η5-C5Me5)Cl(COD)] as
precatalyst, the reaction of alkynes with norbornadiene
does not proceed properly, most likely due to a chelation
effect of this substrate hindering the catalysis.31
(b) [4+2] Cycloa d d ition s of 1,5-Cycloocta d ien e
w ith Alk yn es. The catalytic cycloadditions of 1,5-
cycloctadiene with alkynes in the presence of [Ru(η5-
C9H7)Cl(COD)] (5 mol %) were also examined. The
reactions led chemioselectively to the cycloaddition
products exo-tricyclo [4.2.2.0]dec-7-enes (Scheme 6;
Table 2). The presence of the sp2-carbon substituents,
between normals to least-squares planes defined by C(14),
c
C(6), C(7) and C(8), C(9), C(10), C(11), C(12), C(13). HA
(hinge angle) ) angle between normals to least-squares
planes defined by C(14), C(6), C(7) and C(14), C(7), C(8),
C(13). C* ) centroid of C(14), C(6), C(7), C(8), C(13).
(c) Syn th esis of Ca tion ic Com p lexes [Ru (η5-
C9H7)(COD)L][BF 4] (L ) p y, NCMe). Treatment of
complex 1 in CH2Cl2 with AgBF4 followed by the
addition of an excess of L (L ) py, MeCN) to the filtered
solution containing complex 7 yields [Ru(η5-C9H7)(COD)-
(py)][BF4] (9) and [Ru(η5-C9H7)(COD)(MeCN)][BF4] (10)
in good yield (Scheme 4). The cationic complexes 9 and
10 are isolated as air stable tetrafluoroborate salts. The
1
IR and H and 13C{1H} NMR spectroscopic properties
are in agreement with the presence of the ligands and
are not further discussed here (details are given in the
Experimental Section). The analytical and mass spec-
trometry data of 9 and 10 support the proposed formu-
lation. In addition the structure of 9 has been confirmed
by X-ray crystallography, and an ORTEP-type view of
the structure of the cationic complex is shown in Figure
2. Selected bond distances and angles are given in the
caption. [Ru(η5-C9H7)(COD)(py)]+ cations and [BF4]-
anions, separated by normal contacts, are present in the
crystals. The cation shows a pseudoctahedral geometry
around the ruthenium atom which is bonded to the
indenyl group acting as an η5 ligand, the two double
bonds of COD, and the nitrogen atom of pyridine. As
for the related NBD complex 7 the indenyl group shows
a slight distortion of the five-carbon ring from planarity
(see caption of Figure 2 for HA, FA, and ∆ values).28
(29) This value compares well with other related pyridine ruthe-
nium(II) complexes. (a) Stavrev, K.; Zerner, M. C. J . Am. Chem. Soc.
1995, 117, 8684 ([Ru((NH3)5(py)]2+, 2.156 Å). (b) Faller, J . W.; Grim-
mond, B. J .; Curtis, M. Organometallics 2000, 19, 5174 ([Ru(p-
CH3C6H4CH(CH3)2)(κ2-(P,P)-Ph2PCH-(Me)Ph2P(O)py][SbF6]2, 2.218(3)
Å).
(30) Oshima, N.; Suzuki, H.; Moro-oka, Y. Chem. Lett. 1984, 1164.
(31) [2+2] Cycloaddition of norbornadiene with diphenylacetylene
using 5 mol % of [Ru(η5-C9H7)Cl(COD)] as catalyst affords a 60% yield
of the cycloadduct in 12 h.
(28) The slight distortion toward an η3 binding mode in the solid
state of complex 9 appears to be maintained in solution, according to
the value of ∆δ(C-3a, 7a) ) -22.3(6) ppm.

Indenyl Ruthenium(II) Complexes
Organometallics, Vol. 20, No. 17, 2001 3767
the presence of phosphine additives.35 The addition of
water to the triple bond has also been postulated in the
reactions of terminal alkynes, water, and alkyl vinyl
ketones to give 1,5-diketones, in the presence of a
catalytic system involving the complex [Ru(η5-C5H5)Cl-
(COD)].36 It is known that the formation of carbon-
heteroatom bonds from alkynes is catalyzed by electro-
philic ruthenium centers,32 whereas carbon-carbon
bonds are formed with electron-rich metal centers, or
in the presence of phosphine ligands which favor η1-
vinylidene species with respect to metal-η2-alkyne com-
plexes.37,38 Since the lability of the COD ligand promotes
the formation of an electrophilic ruthenium species, it
is likely that nuclephilic attack of water in this hydra-
tion process occurs at a ruthenium-η2-alkyne intermedi-
ate, formed by substitution/thermal release of COD from
the complex [Ru(η5-C9H7)Cl(COD)].
Sch em e 6
Ta ble 2. P r od u ct An a lysis of th e [4+2]
Cycloa d d ition Rea ction of 1,5-Cycloocta d ien e w ith
Alk yn es, Ca ta lyzed by [Ru (η5-C9H7)Cl(COD)]
entry
alkyne
% conversion % selectivity % yielda
1
2
3
4
5
6
7
MeO2CCtCCO2Me
HOH2CCtCCH2OH
MeCtCPh
5
75
85
70
95
90
50
100
100
100
30
100
80
5b
75b
85b (95)c
21b
PhCtCPh
HCtC(CH2)5Me
HCtCPh
95b
72b
HCtCCH2OH
60
30b
Con clu sion s
a
b
Yield based on the alkyne. GC data. c Isolated product
obtained after complete transformation of the alkyne (20 h) under
preparative reaction conditions (see Experimental Section).
