Five-coordinate complex [RuHCl(CO)(PPri3)2] as a precursor for the preparation of new cyclopentadienylruthenium compounds containing unsaturated η1-carbon ligands

Article abstract of DOI:10.1021/om960124d

The five-coordinate complex [RuHCl(CO)(PPrⁱ₃)₂] (1) reacts with cyclopentadiene in methanol under reflux to give [RuH(η⁵-C₅H₅)(CO)(PPrⁱ ₃)] (2) and [HPPrⁱ₃]Cl. The protonation of 2 in dichloromethane-d₂ leads to the dihydrogen complex [Ru(η⁵-C₅H₅)(η₅-H ₂)(CO)(PPrⁱ₃)]-BF₄ (3) in equilibrium with traces of the dihydrido tautomer [RuH₂(η⁵-C₅H₅)(CO)(PPr ⁱ₃)]-BF₄ (4). The reaction of 2 with HBF₄·Et₂O in acetone affords the solvated complex [Ru(η⁵-C₅H₅)(CO){η ¹-OC(CH₃)₂}(PPrⁱ ₃)]BF₄ (5), which reacts with CO, dimethyl acetylenedicarboxylate, and NaCl to give [Ru(η⁵-C₅H₅)(CO)₂(PPr ⁱ₃)]BF₄ (6), [Ru(η⁵-C₅H₅){η²-C ₂(CO₂CH₃)₂}(CO)(PPrⁱ ₃)]-BF₄ (7), and [Ru(η⁵-C₅H₅)Cl(CO)(PPrⁱ ₃)] (8), respectively. Complex 5 also reacts with alkyn-1-ols. The reaction with 1,1-diphenyl-2-propyn-1-ol leads to the allenylidene complex [Ru(η⁵-C₅H₅)(C=C=CPh ₂)(CO)(PPrⁱ₃)]BF₄ (9), which affords [Ru(η⁵-C₅H₅){C(OH)CH=CPh ₂}-(CO)(PPrⁱ₃)]BF₄ (10) by reaction with water. 10 is converted into the acyl derivative [Ru-(η⁵-C₅H₅){C(O)CH=CPh ₂}(CO)(PPrⁱ₃)] (11), when a CH₂Cl₂ solution of 10 is passed through an Al₂O₃ column. The structure of 11 was determined by an X-ray investigation. The reaction of 5 with 2-propyn-1-ol leads to the α,β-unsaturated hydroxycarbene complex [Ru-(η⁵-C₅H₅){C(OH)CH=CH ₂}(CO)(PPrⁱ₃)]BF₄ (12). Similarly to 10, 12 is converted into [Ru-(η⁵-C₅H₅){C(O)CH=CH ₂}(CO)(PPrⁱ₃)] (13), when the solutions of 12 are passed through an Al₂O₃ column. Treatment of 5 with 1-ethynyl-1-cyclohexanol leads to a mixture of organometallic compounds including [Ru(η⁵-C₅H₅){C(OH)CH=C(CH₂) ₄CH₂}(CO)(PPrⁱ₃)]BF₄ (14). Chromatography of the mixture affords [Ru(η⁵-C₅H₅){C(O)CH=C(CH₂) ₄CH₂}(CO)-(PPrⁱ₃)] (15) and [Ru(η⁵-C₅H₅){C≡CC=CH(CH ₂)₃CH₂}(CO)(PPrⁱ₃)] (16). 9 reacts with alcohols and thiols to give [Ru(η⁵-C₅H₅){C(ER)CH=CPh ₂}(CO)(PPrⁱ₃)]BF₄ (ER = OMe (17), OEt (18), SPrⁿ (21)), which by treatment with NaOMe afford [Ru(η⁵-C₅H₅){C(ER)=C=CPh ₂}(CO)-(PPrⁱ₃)] (ER = OMe (19), OEt (20), SPrⁿ (22)). Similarly, the reaction of 9 with benzophenone imine leads to [Ru(η⁵-C₅H₅){C(CH=CPh ₂)=N=CPh₂}(CO)(PPrⁱ₃)]BF₄ (23), which by reaction with NaOMe gives [Ru(η⁵-C₅H₅){C(N=CPh ₂)=C=CPh₂}(CO)(PPrⁱ₃)] (24). The structure of 23 was also determined by an X-ray investigation. The C=N bond lengths are 1.283(9) and 1.252(9) A?, while the C-N-C angle is 149.9(6)°.

Full text of DOI:10.1021/om960124d

Organometallics 1996, 15, 3423-3435
3423
F ive-Coor d in a te Com p lex [Ru HCl(CO)(P P r i ) ] a s a
3 2
P r ecu r sor for th e P r ep a r a tion of New
Cyclop en ta d ien ylr u th en iu m Com p ou n d s Con ta in in g
Un sa tu r a ted η1-Ca r bon Liga n d s†
Miguel A. Esteruelas,* Angel V. Go´mez, Fernando J . Lahoz, Ana M. Lo´pez,
Enrique On˜ate, and Luis A. Oro
Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received February 20, 1996X
The five-coordinate complex [RuHCl(CO)(PPri )2] (1) reacts with cyclopentadiene in
3
methanol under reflux to give [RuH(η5-C5H5)(CO)(PPri3)] (2) and [HPPri3]Cl. The protonation
of 2 in dichloromethane-d2 leads to the dihydrogen complex [Ru(η5-C5H5)(η2-H2)(CO)(PPri )]-
3
BF4 (3) in equilibrium with traces of the dihydrido tautomer [RuH2(η5-C5H5)(CO)(PPri )]-
3
BF4 (4). The reaction of 2 with HBF4‚Et2O in acetone affords the solvated complex [Ru(η5-
C5H5)(CO){η1-OC(CH3)2}(PPri3)]BF4 (5), which reacts with CO, dimethyl acetylenedicarboxylate,
and NaCl to give [Ru(η5-C5H5)(CO)2(PPri3)]BF4 (6), [Ru(η5-C5H5){η2-C2(CO2CH3)2}(CO)(PPri3)]-
BF4 (7), and [Ru(η5-C5H5)Cl(CO)(PPri )] (8), respectively. Complex 5 also reacts with alkyn-
3
1-ols. The reaction with 1,1-diphenyl-2-propyn-1-ol leads to the allenylidene complex [Ru(η5-
C5H5)(CdCdCPh2)(CO)(PPri )]BF4 (9), which affords [Ru(η5-C5H5){C(OH)CHdCPh2}-
3
(CO)(PPri )]BF4 (10) by reaction with water. 10 is converted into the acyl derivative [Ru-
3
(η5-C5H5){C(O)CHdCPh2}(CO)(PPri )] (11), when a CH2Cl2 solution of 10 is passed through
3
an Al2O3 column. The structure of 11 was determined by an X-ray investigation. The
reaction of 5 with 2-propyn-1-ol leads to the R,â-unsaturated hydroxycarbene complex [Ru-
(η5-C5H5){C(OH)CHdCH2}(CO)(PPri )]BF4 (12). Similarly to 10, 12 is converted into [Ru-
3
(η5-C5H5){C(O)CHdCH2}(CO)(PPri )] (13), when the solutions of 12 are passed through an
3
Al2O3 column. Treatment of 5 with 1-ethynyl-1-cyclohexanol leads to a mixture of
organometallic compounds including [Ru(η5-C5H5){C(OH)CHdC(CH2)4CH2}(CO)(PPri )]BF4
3
(14). Chromatography of the mixture affords [Ru(η5-C5H5){C(O)CHdC(CH2)4CH2}(CO)-
(PPri3)] (15) and [Ru(η5-C5H5){CtCCdCH(CH2)3CH2}(CO)(PPri3)] (16). 9 reacts with alcohols
and thiols to give [Ru(η5-C5H5){C(ER)CHdCPh2}(CO)(PPri )]BF4 (ER ) OMe (17), OEt (18),
3
SPrn (21)), which by treatment with NaOMe afford [Ru(η5-C5H5){C(ER)dCdCPh2}(CO)-
(PPri )] (ER ) OMe (19), OEt (20), SPrn (22)). Similarly, the reaction of 9 with benzophenone
3
imine leads to [Ru(η5-C5H5){C(CHdCPh2)dNdCPh2}(CO)(PPri )]BF4 (23), which by reaction
3
with NaOMe gives [Ru(η5-C5H5){C(NdCPh2)dCdCPh2}(CO)(PPri )] (24). The structure of
3
23 was also determined by an X-ray investigation. The CdN bond lengths are 1.283(9) and
1.252(9) Å, while the C-N-C angle is 149.9(6)°.
In tr od u ction
Bis(phosphine)-cyclopentadienyl3 and -indenyl4 and
chloro-phosphine-arene5 half-sandwich ruthenium com-
plexes containing unsaturated η1-carbon ligands exhibit
a particularly rich and interesting chemistry, which has
formed one of the cornerstones in the development of
organometallic chemistry. Although, it is known that
The chemistry of transition metal complexes contain-
ing unsaturated η1-carbon ligands has received increas-
ing attention in recent years, owing to the possibilities
offered by these compounds in organic synthesis1 and
homogeneous catalysis.2
† Dedicated to Professor J uan Bertra´n on the occasion of his 65th
birthday.
(3) (a) Davies, S. G.; McNally, J . P.; Smallridge, A. J . Adv. Orga-
nomet. Chem. 1990, 30, 1. (b) Selegue, J . P.; Young, B. A.; Logan, S. L.
Organometallics 1991, 10, 1972. (c) Bruce, M. I.; Hinterding, P.;
Tiekink, E. R. T.; Skelton, B. W.; White, A. H. J . Organomet. Chem.
1993, 450, 209. (d) Lomprey, J . R.; Selegue, J . P. Organometallics 1993,
12, 616. (e) Le Lagadec, R.; Roman, E.; Toupet, L.; Mu¨ller, U.; Dixneuf,
P. H. Organometallics 1994, 13, 5030. (f) de los R´ıos, I.; Tenorio, M.
J .; Puerta, M. C.; Valerga, P. J . Chem. Soc., Chem. Commun. 1995,
1757.
(4) (a) Gamasa, M. P.; Gimeno, J .; Mart´ın-Vaca, B. M.; Borge, J .;
Garc´ıa-Granda, S.; Pe´rez-Carren˜o, E. Organometallics 1994, 13, 4045.
(b) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Lastra, E. J . Organomet.
Chem. 1994, 474, C27. (c) Cadierno, V.; Gamasa, M. P.; Gimeno, J .;
Lastra, E.; Borge, J .; Garc´ıa-Granda, S. Organometallics 1994, 13, 745.
(d) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Borge, J .; Garcı´a-Granda,
S. J . Chem. Soc., Chem. Commun. 1994, 2495.
X Abstract published in Advance ACS Abstracts, J une 15, 1996.
(1) (a) Collman, J . P.; Hegedus, L. S.; Norton, J . R.; Finke, R. G.
Principles and Applications of Organotransition-metal Chemistry;
University Science Books: Mill Valey, CA, 1987. (b) Brookhart, M.;
Volpe, A. F., J r.; Yoon, J . Comprehensive Organic Synthesis; Trost, B.
M., Fleming, I., Eds.; Pergamon Press: London, 1991; Vol 4.
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Soc. 1992, 114, 3974. (b) Trost, B. M.; Kulawiec, R. J . J . Am. Chem.
Soc. 1992, 114, 5579. (c) Trost, B. M.; Flygare, J . A. J . Am. Chem.
Soc. 1992, 114, 5476. (d) Trost, B. M.; Mart´ınez, J . A.; Kulawiec, R. J .;
Indolese, A. F. J . Am. Chem. Soc. 1993, 115, 10402. (e) Ruiz, N.; Pe´ron,
D.; Dixneuf, P. H. Organometallics 1995, 14, 1095. (f) Schwab, P.;
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1995, 34, 2039.
S0276-7333(96)00124-0 CCC: $12.00 © 1996 American Chemical Society
+
+

3424 Organometallics, Vol. 15, No. 15, 1996
Esteruelas et al.
the electron density on the metallic center determines
the reactivity of the unsaturated η1-carbon ligands,6 and
starting complexes of the types [Ru(η5-C5H5)Cl(CO)-
(PR3)]7 and [Ru(η5-C5H5)(η2-H2)(CO)(PR3)]+ 8 can be
easily prepared, surprisingly, the chemistry of the less
basic carbonyl-phosphine-cyclopentadienyl-ruthe-
nium systems has rarely been investigated.9
Here, we report the synthesis and characterization
of new allenylidene and R,â-unsaturated-hydroxycar-
bene, -acyl, -alkoxycarbene, -(alkylthio)carbene, -2-
azaallenyl, alkoxyallenyl, (alkylthio)allenyl, and imino-
allenyl derivatives containing the Ru(η5-C5H5)(CO)-
(PPri ) unit. In addition, the X-ray structures of the
3
complexes [Ru(η5-C5H5){C(O)CHdCPh2}(CO)(PPri3)] and
[Ru(η5-C5H5){C(CHdCPh2)dNdCPh2}(CO)(PPri )]BF4
3
We have previously reported that the treatment of
RuCl3‚xH2O with triisopropylphosphine in refluxing
methanol leads to the five-coordinate hydrido-chloro
are also reported.