In this work the reactivity and catalytic applications
of the complex [Ru(η5-C9H7)Cl(COD)] (1) (COD ) 1,5-
cyclooctadiene) have been studied. It is shown that
the labile COD ligand can be substituted under mild
conditions. On the basis of this lability novel mixed
carbonyl-phosphine complexes [Ru(η5-C9H7)Cl(CO)-
(PR3)] (R ) Cy (3a ), iPr (3b)), bis-substituted complexes
containing hemilabile ligands [Ru(η5-C9H7)(Cl){κ2-(P,N)-
o-Ph2PC6H4C(H)dNtBu}] (4) and [Ru(η4-C9H7){κ1-(P)-
Ph2PCH2C(O)tBu}{κ2-(P,O)-Ph2PCHdC(O)tBu}] (5), and
the analogous diene complex [Ru(η5-C9H7)Cl(NBD)] (6)
have been prepared via exchange processes in THF as
solvent either at room or refluxing temperature. This
lability contrasts with that found for the analogous
complex [Ru{HB(pz)3}(COD)Cl], in which the COD
ligand can be substituted only by treating the reaction
mixture above 100 °C.5c The lability of COD in complex
1 appears to be between that of [Ru(η5-C5Me5)Cl(COD)]
and [Ru(HB(pz)3)(COD)Cl].4a,e,f
The lability of COD in complex 1 has proved to be
appropriate for the generation of 16 deficient electron
species [Ru(η5-C9H7)Cl(PR3)]. Nevertheless these species
appear to be unstable in the solid state in contrast to
the analogous complex [Ru(η5-C5Me5)Cl(PiPr3)], which
has been isolated as a stable solid.20 It is apparent that
the C5Me5 ring proves to be a more electron releasing
group than C9H7, therefore allowing the electronic
deficiency in the metal atom to be compensated. Com-
plex 1 is also a good precursor of novel COD derivatives
which are obtained by the reaction with anionic and
neutral ligands in the presence of a chloride abstractor
to give complexes [Ru(η5-C9H7)(FBF3)(COD)] (7), [Ru-
(η5-C9H7)(N3)(COD)] (8), [Ru(η5-C9H7)(COD)(py)][BF4]
(9), and [Ru(η5-C9H7)(COD)(NCMe)][BF4] (10).
carbomethoxy or phenyl, in the alkyne structure lowers
the yield of the expected products (entries 1 and 4), as
it was observed when using [Ru(η5-C5H5)Cl(COD)] as
catalyst.7b The data indicate stronger dependence of the
[4+4] cycloaddition process on the steric and electronic
properties of the alkyne than the corresponding [4+2]
reactions. In both [2+2] and [4+2] cycloaddition reac-
tions, the propargyl alcohol is a poor substrate.
(c) Wa ter Ad d ition to Alk yn es. In the presence of
complex 1 (5 mol %) aliphatic terminal alkynes and
phenylacetylene (Table 3, entries 1-5) undergo addition
of water, affording ketones (Scheme 7) in high yield and
selectivity (Figure 3). No significant transformations
were observed after 15 h of reaction. The presence of a
hydroxy group in the R position of the alkyne (entry 6)
does not seem to affect the efficiency of the reaction.
When the temperature is increased by 10 °C, a small
decrease of selectivity (97 to 94%) is observed in the
reaction of 1-octyne. The formation of ketones via metal-
catalyzed hydration of alkynes is a well-known pro-
cess,32 which occurs selectively due to the preferred
addition of water in a Markovnikov fashion to the
activated triple bond.32b While ruthenium(II) catalyst
precursors have provided selective access to enol esters,
dienes, ketoesters, and furans through electrophilic
activation of terminal alkynes,33 the hydration reaction
has been reported only recently in the case of the
complex [Ru(η6-C6Me6)Cl2{Ph2P(C2H3)}] to form ketones
with moderate yields and selectivities,34 and in the case
of [RuCl2(η6-C6H6)(PR3)] (PR3 ) PPh2(C6F5), P{3-(C6H4-
SO3Na)3}) to form ketones, or preferably aldehydes, in
Complex 1 is an efficient catalyst in [2+2] and [4+2]
cycloadditions of norbonene and 1,5-cyclooctadiene,
respectively, and alkynes, with yields and selectivity in
some cases higher than in the reactions catalyzed by
(32) (a) Kotlyarevskii, L. L.; Vostichno-Sibir, T. Filiala, Akad. Nauk.
SSSR, Ser. Khim. 1956, 58 (Chem. Abstr. 1957, 51, 12815). (b) March,
J . J . Advanced Organic Chemistry; Wiley: New York, 1985; p 863. (c)
Bassetti, M.; Floris, B. J . Chem. Soc., Perkin Trans. 2 1988, 227. (d)
J anout, V.; Regen, S.-L. J . Org. Chem. 1982, 47, 3331. (e) Halpern, J .;
J ames, B. R.; Kemp, A. L. W. J . Am. Chem. Soc. 1961, 83, 4097. (f)
Halpern, J .; J ames, B. R.; Kemp, A. L. W. J . Am. Chem. Soc. 1966,
20, 5142. (g) Hiscox, W.; J ennings, P. J . Am. Chem. Soc. 1990, 9, 1997.
(h) Hartman, J . W.; Hiscox, W.; J ennings, P. W. J . Org. Chem. 1993,
58, 7613. (i) Taqui Khan, M. M.; Halligudi, S. B.; Shukla, S. J . Mol.
Catal. 1990, 58, 299-305. (j) Sasson, Y.; Zoran, A.; Blum, J . J . Mol.
Catal. 1981, 11, 293. (k) Blum, J .; Huminer, H. J . Mol. Catal. 1992,
75, 153. (l) Meier, I. K.; Marsella, J . A. J . Mol. Catal. 1993, 78, 31.
(33) Bruneau, C.; Dixneuf, P. H. Acc. Chem. Res. 1999, 32, 311.