complex [RuHCl(CO)(PPri ) ] in good yield.10 This
Resu lts a n d Discu ssion
3 2
complex, which is an active and highly selective catalyst
for the reduction of unsaturated organic substrates11
and for the addition of HSiEt3 to phenylacetylene,12 has
been also the master key for the development of an
extensive organometallic chemistry, including alkynyl,13
vinyl,14 acetatovinyl,6 carbene, vinylcarbene,15 acetato-
carbene,6 acyl,16 π-butadiene,17 dihydrogen,18 and mono-
and binuclear tetrahydridoborato derivatives.19 We
have now observed that the reaction of the complex
1. Syn th esis a n d P r oton a tion of [Ru H(η5-C5H5)-
(CO)(P P r i )] (2). Treatment of a refluxing suspension
3
of [RuHCl(CO)(PPri ) ] (1) in methanol with freshly
3 2
distilled cyclopentadiene in a 1:22 molar ratio for 4 h
gives, after filtration and solvent removal, a sticky
residue. Pentane extraction of the residue and filtration
to remove the salt [HPPri ]Cl affords a yellow solution,
3
from which the hydrido-cyclopentadienyl complex [RuH-
(η5-C5H5)(CO)(PPri )] (2) was isolated as a white solid
3
[RuHCl(CO)(PPri ) ] with cyclopentadiene leads to the
in 86% yield (eq 1). The related complexes [RuH(η5-
C5H5)(CO)(PR3)] (PR3 ) PCy3, PPh3, PMe2Ph, PMe3)
have been previously prepared by phosphine substitu-
tion of [RuH(η5-C5H5)(CO)2] in overall lower yield.8b
3 2
cyclopentadienyl complex [RuH(η5-C5H5)(CO)(PPri )],
3
which affords the dihydrogen derivative [Ru(η5-C5H5)-
(η2-H2)(CO)(PPri )]BF4 by reaction with HBF4. Interest
3
in the change of properties of the unsaturated η1-carbon
ligands on moving from the more basic ruthenium
systems led us to prepare carbonyl-triisopropylphos-
phine-cyclopentadienyl complexes of ruthenium con-
taining unsaturated η1-carbon ligands.
(5) (a) Le Bozec, H.; Touchard, D.; Dixneuf, P. H. Adv. Organomet.
Chem. 1989, 29, 163. (b) Le Bozec, H.; Ouzzine, K.; Dixneuf, P. H. J .
Chem. Soc., Chem. Commun. 1989, 219. (c) Romero, A.; Vegas, A.;
Dixneuf, P. H. Angew. Chem., Int. Ed. Engl. 1990, 29, 215. (d) Le Bozec,
H.; Ouzzine, K.; Dixneuf, P. H. Organometallics 1991, 10, 2768. (e)
Pilette, D.; Ouzzine, K.; Le Bozec, H.; Dixneuf, P. H.; Rickard, C. E.
F.; Roper, W. R. Organometallics 1992, 11, 809. (f) Lavastre, O.;
Dixneuf, P. H.; Pacreau, A.; Vairon, J . P. Organometallics 1994, 13,
2500. (g) Pilette, D.; Moreau, S.; Le Bozec, H.; Dixneuf, P. H.; Corrigan,
J . F.; Carty, A. J . J . Chem. Soc., Chem. Commun. 1994, 409. (h) Pe´ron,
D.; Romero, A.; Dixneuf, P. H. Organometallics 1995, 14, 3319.
(6) Esteruelas, M. A.; Lahoz, F. J .; Lo´pez, A. M.; On˜ate, E.; Oro, L.
A. Organometallics 1994, 13, 1669.
The IR spectrum of 2 in Nujol shows absorptions due
to ν(RuH) at 1985 cm-1 and ν(CO) at 1920 cm-1. The
presence of the hydrido ligand is confirmed by the H
1
NMR spectrum in benzene-d6, which contains a doublet
at -12.05 ppm with a P-H coupling constant of 30.7
Hz together with the expected singlet at 4.87 ppm for
the cyclopentadienyl ligand and the characteristic sig-
(7) Davies, S. G.; Simpson, S. J . J . Chem. Soc., Dalton Trans. 1984,
993.
(8) (a) Chinn, M. S.; Heinekey, D. M. J . Am. Chem. Soc. 1987, 109,
5865. (b) Chinn, M. S.; Heinekey, D. M. J . Am. Chem. Soc. 1990, 112,
5166. (c) J ia, G.; Morris, R. H. J . Am. Chem. Soc. 1991, 113, 875. (d)
Ryan, O. B.; Tilset, M. J . Am. Chem. Soc. 1991, 113, 9554. (e) Ryan,
O. B.; Tilset, M.; Parker, V. D. Organometallics 1991, 10, 298. (f)
Scharrer, E.; Chang, S.; Brookhart, M. Organometallics 1995, 14, 5686.
(9) Bruce, M. I.; Duffy, D. N.; Humphrey, M. G.; Swincer, A. G. J .
Organomet. Chem. 1985, 282, 383.
(10) Esteruelas, M. A.; Werner, H. J . Organomet. Chem. 1986, 303,
221.
(11) (a) Esteruelas, M. A.; Sola, E.; Oro, L. A.; Werner, H.; Meyer,
U. J . Mol. Catal. 1988, 45, 1. (b) Esteruelas, M. A.; Sola, E.; Oro, L.
A.; Werner, H.; Meyer, U. J . Mol. Catal. 1989, 53, 43.
(12) Esteruelas, M. A.; Herrero, J .; Oro, L. A. Organometallics 1993,
12, 2377.
nals for the PPri ligand. The 31P{1H} NMR spectrum
3
shows a singlet at 91.6 ppm, which under off-resonance
conditions is split into a doublet due to the P-H
coupling.
The addition of 1 equiv of HBF4‚OEt2 to a solution of
2 in dichloromethane-d2 leads, after a few seconds, to
the dihydrogen complex [Ru(η5-C5H5)(η2-H2)(CO)(PPri3)]+
(3) in equilibrium with traces of the dihydrido tautomer
[RuH2(η5-C5H5)(CO)(PPri )]+ (4) (eq 2).20 At room tem-
3
(13) (a) Werner, H.; Meyer, U.; Esteruelas, M. A.; Sola, E.; Oro, L.
A. J . Organomet. Chem. 1989, 366, 187. (b) Bohanna, C.; Esteruelas,
M. A.; Herrero, J .; Lo´pez, A. M.; Oro, L. A. J . Organomet. Chem. 1995,
498, 199.
(14) Werner, H.; Esteruelas, M. A.; Otto, H. Organometallics 1986,
5, 2295.
(15) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Zeier, B.
Organometallics 1994, 13, 4258.
(16) Bohanna, C.; Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro,
L. A. Organometallics 1995, 14, 4685.
(17) Bohanna, C.; Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro,
L. A.; Sola, E. Organometallics 1995, 14, 4825.
(18) Buil, M. L.; Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L.
A. J . Am. Chem. Soc. 1995, 117, 3619.
(19) (a) Werner, H.; Esteruelas, M. A.; Meyer, U.; Wrackmeyer, B.
Chem. Ber. 1987, 120, 11. (b) Esteruelas, M. A.; Garc´ıa, M. P.; Lo´pez,
A. M.; Oro, L. A.; Ruiz, N.; Schlu¨nken, C.; Valero, C.; Werner, H. Inorg.
Chem. 1992, 31, 5580.
perature, the 1H NMR spectrum of the equilibrium
+
+

[RuHCl(CO)(PPri )2]
Organometallics, Vol. 15, No. 15, 1996 3425
3
Sch em e 1
F igu r e 1. 1H NMR spectrum (300 MHz, 293 K, CD2Cl2)
in the hydride region for the mixture of [Ru(η5-C5H5)(η2-
H2)(CO)(PPri )]BF4 (3) and [RuH2(η5-C5H5)(CO)(PPri )] (4).
3
3
mixture shows, in the hydrido region (Figure 1), a very
broad resonance centered at -7.95 ppm (ω1/2 ) 75 Hz)
for the dihydrogen ligand and a doublet at -7.17 ppm
with a P-H coupling constant of 19.8 Hz for the
dihydrido tautomer. T1 measurements for the broad
resonance at 300 MHz gave a value of 34 ms at 253 K
which decreases to 6 ms at 193 K. The reaction is
reversible, and 2 may be regenerated by addition of the
1053 cm-1, along with the ν(CO) band of the carbonyl
group of the acetone ligand at 1652 cm-1. This value
suggests that the acetone molecule coordinates to the
ruthenium atom by the oxygen atom.23 In agreement
with this, the 13C{1H} NMR spectrum contains a singlet
at 230.4 ppm for the carbon atom of the carbonyl group
of the acetone.
The acetone ligand of 5 is easily displaced by strong
π-acceptor ligands such as carbon monoxide and di-
methyl acetylenedicarboxylate and by chloride (Scheme
1). By passage of a slow stream of carbon monoxide
through a dichloromethane solution of 5, the dicarbonyl
complex 6 is formed (Scheme 1). Similarly, treatment
of 5 with dimethyl acetylenedicarboxylate affords 7, and
the addition of sodium chloride to a methanol solution
of 5 leads to 8.
The presence of the π-alkyne ligand in 7 is inferred
by the IR and 13C{1H} NMR spectra. The IR spectrum
in Nujol shows a strong absorption at 1869 cm-1, which
is characteristic of the ν(CtC) vibration,24 while in the
13C{1H} NMR spectrum the acetylenic carbon atoms
appear at 73.4 and 72.5 ppm as broad resonances.
2. Rea ction s of [Ru (η5-C5H5)(CO){η1-OC(CH3)2}-
(P P r i3)]BF 4 (5) w ith Alk yn -1-ols. The investigation
aimed at elucidating the reactivity of 5 toward alkyn-
1-ols is summarized in Scheme 2.
Treatment of a dichloromethane solution of 5 with a
stoichiometric amount of 1,1-diphenyl-2-propyn-1-ol
leads to a red solution, from which the allenylidene
complex 9 can be isolated as a dark red solid in 87%.
The IR spectrum of 9 in Nujol shows the characteristic
ν(CdCdC) band of the allenylidene ligand25 at 2002
cm-1. In the 13C{1H} NMR spectrum the most notice-
able resonances of this ligand are two doublets at 288.3
and 188.5 ppm with P-C coupling constants of 13.8 and
2.3 Hz, which were assigned to the CR and Câ carbon
atoms, respectively, and a singlet at 164.4 ppm due to
the Cγ carbon atom.
stoichiometric amount of triethylamine, suggesting that
+
the pKa of 3 is lower than the pKa of HNEt3
.
In methanol-d4 as solvent, deuteration of the hydrido
of 2 is observed. The protonation in chloroform-d1 of
the deuterated complex 2 yields the partial deuterated
dihydrogen derivative 3, which shows a H-D coupling
constant of 28.5 Hz at 213 K in good agreement with
those previously reported for related compounds.8b The
related iron complexes [Fe(η5-C5H5)(η2-H2)(CO)(L)]+
have been recently reported. They react with silanes
to generate [Fe(η5-C5H5)(η2-HSiR3)(CO)(L)]+ (L ) PEt3,
PPh3).8f
There is a marked difference toward protonation
between 2 and the related osmium complex [OsH(η5-
C5H5)(CO)(PPri )]. We have previously observed that
3
the reaction of the osmium compound with the stoichio-
metric amount of HBF4‚OEt2 exclusively leads to the
dihydrido derivative [OsH2(η5-C5H5)(CO)(PPri )]BF4.21
3
In this context, it should be noted that ruthenium is a
poorer π-back-bonder than osmium, because the osmium
valence orbitals have better overlap with ligand orbit-
als.22 Therefore, the dihydrido tautomers are more
favored with osmium than with ruthenium.
The protonation of 2 with HBF4‚OEt2 in acetone leads
to the solvated complex [Ru(η5-C5H5){η1-OC(CH3)2}-
(CO)(PPri )]BF4 (5) (eq 3), which was isolated as an
3
orange solid in 99% yield.
The allenylidene complex 9 reacts with an excess of
water to give the R,â-unsaturated hydroxycarbene 10,
which was isolated as a yellow solid in 78% yield. The
IR spectrum of 10 in Nujol contains a resonance at about
3050 cm-1, characteristic of a ν(OH) absorption, along
with a ν(CdC) band at 1560 cm-1 and absorptions due
to [BF4]- at 1093, 1032, and 976 cm-1. The splitting of
The IR spectrum of 5 in Nujol shows the absorption
due to the [BF4]- anion with Td symmetry centered at
(20) The trans disposition of the hydrido ligands of 4 is proposed on
the basis of the single doublet observed in the 1H NMR spectrum. An
alternative cisoid dihydrido structure should give rise to two hydrido
resonances.
(21) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez A. M.; Oro, L. A.
Organometallics 1996, 15, 878.
(22) Bautista, M. T.; Cappellani, E. P.; Drouin, S. D.; Morris, R. H.;
Schweitzer, C. T.; Sella, A.; Zubkowski, J . J . Am. Chem. Soc. 1991,
113, 4876.
(23) Atencio, R.; Bohanna, C.; Esteruelas, M. A.; Lahoz, F. J .; Oro,
L. A. J . Chem. Soc., Dalton Trans. 1995, 2171.
(24) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Rodr´ıguez,
L. Organometallics 1995, 14, 263.
(25) Bruce, M. I. Chem. Rev. 1991, 91, 197.
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3426 Organometallics, Vol. 15, No. 15, 1996
Esteruelas et al.
Sch em e 2
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e Com p lex
[Ru (η5-C5H5){C(O)CHdCP h 2}(CO)(P P r i3)] (11)
Ru-P
2.3288(9)
2.060(2)
1.836(3)
2.266(4)
2.275(3)
2.298(3)
2.305(4)
Ru-C(30)
O(1)-C(1)
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
C(3)-C(10)
O(2)-C(16)
2.258(5)
1.212(3)
1.502(3)
1.333(4)
1.487(4)
1.497(3)
1.152(3)
Ru-C(1)
Ru-C(16)
Ru-C(26)
Ru-C(27)
Ru-C(28)
Ru-C(29)
P-Ru-C(1)
91.82(8)
Ru-C(1)-C(2)
116.1(2)
119.6(2)
129.2(2)
123.2(2)
120.0(2)
116.8(2)
P-Ru-C(16)
93.8(1)
126.5(1)
92.6(1)
117.1(1)
125.8(1)
123.9(2)
O(1)-C(1)-C(2)
C(1)-C(2)-C(3)
C(2)-C(3)-C(4)
C(2)-C(3)-C(10)
C(4)-C(3)-C(10)
P-Ru-G(1)a
C(1)-Ru-C(16)
C(1)-Ru-G(1)a
C(16)-Ru-G(1)a
Ru-C(1)-O(1)
a
F igu r e 2. Molecular diagram of complex [Ru(η5-C5H5)-
G(1) is the midpoint of the C(26)-C(30) Cp ligand.