(34) Hansen, H. D.; Nelson, J . H. Organometallics 2000, 23, 4740.
(35) Tokunaga, M.; Wakatsuki, Y. Angew. Chem., Int. Ed. 1998, 37,
2867-2869.
(36) Trost, B. M.; Portnoy, M.; Kurihara, H. J . Am. Chem. Soc. 1997,
119, 836.
(37) (a) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Pe´rez-Carren˜o,
E.; Garc´ıa-Granda, S. Organometallics 1999, 18, 2821. (b) Bullock, R.
M. J . J . Chem. Soc., Chem. Commun. 1986, 165.
(38) Gamasa, M. P.; Gimeno, J .; Gonza´lez-Bernardo, C.; Borge, J .;
Garc´ıa-Granda, S. Organometallics 1997, 16, 2483.

3768 Organometallics, Vol. 20, No. 17, 2001
Alvarez et al.
Ta ble 3. P r od u ct An a lysis of th e Hyd r a tion Rea ction of Alk yn es to Keton es, Ca ta lyzed by
[Ru (η5-C9H7)Cl(COD)]
entry
alkyne
T (°C)
t (h)
% ketonea
% aldehydea
% selectivity
1
2
3
4
5
6
CH3(CH2)5CtCH
CH3(CH2)5CtCH
CH3(CH2)5CtCH
PhCtCH
CH3(CH2)4CtCH
(C6H10)(OH)CtCH
100
100
90
100
100
90
12
24
30
48
48
24
58
75
77
98
89
93
4
4
2
1
4
2
92
94
97
98
95
97
a
GC Data.
Gas chromatography analyses were recorded on a HP 6890
GC (HP fused silica capillary column HP-INNOWAX cross-
linked poly(ethylene glycol) 30 m × 0.25 mm). GC-MS
analyses were obtained on a HP5890 GC (OV1 capillary
column 12 m × 0.2 mm) coupled with a HP5970 MSD.
Sch em e 7
Syn th esis of [Ru (η5-C9H7)Cl(COD)] (1): Meth od A. A
freshly prepared solution of KInd (1.5 mol) was added at room
temperature to a solution of [RuCl2(COD)]n (0.32 g, 1 mol) in
THF (30 mL). The mixture was then stirred for 1 h and, after
that, evaporated to dryness. The resulting solid residue was
extracted with CH2Cl2 (20 mL) and filtered. The solution was
evaporated to dryness and washed with hexane (2 × 20 mL).
The volatiles were removed under vacuum to give 1 as an
orange solid (0.338 g, 80% yield). 1H NMR (δ, CDCl3): 1.79
(m, 2H, CH2), 1.96 (m, 2H, CH2), 2.27 (m, 2H, CH2), 2.48 (m,
2H, CH2), 3.75 (m, 2H, CH), 4.16 (m, 2H,CH), 5.25 (d, 2H, J HH
) 2.7 Hz, H-1,3), 5.47 (t, 1H, J HH ) 2.7 Hz, H-2), 6.90-7.45
(m, 4H, H-4,7 and H-5,6). 13C{1H} NMR (δ, CDCl3): 28.1 (s,
CH2), 32.3 (s, CH2), 77.6 (s, CH), 79.1 (s, CH), 94.9 (s, C-1,3),
83.6 (s, C-2), 111.1 (s, C-3a,7a), 124.0 and 129.0(s, C-4,7 and
C-5,6). Anal. Calcd for RuC17H19Cl: (359.8): C, 56.7; H, 5.3.
Found: C, 56.3; H 5.0. MS(FAB+): m/e 360 (M+), 323 (M+
HCl).
-
Meth od B. HCl (33% aqueous, 0.5 mL) was added to a
solution of [Ru(η5-C9H7)(C8H11)] (2) (0.32 g, 1 mol) in CH2Cl2
(10 mL). The mixture was stirred at room temperature for 10
min. Then, water (10 mL) was added and the organic phase
was separated and dried with magnesium sulfate. Solvents
were then removed, affording an orange solid (1) with 75%
yield, which was washed with hexane (2 × 20 mL) and
vacuum-dried.
F igu r e 3. Hydration of phenylacetylene. GC data.
the analogous cyclopentadienyl and pentamethylcyclo-
pentadienyl complexes.7a,b The formation of ketones via
catalytic hydration of alkynes has been a synthetic
approach of interest since the use of water as reagent
and solvent is an important factor on the basis of
economic safety and environment protection.39 The use
of complex [Ru(η5-C9Me7)Cl(COD)] as catalyst not only
offers an efficient and selective method to hydrate
terminal alkynes but also is the first Ru(II) catalyst
active in the hydration of R-hydroxy alkynes to form
ketones.
Syn th esis of [Ru (η5-C9H7)(C8H11)] (2). To a solution of
[RuCl2(COD)]n (0.32 g, 1 mol) in THF (30 mL) was added a
freshly prepared solution of NaInd (0.19 g, 1.5 mol) at room
temperature. The mixture was stirred for 4 h and then filtered.
The solution was evaporated to dryness, and the resulting solid
residue was extracted with CH2Cl2 (2 × 20 mL) and filtered.