{C(O)CHdCPh2}(CO)(PPri )] (11). Thermal ellipsoids are
3
shown at 50% probability.
is close to octahedral with the cyclopentadienyl ligand
occupying three sites of a face. The angles formed by
the triisopropylphosphine, carbonyl, and alkenylacyl
ligands are all close to 90°. The most interesting
features of the structure are those related to the R,â-
unsaturated acyl ligand. The Ru-C(1) bond length of
2.060(2) Å is similar to those found in the complexes
[PPN][Ru6C(CO)16{C(O)Me}] (2.099(12) Å)26 and [Ru-
{C(O)Me}I(CO)2(Pri-DAB)] (2.078(8) Å)27 and about 0.1
Å longer than that found in the five-coordinate deriva-
the Td symmetry of the anion suggests that it interacts
with the OH group of the hydroxycarbene ligand. The
presence of the hydroxycarbene is also supported by the
1H and 13C{1H} NMR spectra. The H NMR spectrum
1
shows a singlet at 7.09 ppm due to the CHd proton and
a broad resonance at 12.8 ppm corresponding to the
-OH proton. In the 13C{1H} NMR spectrum, the
RudC(OH) carbon atom of the unsaturated η1-carbon
ligand appears as a doublet at 298.7 ppm with a P-C
coupling constant of 9.8 Hz, while the CHd and CPh2
carbon atoms of the alkenyl group were observed as
singlets at 140.0 and 145.3 ppm, respectively.
When a dichloromethane solution of 10 was passed
through an Al2O3 (neutral, activity grade V) column, the
R,â-unsaturated acyl derivative 11 was formed. This
complex was isolated as a white solid in 85% yield and
characterized by elemental analysis, IR and 1H, 31P{1H},
and 13C{1H} NMR spectroscopy, and X-ray diffraction.
A view of the molecular geometry of 11 is shown in
Figure 2. Selected bond distances and angles are listed
in Table 1. The geometry around the ruthenium center
tive [Ru{C(O)Me}Cl(CO)(PPri ) ] (1.957(6) Å).16 The
3 2
Ru-C(1)-O(1) and Ru-C(1)-C(2) angles are 123.9(2)
and 116.1(2)°, and the C(1)-O(1) bond length is 1.212-
(3) Å, as expected for a CdO double bond of an η1-acyl
ligand. The C(2)-C(3) (alkene) bond distance of 1.333-
(4) Å is similar to those observed in the complexes [Fe-
(η5-C5H 5){(E )-C(O)C(CH 2OMe)dC(Me)P h }(CO){P -
(OPh)3}] (1.329(4) Å),28 [Fe(η5-C5H5){(E)-C(O)CHdCH-
(26) Chihara, T.; Aoki, K.; Yamazaki, H. J . Organomet. Chem. 1990,
383, 367.
(27) Kraakman, M. J . A.; de Klerk-Engels, B.; de Lange, P. P. M.;
Vrieze, K.; Smeets, W. J . J .; Spek, A. L. Organometallics 1992, 11,
3774.
+
+

[RuHCl(CO)(PPri )2]
Organometallics, Vol. 15, No. 15, 1996 3427
3
Me}(CO)(PPh3)] (1.316(6) Å),29 [Fe(η5-C5H5){(Z)-C(O)C-
(Me)dC(Ph)Me}(CO){P(OPh)3}] (1.332(4) Å), and [Fe-
(η5-C5H5){(E)-C(O)C(Me)dC(Me)SPh}(CO){P(OPh)3}]
(1.327(6) and 1.314(6) Å)30 and does not seem to be
lengthened by any appreciable conjugation with the acyl
group.
In agreement with the presence of an R,â-unsaturated
acyl ligand in 11, the IR spectrum in Nujol shows a ν-
(CdO) band at 1581 cm-1, and the 13C{1H} NMR
spectrum contains a doublet at 249.5 (J (PC) ) 10.1 Hz)
ppm and two singlets at 144.5 and 130.6 ppm, corre-
sponding to Ru-CdO, CHd, and dCPh2 carbon atoms,
respectively.
Treatment of a dichloromethane solution of 5 with the
stoichiometric amount of 2-propyn-1-ol leads to a yellow
solution from which the R,â-unsaturated-hydroxycar-
bene complex 12 was isolated as a yellow solid in 90%
yield. Similarly to 10, the IR spectrum of 12 in Nujol
contains the ν(OH) and ν(CdC) absorptions of the R,â-
unsaturated-hydroxycarbene ligand. The first one ap-
pears between 3400 and 3050 cm-1, as a very broad
band, and the second one at 1595 cm-1. In addition two
absorptions due to [BF4]- at 1091 and 1002 cm-1 are
also observed. The splitting of the expected Td sym-
metry of the [BF4]- group suggests that, in this case,
the anion also interacts with the -OH group of the
carbene ligand. In the 1H NMR spectrum of 12 the most
noticeable resonances include a double doublet at 7.24
ppm with H-H coupling constants of 17.0 and 10.7 Hz,
which was assigned to the CHd proton, two doublets
at 5.94 and 5.45 ppm with H-H coupling constants of
17.0 and 10.7 Hz, respectively, which were assigned to
the dCH2 protons, and a broad resonance at 13.1 ppm
corresponding to the -OH proton. In the 13C{1H} NMR
spectrum, the RudC(OH) carbon atom of the unsatur-
ated η1-carbon ligand gives rise to a doublet at 296.3
ppm with a P-C coupling constant of 9.9 Hz, while the
olefinic carbon atoms display singlets at 150.0 and 121.2
ppm.
the R,â-unsaturated-hydroxycarbene complex 14 (vide
infra). In agreement with the presence of 14 in the
mixture, the acyl derivative 15 was separated as main
product (60%) from this, by column chromatography
(Al2O3 neutral, activity grade V). In addition, the R,â-
unsaturated-alkynyl complex 16 was also obtained in a
5% yield.
Complex 15 was isolated as a yellow solid an char-
1
acterized by elemental analysis and IR and H, 31P{1H},
and 13C{1H} NMR spectroscopy. In the IR spectrum in
Nujol, the most noticeable absorptions are those corre-
sponding to the ν(CdO) and ν(CdC) vibrations of the
alkenylacyl ligand, which appear at 1557 and 1612
cm-1, respectively. In the 1H NMR spectrum, the
presence of the acyl ligand is mainly supported by a
singlet at 6.85 ppm and in the 13C{1H} NMR spectrum
by a doublet at 247.8 ppm with a P-C coupling constant
of 9.6 Hz (Ru-CdO) and two singlets at 141.0 (CHd)
and 137.7 (dCPh2) ppm.
The alkynyl complex 16 was isolated as a white solid.
The presence of an alkynyl ligand in this complex was
inferred from its IR and 13C{1H} NMR spectra. Thus,
the IR spectrum contains bands at 2088 and 1618 cm-1
,
characteristic of the ν(CtC) and ν(CdC) vibrations of
an R,â-unsaturated-alkynyl group. In the 13C{1H} NMR
spectrum, the carbon atoms of the alkynyl fragment
appear as doublets at 92.4 (Ru-Ct) and 126.1 (tC-)
ppm, with P-C coupling constants of 23.0 and 0.9 Hz,
respectively, while the olefinic carbon atoms display
singlets at 113.3 (Cd) and 125.2 (CHd) ppm.
The acyl complexes 11, 13, and 15 react with the
stoichiometric amount of HBF4‚OEt2 to afford the cor-
responding hydroxycarbene derivatives 10, 12, and 14.
By this procedure complex 14 was obtained as an
analytically pure yellow solid in 84% yield. As for 10
and 12, the IR spectrum of 14 shows ν(OH) and ν(CdC)
vibrations, at 3331 and 1586 cm-1, respectively, along
with two bands due to [BF4]- at 1094 and 968 cm-1
,
suggesting that, also in this case, the anion interacts
with the -OH group. The 1H NMR spectrum of 14
shows the -OH resonance, at 13.2 ppm, and a singlet
at 6.94 ppm, due to the CHd proton. In the 13C{1H}
NMR spectrum, the RudC(OH) carbon atom appears
at 295.6 ppm as a doublet, with a P-C coupling constant
of 8.7 Hz. The olefinic CHd and dCPh2 carbons give
rise to singlets at 138.6 and 155.3 ppm, respectively.
As has been previously mentioned, the 31P{1H} NMR
spectrum shows a singlet at 66.7 ppm.
On the basis of the reaction of 5 with 1,1-diphenyl-
2-propyn-1-ol to give 9, and the reaction of the alle-
nylidene complex 9 with water to afford 10, the forma-
tion of 12 and 14 from 5 and the corresponding alkyn-
1-ols can be rationalized according to Scheme 3. It is
well-known that the addition of terminal alkynes to
solvated complexes and coordinatively unsaturated
metallic fragments leads to vinylidene derivatives
through π-alkyne intermediates.25 The dehydration of
hydroxyvinylidenes, containing hydrogen atoms adja-
cent to the hydroxy group, can occur in two different
directions to give either vinylvinylidene or allenylidene
derivatives, depending on the electronic and steric
properties of the metal.31 In our case, the dehydration
to the allenylidene seems to be favored, even for
When a dichloromethane solution of 12 was passed
through an Al2O3 (neutral, activity grade V) column, the
R,â-unsaturated-acyl compound 13 was also formed.
This complex was isolated as a yellow microcrystalline
solid in 42% yield. The presence of the R,â-unsaturated-
1
acyl ligand is supported by the IR and H and 13C{1H}
NMR spectra. The IR spectrum in Nujol contains two
bands at 1606 and 1562 cm-1, which were assigned to
the ν(CdC) and ν(CdO) vibrations of the alkenylacyl
1
ligand. In the H NMR spectrum, the olefinic protons
appear as double doublets at 6.94 (J (HH) ) 16.9 and
9.7 Hz), 5.63 (J (HH) ) 16.9 and 2.3 Hz), and 4.73
(J (HH) ) 9.7 and 2.3 Hz) ppm. In the 13C{1H} NMR
spectrum, the Ru-CdO carbon atom of the acyl ligand
gives rise to a doublet at 247.2 ppm with a P-C coupling
constant of 10.6 Hz, while the olefinic carbon atoms
display singlets at 152.6 and 113.2 ppm.
The reaction of 5 with 1-ethynyl-1-cyclohexanol leads
to a mixture of organometallic compounds. The most
noticeable resonance of the 31P{1H} NMR spectrum of
the mixture is a singlet at 66.7 ppm, corresponding to
(28) Reger, D. L.; Klaeren, S. A.; Babin, J . E.; Adams, R. D.
Organometallics 1988, 7, 181.
(29) Davies, S. G.; Dordor-Hedgecock, I. M.; Sutton, K. H.; Walker,
J . C.; J ones, R. H.; Prout, K. Tetrahedron 1986, 42, 5123.
(30) Reger, D. L.; Mintz, E.; Lebioda, L. J . Am. Chem. Soc. 1986,
108, 1940.
(31) (a) Selegue, J . P. Organometallics 1982, 1, 217. (b) Selegue, J .
P. J . Am. Chem. Soc. 1983, 105, 5921.
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3428 Organometallics, Vol. 15, No. 15, 1996
Esteruelas et al.
3. Rea ction s of [Ru (η5-C5H5)(CdCdCP h 2)(CO)-
Sch em e 3
(P P r i )]BF 4 (9). The allenylidene complex 9 reacts not
3
only with water but also with alcohols, thiols, and
benzophenone imine (Scheme 4). In methanol and
ethanol as solvents, the allenylidene complex 9 evolves
to the R,â-unsaturated-alkoxycarbene derivatives 17
and 18, respectively, which were isolated as yellow
solids in high yields (about 85%).
The presence of R,â-unsaturated-alkoxycarbene ligands
1
in these compounds is inferred from their H and 13C-
1
{1H} NMR spectra. In the H NMR spectrum of 17, the
unsaturated η1-carbon ligand gives rise to two singlets
at 6.47 and 4.26 ppm, which correspond to the CHd and
OCH3 protons, respectively, while, in the 13C{1H} NMR
spectrum, the most noticeable signals are two broad
resonances at 305.0 and 136.7 ppm due to the RudC
and CHd carbon atoms and a singlet at 66.8 ppm, which
was assigned to the carbon atom of the methoxy group.
In the 1H NMR spectrum of 18, the alkoxycarbene
ligand displays a singlet at 6.56 ppm (CHd), a quartet
at 4.73 ppm (OCH2), and a triplet at 1.52 ppm (CH3),
while, in the 13C{1H} NMR spectrum, the RudC and
CHd carbon atoms appear at 303.8 and 137.0 ppm, as
broad resonances, and the carbon atoms of the ethoxy
group are observed at 77.2 (OCH2) and 14.6 (CH3) ppm,
as singlets.
1-ethynyl-1-cyclohexanol. In addition, MO calculations
on the model compound [Mn(η5-C5H5)(CdCdCH2)(CO)2]
have shown that the CR and Cγ carbon atoms of
allenylidene ligands are electrophilic centers, while the
Câ carbon atom is nucleophilic.32 According to this, the
addition of water to allenylidene intermediates affords
the R,â-unsaturated hydroxycarbene derivatives 12 and
14.