The solution was evaporated to dryness, resulting in a dark
orange oil, which was purified using a silica column, recovering
the orange fraction eluted with hexane. Evaporation affords
2 as a dark orange oil. Yield: 0.75 g, (90%). 1H NMR (δ,
CDCl3): 1.03 (m, 1H, CH2), 1.67 (m, 1H, CH2), 1.89 (m, 1H,
CH2), 2.14 (m, 3H, CH-CH2), 2.58 (m, 1H, CH2), 2.91(m, 1H,
CH), 3.22 (vt, 1H, J HH ) 6.8 Hz, CH), 3.88 (m, 1H, CH), 4.28
(m, 1H, CH), 4.80 (s, 1H, H-1), 5.28 (m, 1H, C-3), 5.33 (s, 1H,
C-2), 6.90-7.31 (m, 4H, H-4,7 and H-5,6). 13C{1H} NMR (δ,
CDCl3): 10.4 (s, CH), 22.1 (s, CH2), 24.1 (s, CH), 30.1 (s, CH2),
36.5 (s, CH2), 62.9 (s, CH), 68.6 (s, CH), 70.1 (s, C-1), 72.4 (s,
C-3), 73.6 (s, CH), 84.8 (s, C-2), 102.0, 102.9 (both s, C-3a,7a),
122.7, 122.9, 123.5, and 124.0 (all s, C-4,5,6,7). MS(FAB+): m/e
323 (M+).
Syn th esis of [Ru (η5-C9H7)Cl(CO)(P R3)] (R ) Cy (3a ),
iP r (3b)). To a solution of 1 (0.35 g, 1 mol) in THF (20 mL)
was added the corresponding phosphine (1.2 mol) at room
temperature. The solution was then monitored by 31P NMR
until a band at 53.7 ppm for 3a and 45.7 ppm for 3b appeared.
Solvents were then reduced and CO was bubbled through the
solution at room temperature for 5 min, yielding orange solids.
Solvents were removed, and the solid was washed with hexane
Exp er im en ta l Section
Gen er a l Com m en ts. All manipulations involving organ-
oruthenium complexes were performed under an inert atmo-
sphere of nitrogen, using standard Schlenk techniques. All
solvents were dried by standard methods and distilled under
nitrogen before use. [RuCl2(COD)]n,2 o-Ph2PC6H4C(H)dNtBu,22
and Ph2PCH2C(O)tBu23a were prepared according to the lit-
erature procedure. All other chemicals were obtained from
Aldrich Chemical Co. and used without further purification.
Infrared spectra were recorded on a Perkin-Elmer 1720-XFT
spectrometer. The C, H, and N analyses were carried out with
a Perkin-Elmer 240-B microanalyzer. High-resolution mass
spectra were recorded using a MAT-95 spectrometer. NMR
spectra were recorded on a Bruker AC300 instrument, a
AC200 instrument, or a 300 DPX instrument at 300 MHz (1H),
121.5 MHz (31P), 188.3 MHz (19F), or 75.4 MHz (13C) using
SiMe4 or 85% H3PO4 as standards. DEPT experiments have
been carried out for all the compounds.
(39) Tokunaga, M.; Larrow, J . F.; Kakivchi, F.; J acovsen, E. N.
Science 1997, 277, 936.

Indenyl Ruthenium(II) Complexes
Organometallics, Vol. 20, No. 17, 2001 3769
(2 × 20 mL) and vacuum-dried. 3a : yield: 0.41 g (75%). IR
(Nujol): ν 1935.5 cm-1 (CO). 31P{1H} (δ, CDCl3): 56.75 (s). 1H
NMR (δ, CDCl3): 1.07-2.10 (m, 33H, Cy), 5.06, 5.42, 5.54 (s,
1H, H-1,2,3), 7.29-7.44 (m, 4H, H-4,7 and H-5,6). 13C{1H}
NMR (δ, CDCl3): 26.8 (m, Cy), 27.4 (m, Cy), 29.4 (m, Cy), 30.5
(m, Cy), 35.8 (m, Cy), 64.1 (s, C1), 71.6 (s, C2), 90.4 (s, C3),
112.4, 116.0 (s, C3a,7a), 122.4, 124.6, 127.3 and 128.1 (all s,
C-4,5,6,7), 205.3 (d, J PC ) 20.7 Hz, CO). Anal. Calcd for
RuC28H40ClOP (560.12): C, 60.0; H, 7.2. Found: C, 59.7; H,
6.9. 3b: Yield: 0.34 g, 80%. IR (Nujol): ν 1936.6 cm-1 (CO).
solid, which was washed with hexane (2 × 20 mL) and dried
1
under vacuum. 6: Yield: 0.15 g, (40%). H NMR (δ, CDCl3):
1.22 (s, 1H, H-bridged-head), 3.60 (m, 1H, CH), 3.71 (m, 1H,
CH), 3.78 (vt, 2H, J HH ) 3.9 Hz, dCH), 3.88 (vt, 2H, J HH
)
3.9 Hz, dCH), 5.44 (s, 1H, H-2), 5.53 (s, 2H, H-1,3), 7.22-
7.38 (m, 4H, H-4,7 and H-5,6). 13C{1H} NMR (δ, CDCl3): 45.3
(s, dCH), 48.6 (s, CH), 48.8 (s, CH), 60.2 (s, C-bridged-head),
65.1 (s, CH), 76.1 (s, C-1,3), 93.5 (s, C-2), 110.4 (s, C-3a,7a),
123.4 and 128.2 (both s, C-4,7 and C-5,6). Anal. Calcd for
RuC16H17Cl (345.8): C, 55.5; H, 5.0. Found: C, 55.3; H, 5.2.
Syn th esis of [Ru (η5-C9H7)(F BF 3)(COD)] (7): Meth od A.
HBF4‚Et2O (1.5 mol) was added dropwise at room temperature
to a solution of 2 (0.323 g, 1 mol) in THF (20 mL). The solution
was stirred for 10 min and then evaporated to dryness. The
solid residue was washed with hexane (2 × 20 mL), affording
a yellow-brown solid purified on a silica gel column, recovering
the fraction eluted with Et2O.
1
31P{1H} (δ, CDCl3): 65.54 (s). H NMR (δ, CDCl3): 1.02-1.45
i
i
(m, 18H, Pr), 2.11-2.31 (m, 3H, Pr), 5.11 (t, 1H, J HH ) 1.9
Hz, C-2), 5.53 (d, 2H, J HH ) 1.9 Hz, C-1,3), 7.22-7.31 (m, 4H,
H-4,7 and H-5,6). 13C{1H} NMR (δ, CDCl3): 19.2 (m, iPr), 25.8
i
(m, Pr), 62.9 (s, C-1), 72.5 (s, C-3), 89.7 (s, C-2), 112.7 and
113.7 (both s, C-3a,7a), 122.4, 123.0, 125.7, and 128.6 (all s,
C-4,5,6,7), 205.5 (d, J PC ) 20.7 Hz, CO). Anal. Calcd for
RuC22H34ClOP (481.27): C, 54.8; H, 7.1. Found: C, 54.3; H,
7.2.
Meth od B. AgBF4 (0.194 g, 1 mol) was added at room
temperature to a solution of 1 in CH2Cl2 (15 mL). The solution
was stirred at room temperature for 30 min. The solution was
then filtered and evaporated to dryness, affording a brown
solid. Yield: 70%. IR (Nujol): ν 1134, 870, 735 cm-1 (FBF3).
19F{1H} NMR (δ, toluene/D2O): -158.9 (s, free BF4-), -160.1
(s, br, F-BF3), -301.1 (m, br, F-BF3). 1H NMR (δ, CDCl3): 0.39
(m, 1H, CH2), 0.75 (m, 1H, CH2), 1.28-1.51 (m, 4H, CH2), 2.51
(m, 2H, CH2), 3.65 (m, 2H, CH), 4.61 (m, 2H,CH), 5.33 (m,
2H, H-1,3), 5.53 (m, H-2), 6.90-7.17 (m, 4H, H-4,7 and H-5,6).
13C{1H} NMR (δ, CDCl3): 20.2 (s, CH2), 29.2 (s, CH2), 44.8 (s,
CH), 75.2 (s, CH), 81.9 (s, C-2), 101.4 (s, C-3a,7a), 103.9, 107.6
(s, C-1,3), 122.4 and 123.5 (s, C-4,7 and C-5,6). Anal. Calcd
for RuC17H19BF4 (411.2): C, 49.6; H, 4.6. Found: C, 49.5; H,
4.9. MS(FAB+): m/e 411 (M+), 392 (M+ - F), 373 (M+ - F2),
324 (M+ - BF4).
Syn th esis of [Ru (η5-C9H7)Cl{K2-(P ,N)-o-P h 2P C6H4C(H)d
NtBu }] (4). o-Ph2PC6H4C(H)dNtBu (1.5 mol) was added to a
solution of 1 (0.359 g, 1 mol) in THF (25 mL). The solution
was refluxed for 30 min. After cooling, solvents were removed
under vacuum. The solid residue was purified by a silica gel
column, recovering the red fraction eluted with Et2O. 4 was
obtained, removing all solvents under vacuum as a red solid
in 80% yield. 31P{1H} (δ, CDCl3): 82.25 (s). 1H NMR (δ,
t
CDCl3): 1.11 (s, 9H, Bu), 4.08 (s, 1H, H2), 4.57 (s, 2H, H1,3),
7.10, 7.23-7.50, 7.79 (m, 18H, H4,5,6,7, Ph), 8.14 (s, 1H, Nd
CH). 13C{1H} NMR (δ, CDCl3): 32.1 (s, CCH3), 59.2-62.4 (s,
C1,3), 71.3 (s, CCH3), 89.4 (s, C2), 120.5, 120.6 (s, C3a,7a),
124.4-140.8 (m, C-4,5,6,7, Ph), 164.4 (s, CHdN). Anal. Calcd
for RuC32H31ClNP (597.1): C, 64.3; H, 5.2. Found: C, 64.0; H,
4.5.
Syn th esis of [Ru (η5-C9H7){K1-(P )-P h 2P CH2C(O)tBu }{K2-
(P ,O)-P h 2P CHdC(O)tBu }] (5). Ph2PCH2C(O)tBu (0.6 g, 2.1
mol) was added to a stirred solution of 1 (0.53 g, 1 mol) in
CH2Cl2 (25 mL) and the resulting solution refluxed for 1 h.
The solution was then evaporated to dryness, and the solid
residue was filtered through a column of Basic Alumine,
recovering the fraction eluted with MeOH. Solvents were
removed under vacuum, affording a red solid. Yield: 80%. IR
Syn th esis of [Ru (η5-C9H7)(N3)(COD)] (8). NaN3 (0.06 g,
1 mol, in 2 mL of MeOH) was added to a solution of 1 (0.359
g, 1 mol) in THF/MeOH (10:1) (20 mL). The solution was
stirred at room temperature for 30 min. The solid residue was
removed by filtration. Solvents were then removed, and the
yellow solid was obtained, washed with hexane (2 × 20 mL),
and vacuum-dried. Yield: 0.31 g (85%). IR (Nujol): ν 2029 cm-1
(N3). 1H NMR (δ, CDCl3): 1.77 (m, 2H, CH2), 2.06 (m, 2H, CH2),
2.26 (m, 2H, CH2), 3.37 (m, 4H, CH), 4.29 (m, 2H, CH), 5.37
(m, 1H, H-2), 5.47 (m, 2H, H-1,3), 7.29-7.44 (m, 4H, H-4,7
and H-5,6). 13C{1H} NMR (δ, CDCl3): 27.87 (s, CH2), 33.42 (s,
CH2), 75.07 (s, CH), 79.25 (s, CH), 83.76 (s, C-1,3), 97.32 (s,
C-2), 110.19 (s, C-3a,7a), 123.46 and 128.66 (s, C-4,7 and
C-5,6). Anal. Calcd for RuC17H19N3 (366.43): C, 55.7; H, 5.2;
N, 11.4. Found: C, 56.0; H, 5.5; N, 10.9.