Hydroxycarbene complexes have been previously pro-
posed as reaction intermediates in the transformation,
in the presence of water, of cationic vinylidene com-
pounds into alkyl-carbonyl derivatives.33 The reactions
of alkyn-1-ols with metallic fragments to give R,â-
unsaturated hydroxycarbene compounds have no pre-
cedent. As has been above mentioned, the formation
of these complexes suggests that the dehydration of the
hydroxyvinylidene intermediates leads to allenylidenes,
although small amounts of a vinylvinylidene complex
can be formed from the reaction of 5 with 1-ethynyl-1-
cyclohexanol, as it is supported by the isolation of the
alkynyl complex 16. This compound is most probably
the result of the deprotonation of a vinylvinylidene
complex in the chromatography column. Dixneuf has
closely studied related reactions of alkynols with
[RuCl2(η6-C6H6)(PMe3)] in MeOH/NH4PF6. In agree-
ment with the results collected in Scheme 2, for 1,1-
diphenyl-2-propyn-1-ol, the allenylidene complex [RuCl-
(η6-C6H6){CdCdCPh2}(PMe3)]PF6 was isolated, whereas
for 1,1-dimethyl-2-propyn-1-ol and 1-ethynyl-1-cyclo-
hexanol, the R,â-unsaturated methoxycarbene com-
pounds [RuCl(η6-C6H6){C(OMe)CHdCR2}(PMe3)]PF6 (R
) Me, R2 ) C5H10) were obtained exclusively, via
allenylidene intermediates.5 On the other hand, the
The reactivity previously reported toward methanol
and ethanol of the allenylidene ligands bonded to
ruthenium(II) fragments depends upon the remaining
ligands of the complexes. Thus, in agreement with the
behavior of 9, the allenylidene ligands of compounds of
the type [RuCl(η6-arene){CdCdCR2}(PR3)]+ add alco-
hols at the CR and Câ atoms to afford R,â-unsaturated-
alkoxycarbene derivatives,5g whereas the cumulene
ligands stabilized by the electron-rich fragments [Ru-
(η5-C5H5)(PMe3)2]+,31a [RuCl(dppm)2]+ (dppm ) bis-
(diphenylphosphino)methane),34 [RuCl(NP3)]+ (NP3
)
N(CH2CH2PPh2),35 and [Ru(η5-C9H7)L2]+ (L2 ) 2 PPh3,
dppm, dppe)4b are inert. This suggest that the electronic
nature of unit [Ru(η5-C5H5)(CO)(PPri )]+ is similar to
3
that of the fragments [RuCl(η6-arene)(PR3)]+.
Treatment of 17 and 18 with sodium methoxide in
tetrahydrofuran produces the deprotonation of the ole-
finic groups of the alkoxycarbene ligands to give the
allenyl derivatives 19 and 20 (Scheme 4). Complex 19
was isolated as a pale yellow solid in 80% yield, and
complex 20 as a yellow oil in 93% yield. Characteristic
spectroscopic features of 19 and 20 are the CdCdC
stretching frequency in the IR spectra at 1871 (19) and
1890 (20) cm-1 and the three resonances in the 13C{1H}
NMR spectra at 197.8 (s), 138.1 (d, J (PC) ) 13.6 Hz),
and 107.7 (s) (19) and 197.6 (s), 135.7 (d, J (PC) ) 13.3
Hz), and 106.6 (s) (20) ppm for the Câ, CR, and Cγ allenyl
carbon atoms, respectively.
There are a variety of η1-allenyl transition-metal
compounds known, but most of them have been pre-
pared by oxidative addition of propargyl or allenyl
halides to electron-rich metal precursors.36 Recently,
Werner has observed that the alkynyl(hydrido)osmium
complexes [OsHCl{CtCC(OH)Ph2}(NO)(PR3)2] react with
acidic alumina to afford the allenylosmium(II) deriva-
behavior of the [Ru(η5-C5H5)(CO)(PPri )]+ fragment
3
contrasts with that previously observed for the related
osmium fragment [Os(η5-C5H5)(CO)(PPri )]+, which re-
3
acts with 1-ethynyl-1-cyclohexanol to afford the vinylvi-
nylidene [Os(η5-C5H5){CdC(H)CdCH(CH2)3CH2}(CO)-
(PPri )]+ in 78% yield.21 Vinylvinylidene products are
3
also obtained exclusively from reactions of the rich-
electron fragment [Ru(η5-C5H5)(PMe3)2]+ with alkyn-1-
ols containing hydrogen atoms adjacent to the hydroxy
group.3b
(32) (a) Schilling, B. E. R.; Hoffmann, R.; Lichtenberger, D. L. J .
Am. Chem. Soc. 1979, 101, 585. (b) Berke, H.; Huttner, G.; Von Seyerl,
J . Z. Naturforsch., B 1981, 36, 1277.
(33) (a) Bruce, M. I.; Swincer, A. G. Aust. J . Chem. 1980, 33, 1471.
(b) Gamasa, M. P.; Gimeno, J .; Lastra, E.; Lanfranchi, M.; Tiripicchio,
A. J . Organomet. Chem. 1992, 430, C39.
(34) Pirio, N.; Touchard, D.; Toupet, L.; Dixneuf, P. H. J . J . Chem.
Soc., Chem. Commun. 1991, 980.
(35) Wolinska, A.; Touchard, D.; Dixneuf, P. H.; Romero, A. J .
Organomet. Chem. 1991, 420, 217.
+
+

[RuHCl(CO)(PPri )2]
Organometallics, Vol. 15, No. 15, 1996 3429
3
Sch em e 4
Sch em e 5
tives [OsCl2(CHdCdCPh2}(NO)(PR3)2] (PR3 ) PPri ,
3
PPhPri ).37 Fischer has also reported that the alle-
2
nylidene complex [Cr(CO)5{CdCdC(C6H4NMe2-p)2}] adds
phosphines at the CR carbon atom to give ylide com-
plexes [Cr(CO)5{η1-C(PR3)dCdC(C6H4NMe2-p)2}] (PR3
) PMe3, PHPh2, PH2Mes). At room temperature, the
complex [Cr(CO)5{η1-C(PHPh2)dCdC(C6H4NMe2-p)2}]
rearranges to [Cr(CO)5{PPh2[CHdCdC(C6H4NMe2-
p)2]}].38
Attempts to obtain (alkoxyallenyl)ruthenium(II) com-
pounds by attack of alkoxy groups at the CR carbon of
an allenylidene ligand have been unsuccessful. Thus,
Gimeno has found that CH3O- is added to the Cγ carbon
atom of the allenylidene ligand of the complexes [Ru-
(η5-C9H7)(CdCdCPh2)L2]PF6 (L2 ) 2 PPh3, dppm,
dppe).4b In agreement with this, we have recently
observed that complex 9 reacts with CH3O- to afford
[Ru(η5-C5H5){CtCC(OMe)Ph2}(CO)(PPri3)].39 This seems
to suggest that in order to obtain (alkoxyallenyl)-
ruthenium(II) derivatives, route a of Scheme 5 is more
useful than route b.
In a similar way to that shown in route a of Scheme
5, it is also possible to obtain (alkylthio)allenyl and
iminoallenyl derivatives (Scheme 4). Treatment of a
dichloromethane solution of 9 with the stoichiometric
amount of 1-propanethiol leads to the R,â-unsaturated
(alkylthio)carbene complex 21, which reacts with so-
dium methoxide to afford the (alkylthio)allenyl 22.
Similarly, the reaction of 9 with benzophenone imine
leads to 23, which by reaction with sodium methoxide
gives 24.