(Nujol): ν 1701 (CdO), 1495 (CdCO) cm-1
.
31P{1H} (δ,
CDCl3): 69.9 (d, J PP ) 36.9 Hz), 41.4 (d, J PP ) 36.9 Hz). 1H
t
t
NMR (δ, CDCl3): 0.45 (s, 9H, Bu), 1.12 (s, 9H, Bu), 2.25 (m,
1H, CH), 2.85 (m, 1H, CH), 3.51 (m, 1H, CH), 4.05 (m, 2H,
H1,3), 4.79 (m, 1H, H2), 6.71-7.75 (m, 24H, Ph, H-4,5,6,7).
t
t
13C{1H} NMR (δ, CDCl3): 27.7 (s, Bu), 32.3 (s, Bu), 33.9 (d,
3
2J PC ) 10.8 Hz, CH2), 40.8 (d, J PC ) 11.6 Hz, CMe3), 47.5 (s,
Syn t h esis of [R u (η5-C9H 7)(p y)(COD)][BF 4] (9) (p y )
p yr id in e). AgBF4 (0.194 g, 1 mol) was added to a solution of
1 (0.356 g, 1 mol) in CH2Cl2 (10 mL), and the mixture was
stirred at room temperature for 2 h in the dark. Then, pyridine
(0.79 g, 1 mol) was added and the mixture stirred at room
temperature for 20 min. The solution was then filtered and
the solvents were removed, yielding an yellow solid, which was
crystallized with CH2Cl2 (10 mL), vacuum-dried, and washed
with hexane (2 × 20 mL). Removing all solvents afforded a
2
1
CMe3), 66.0 (d, J PC ) 12.8 Hz, C2), 66.2 (s, C1), 77.6 (d, J PC
) 57.9 Hz, CHdCO), 87.1 (s, C3), 107.1, 114.0 (s, C3a,7a),
124.4, 127.0, 127.3, 128.5 (all s, C4,5,6,7), 129.3 (d, J PC ) 9.1
Hz, o,m-Ph), 129.4 (d, J PC ) 10.0 Hz, o,m-Ph), 129.9 (d, J PC
9.7 Hz, o,m-Ph), 130.2 (d, J PC ) 2.4 Hz, p-Ph), 130.6 (d, J PC
2.2 Hz, p-Ph), 130.8 (d, J PC ) 1.8 Hz, p-Ph), 130.9 (d, J PC
2.1 Hz, p-Ph), 131.6 (d, J PC ) 2.2 Hz, p-Ph), 133.3 (d, J PC
)
)
)
)
10.0 Hz, o,m-Ph), 133.5 (d, J PC ) 9.8 Hz, o,m-Ph), 134.4 (d,
J PC ) 10.2 Hz, o,m-Ph), 135.2 (d, J PC ) 9.9 Hz, o,m-Ph), 135.5
(d, J PC ) 34.7 Hz, ip-Ph), 136.2 (d, J PC ) 12.2 Hz, o,m-Ph),
1
yellow solid (0.35 g, 85%). IR (KBr): ν 1077 (BF4-). H NMR
(δ, CDCl3): 1.64 (m, 2H, CH2), 1.82 (m, 2H, CH2), 2.06 (m,
2H, CH2), 2.43 (m, 2H, CH2), 3.38 (m, 2H, CH), 5.45 (s, 2H,
H-1,3), 5.80 (m, 2H, CH), 5.91 (s, 1H, H-2), 6.95-7.32 (m, 4H,
H-4,7 and H-5,6), 7.48 (t, 2H, J HH ) 6.3 Hz, py), 7.98 (t, 1H,
J HH ) 7.3 Hz, py), 8.42 (d, 2H, J HH ) 4.9 Hz, py). 13C{1H} NMR
(δ, CDCl3): 27.1 (s, CH2), 32.6 (s, CH2), 74.2 (s, CH), 85.3 (s,
CH), 87.3 (s, C-1,3), 99.4 (s, C-2), 108.4 (s, C-3a,7a), 123.9 and
128.9 (both s, C-4,7 and C-5,6), 135.3 (s, py), 138.9 (s, py), 156.4
(s, py). Anal. Calcd for RuC22H24F4NB (452.2): C, 53.9; H, 4.9;
N, 2.9. Found: C, 54.1; H, 4.7; N, 3.0.
2
140.0 (d, J PC ) 44.5 Hz, ip-Ph), 140.1 (dd, J PC ) 45.7 Hz, J PC
2
) 4.9 Hz, ip-Ph), 146.9 (dd, J PC ) 39.2 Hz, J PC ) 3.1 Hz, ip-
Ph), 202.2 (d, J PC ) 15.2 Hz, CdCO), 212.8 (d, J PC ) 10.9 Hz,
CdO). Anal. Calcd for RuC28H40ClOP (560.12): C, 60.0; H, 7.2.
Found: C, 59.8; H, 6.9.
Syn th esis of [Ru (η5-C9H7)Cl(NBD)] (6). Norbornadiene
(0.1 g, 1 mol) was added at room temperature to a solution of
1 (0.35 g, 1 mol) in THF (20 mL). The solution was then
refluxed for 30 min. After evaporation, the solid residue was
extracted with dichloromethane (ca. 25 mL) and filtered (the
excess of norbornadiene was separated as a polymer, charac-
terized as the correspondent ROMP, not soluble in CH2Cl2).
The extract was evaporated to dryness, yielding an orange
Syn th esis of [Ru (η5-C9H7)(COD)(NCMe)][BF 4] (10). The
same procedure as above was used with acetonitrile (1 mL).
10 was isolated as an orange solid. Yield: 0.40 g (85%). IR

3770 Organometallics, Vol. 20, No. 17, 2001
Alvarez et al.
1
(KBr): ν 2226 cm-1 (CtN), 1069 (BF4-). H NMR (δ, CDCl3):
Ta ble 4. Cr ysta llogr a p h ic Da ta for Com p lexes 6
a n d 9
1.89 (m, 2H, CH2), 2.06 (m, 2H, CH2), 2.43 (m, 2H, CH2), 2.54
(m, 2H, CH2), 2.58 (s, 3H, Me), 3.67(m, 2H, CH), 4.61 (m, 2H,
CH), 5.49 (s, 2H, H-1,3), 5.76 (s, 1H, H-2), 7.38-7.54 (m, 4H,
H-4,7 and H-5,6). 13C{1H} NMR (δ, CDCl3): 4.5 (s, 3H, Me),
27.6 (s, CH2), 32.3 (s, CH2), 73.9 (s, CH), 83.0 (s, CH), 85.0 (s,
C-1,3), 96.13 (s, C-2), 101.1 (s, C-3a,7a), 124.4 and 130.0 (both
s, C-4,7 and C-5,6), 131.45 (s, CtN). Anal. Calcd for RuC19H22F4-
NB (452.2): C, 50.4; H, 4.9; N, 3.0. Found: C, 50.0; H, 4.7; N,
3.4.
formula
C16H15RuCl (6),
22H24BF4NORu (9)
C
fw
temp
wavelength
cryst syst
space group
unit cell dimens
343.80 (6), 490.30 (9)
293(2) K
0.71073 Å
monoclinic
P21/n
(6) a ) 7.171(3) Å, R ) 90°
b ) 10.255(5) Å, â ) 94.01(3)°
c ) 17.992(6) Å, γ ) 90°
(9) a ) 8.483(2), Å R ) 90°
b ) 24.966(7) Å, â ) 105.34(4)°
c ) 9.880(8) Å, γ ) 90°
1320(1) Å3 (6), 2018(2) Å3 (9)
4
[2+2] Cycloa d d ition s Rea ction s of Nor bor n en e, w ith
Alk yn es (Gen er a l P r oced u r e). A mixture of norbornene
(0.018 g, 0.2 mol), the catalyst 1 (0.0017 g, 0.005 mol), and
the alkyne (0.1 mol) under argon was heated in a sealed flask
fitted with a Teflon septum at 80 °C in a thermostated bath.
The reaction was monitored by gas chromatography-MS
(nonane or undecane as internal standard). Formation of the
coupling products was further confirmed by comparison with
the literature NMR data.40 Preparative conditions: Norbornene
(0.18 g, 2 mol), complex 1 (0.017 g, 0.05 mol), and the alkyne
were reacted at 80 °C. The reaction was monitored by GC until
complete transformation of the alkyne (Table 1, entry 1: 20
h, entry 3: 24 h). The crude reaction mixture, after removal
of solvent, was washed several times with hexane. The extracts
were vacuum-dried, and the residue was purified by column
chromatography (silica gel, hexane as eluant) (phenylacetilene)
or vacuum distillation (1-octine), to give the pure products.
[4+2] Cycloa d d ition s Rea ction s of 1,5-Cycloocta d ien e
w ith Alk yn es (Gen er a l P r oced u r e). 1,5-Cyclooctadiene
(0.021 g, 0.2 mol), complex 1 (1.7 mg, 0.005 mol), and the
alkyne (0.01 mol) were reacted at 80 °C. Workup and analysis
were carried out as indicated for the [2+2] cycloaddition
reactions of norbonene. The formation of free COD during the
reaction was detected by GC. Preparative conditions: 1,5-
cyclooctadiene (0.21 g, 2 mol), complex 1 (0.017 g, 0.05 mol),
and 1-phenyl-1-propyne (0.011 g, 0.1 mol) were reacted at 80
°C until complete conversion of the alkyne (Table 2, entry 3:
20 h). Once the reaction was finished, the mixture was
extracted with diethyl ether (5 mL), solvents were removed
volume
Z
density (calcd)
abs coeff
F(000)
1.730 g/cm3 (6), 1.614 g/cm3 (9)
1.367 mm-1 (6), 0.821 mm-1 (9)
688 (6), 992 (9)
0.198 × 0.132 × 0.099 mm (6),
0.132 × 0.132 × 0.033 mm (9)
2.27-25.98° (6), 1.63-25.97° (9)
-8 e h e 8, -12 e k e 12,
0 e l e 22 (6),
cryst size
θ range for data collection
index ranges
-10 e h e 10, 0 e k e 30,
0 e l e 12 (9)
no. of reflns collected
no. of ind reflns
4827 (6), 4183 (9)
2599 [R(int) ) 0.035] (6)
3955 [R(int) ) 0.067] (9)
semiempirical (6),
abs corr
empirical over F2 (9)
0.906 and 0.675 (6),
0.871 and 0.577 (9)
max. and min. transmn
refinement method
full-matrix least-squares on F2
no. of data/restraints/params 2599/0/223 (6), 3955/0/277 (9)
goodness-of-fit on F2
1.013 (6), 0.990 (9)
final R indices [I>2σ(I)]
R1 ) 0.0284, wR2 ) 0.0560 (6)
R1 ) 0.0568, wR2 ) 0.1354 (9)
R1 ) 0.0689, wR2 ) 0.0658 (6)
R1 ) 0.2222, wR2 ) 0.1982 (9)
0.464 and -0.603 e Å-3 (6)
1.018 and -1.512 e Å-3 (9)
R indices (all data)
largest diff peak and hole
pirical absorption correction was applied for 6 by using the
ψ-scan technique,41g while for 9, an empirical absorption
correction was applied using the program SHELXA.41h A full
matrix anisotropic least-squares refinement over F2, using the
program SHELXL-9741h followed by a difference Fourier
synthesis, allowed the location of every hydrogen atom of 6
and some H atoms for 9. Positional parameters and anisotropic
displacement parameters of the non-hydrogen atoms were
refined. Hydrogen atoms were left free and isotropically refined
for 6, while H atoms were refined using geometrical and
thermal restrictions for compound 9.
Final conventional agreement factors were R(F) ) 0.028 for
the 1792 “observed” reflections and 223 variables, and wR(F2)
) 0.066 for the whole set of 2599 reflections for 6 and R(F) )
0.057 for the 1560 “observed” reflections and 277 variables,
and wR(F2) ) 0.198 for the whole set of 3955 reflections for 9.
1
under vacuum, and the oil was obtained vacuum distilled. H
and 13C{1H} NMR of the final product was in agreement with
the literature data.7b
Hyd r a tion of Alk yn es (Gen er a l P r oced u r e). A stirred
solution of 1 (0.017 g, 0.05 mol) and the alkyne (1 mol) in
2-propanol/water (2.5/0.75 mL) was kept in a sealed vessel and
heated in a thermostated bath. The reaction was monitored
by gas chromatography-MS (nonane or undecane as internal
standard). The product was purified by column chromatogra-
phy on silica gel (hexane/Et2O, 1:1) to give the pure products.
Formation of ketones was confirmed by comparison of the
NMR data (1H NMR) and GC-mass data with those of
commercially available samples or with those of the literature
(Table 3, entry 6).35
X-r a y Str u ctu r e Deter m in a tion of 6 a n d 9.41 Crystal
data, resolution, and refinement details are collected in Table
4. Unit cell dimensions were determined from the angular
settings of 25 reflections (with 12.21° < θ < 15.26° (6) and
10.30° < θ < 12.29° (9)). A Nonius CAD4 single-crystal
diffractometer provided with a Mo KR radiation graphite
crystal monochromator (λ ) 0.71073 Å) was used for collecting
data; ω-2θ scan technique with a variable scan rate and a
maximum scan time of 60 s per reflection was used. The
intensity was checked throughout data collection by monitor-
ing three standard reflections every 60 min. Final drift
correction factors were between 1.00 and 1.03 (6) and 0.98 and
1.01 (9). On all reflections a profile analysis was performed.41b,e
Both structures were solved by Patterson interpretation and
phase expansion using the program DIRDIF92.41a,i A semiem-
(41) (a) 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: The Netherlands, 1992. (b) Grant,
D. F.; Gabe, E. J . J . Appl. Cryst. 1978, 11, 114-120. (c) Hall, S. R.; du
Boulay, D. Xtal_GX package manual; University of Western Australia,
1995. (d) International Tables for Crystallography; The International
Union of Crystallography and Kluwer Academic Publishers: Dor-
drecht, The Netherlands, 1995; Vol. C, Tables 4.2.6.8 and 6.1.1.4. (e)
Lehman, M. S.; Larsen, F. K. Acta Crystallogr. A 1974, 30, 580-584.
(f) Nardelli, M, Comput. Chem. 1983, 7, 95-98. (g) North, A. C. T.;
Philips, D. C.; Mathews, F. S. Acta Crystallogr. A 1968, 24, 351-359.
(h) Sheldrick, G. M. SHELX97 Program Package Manual; Universita¨t
Go¨ttingen: Germany, 1997. (i) Smykalla, C.; Beurskens, P. T.; Bosman,
W. P.; Garc´ıa-Granda, S. J . Appl. Crystallogr. 1994, 27, 661-665. (j)
Spek, A. L. The EUCLID Package. In Computational Crystallography;
Sayre, D., Ed.; Clarendon Press: Oxford, England, 1982; p 528. (k)
Van der Maelen Ur´ıa, J . F.; Sheldrick, G. M. Anal. Quim. Int. Ed. 1996,
92, 7-12. (l) Van der Maelen Ur´ıa, J . F. Crystallogr. Rev. 1999, 7, 125-
187.
(40) Mitsudo, T.; Kokuryo, K.; Shinugi, T.; Nakagawa, Y.; Watanabe,
Y.; Takegami, Y. J . Org. Chem. 1979, 44, 25, 4492.

Indenyl Ruthenium(II) Complexes
Organometallics, Vol. 20, No. 17, 2001 3771
The refinement of the rather disordered BF4- group, present
Ack n ow led gm en t. This work was supported by the
FEDER (1FD97-0565), NATO (CRG950794), and COST
Chemistry Project “Ruthenium Catalysts for Fine Chem-
istry” (D12/0025/99) and by the Ministerio de Ciencia y
Tecnolog´ıa (PB96-0556, Spain).
in structure 9, was performed using procedures described
elsewhere.41k,l Coordinates for the atoms of the BF4 group
-
were first restrained to have similar 1,2 and 1,3 distances
and then constrained and refined as a variable-metric rigid
group.
Atomic scattering factors were taken from the International
Tables for Crystallography.41d The plots in Figure 1 and Figure
2, showing the atomic numbering scheme, were made with the
Xtal_GX package.41c Further geometrical calculations were
made with PARST41f and the EUCLID program package.41j
All calculations were made on an Alpha AXP200/166 work-
station at the Scientific Computer Center, University of
Oviedo.
Su p p or tin g In for m a tion Ava ila ble: Crystal structure
data for 6 and 9, including tables of atomic parameters,
anisotropic displacement parameters, bond distances, and
bond angles. This material is available free of charge via the
Internet at http://pubs.acs.org.
OM010205W