Complex 21 was isolated as an orange solid in 98%
yield. In the 1H NMR spectrum of 21, the most
noticeable resonances are a singlet at 6.91 ppm due to
the CHd proton and the signals corresponding to the
thiol group, which appear at 3.34 (SCH2-), 1.76
(-CH2-), and 1.01 (-CH3) ppm. The 13C{1H} NMR
spectrum shows a doublet at 311.6 ppm with a P-C
coupling constant of 6.8 Hz assigned to the RudC
carbon atom and two singlets at 142.9 and 138.1 due to
the CHd and dCPh2 carbon atoms of the olefinic group
of the R,â-unsaturated η1-carbon ligand.
Complex 22 was isolated as a yellow solid in a 68%
yield. Characteristic spectroscopic features of 22 are
the CdCdC stretching frequency in the IR spectrum
at 1887 cm-1 and the three resonances in the 13C{1H}
NMR spectrum at 195.9, 103.4, and 90.1 ppm for the
Câ, Cγ, and CR allenyl carbon atoms. The first and the
second resonances appear as singlets, whereas the third
one appears as a doublet with a P-C coupling constant
of 11.3 Hz.
(36) (a) J acobs, T. L. The Chemistry of the Allenes; Landor, S. R.,
Ed.; Academic Press: London, 1982; Vol. 2, p 334. (b) Schuster, H. F.;
Coppola, G. M. Allenes in Organic Chemistry; Wiley-Interscience: New
York, 1984. (c) Wojcicki, A.; Shuchart, C. E. Coord. Chem. Rev. 1990,
105, 35. (d) Keng, R.-S.; Lin, Y.-C. Organometallics 1990, 9, 289. (e)
Shuchart, C. E.; Willis, R. R.; Wojcicki, A. J . Organomet. Chem. 1992,
424, 185. (f) Wouters, J . M. A.; Klein, R. E.; Elsevier, C. J .; Ha¨ming,
L.; Stam, C. H. Organometallics 1994, 13, 4586.
(37) Werner, H.; Flu¨gel, R.; Windmu¨ller, B.; Michenfelder, A.; Wolf,
J . Organometallics 1995, 14, 612.
(38) Fischer, H.; Reindl, D.; Troll, C.; Leroux, F. J . Organomet.
Chem. 1995, 490, 221.
Complex 23 was isolated as an orange solid in 91%
yield and characterized by elemental analysis, IR and
(39) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.;
On˜ate, E.; Oro, L. A. Manuscript in preparation.
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3430 Organometallics, Vol. 15, No. 15, 1996
Esteruelas et al.
Cl(CO)(Me2Hpz)(PPh3)2] (2.063(7) Å),43 and [Ru{(E)-
CHdCHCMe3}(CO){NHdC(Me)(Me2pz)}(PPh3)2]PF6
(2.067(8) Å)44 and is slightly shorter than the Ru-C
bond in the complexes [Ru(η5-C5H5){C(dCHPh)OPri}-
(CO)(PPh3)] (2.103(6) Å)9 and Ru{C(dCHCO2CH3)CO2-
CH3}(CO)(NCCH3)2(PPh3)2]ClO4 (2.12(5) Å),45 where a
Ru-C(sp2) single bond has been also proposed. The
C(1)-N distance (1.283(9) Å) is statistically identical
with the N-C(16) bond length (1.252(9) Å), and they
are consistent with those found in the 2-azaallenyl
complexes [Cr{C(OEt)dNdCBut }(CO)5] (1.272(5) and
2
1.264(5) Å)46 and [Cr{C(Ph)dNdCHPh}(CO)5] (1.260-
(4) and 1.265(4) Å)47 and in organic azaallenium cations
(between 1.23 and 1.33 Å).48 The C(1)-C(2) (1.486(9)
Å) and C(2)-C(3) (1.333(10) Å) distances also are in
agreement with the sample mean of carbon-carbon
bond lengths for single C(sp2)-C(sp2) (1.48(1) Å) and
double C(sp2)-C(sp2) (1.32(1) Å) bonds.49 In accordance
with the sp2 hybridization for C(1), the angles Ru-C(1)-
C(2) and Ru-C(1)-N are 120.8(4) and 123.3(5)°, re-
spectively. The angle C(1)-N-C(16) is 149.9(6)°, indi-
cating that the fragment CdNdC is not strictly linear.
Although the related angles in the complexes [Cr-
F igu r e 3. Molecular diagram of complex [Ru(η5-C5H5)-
{C(CHdCPh2)dNdCPh2}(CO)(PPri3)]BF4 (23). Thermal el-
lipsoids are shown at 50% probability.
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e Com p lex
[Ru (η5-C5H5){C(CHdCP h 2)dNdCP h 2}(CO)(P P r i3)]BF 4
(23)
{C(OEt)dNdC(CBut ) }(CO)5] and [Cr{C(Ph)dNdC-
2 2
HPh}(CO)5] are 171.7(4)46 and 174.3(3)°,47 close to the
ideal value of 180°, angular distortions in this type of
systems are not unusual. Thus, we note that for organic
2-azaallenium cations with CdN distances similar to
those of 23, the C-N-C angles are between 156 and
160°.48d Substituted 2-azaallenium cations are flexible,
assuming conformations which are mainly determined
by steric and electronic demands of substituents.48 In
addition, it should be mentioned that there seems to
exist a rough linear proportionality between the C-N-C
bond angle (R) and the wave number of the antisym-
Ru-P
2.353(2)
2.027(7)
1.834(7)
2.244(7)
2.251(7)
2.253(8)
2.253(7)
2.210(7)
1.486(9)
C(2)-C(3)
C(3)-C(4)
C(3)-C(10)
N-C(1)
1.333(10)
1.485(9)
1.485(10)
1.283(9)
1.252(9)
1.486(8)
1.478(9)
1.136(9)
Ru-C(1)
Ru-C(29)
Ru-C(39)
Ru-C(40)
Ru-C(41)
Ru-C(42)
Ru-C(43)
C(1)-C(2)
N-C(16)
C(16)-C(17)
C(16)-C(23)
O(1)-C(29)
P-Ru-C(1)
98.1(2)
Ru-C(1)-N
123.3(5)
115.6(5)
129.9(6)
119.0(6)
125.7(6)
149.9(6)
118.9(6)
120.7(6)
P-Ru-C(29)
90.8(2)
124.2(2)
89.2(3)
121.2(3)
124.3(3)
175.4(6)
120.8(4)
N-C(1)-C(2)
P-Ru-G(1)a
C(1)-C(2)-C(3)
C(2)-C(3)-C(4)
C(2)-C(3)-C(10)
C(1)-N-C(16)
N-C(16)-C(17)
N-C(16)-C(23)
C(1)-Ru-C(29)
C(1)-Ru-G(1)a
C(29)-Ru-G(1)a
Ru-C(29)-O(1)
Ru-C(1)-C(2)
metric stretching vibration of this unit (R ) 0.165 νas
-
147). Increasing the C-N-C bond angle decreases the
CdN distance, enhancing the force constant for the
stretching vibration.48d According to this, the IR spec-
trum of 23 in Nujol shows a νas(CdNdC) band at 1813
cm-1, which gives rise to a value for the C-N-C angle
of 152.0°, in good agreement with that determined by
X-ray diffraction (149.9(6)°).
a
G(1) is the midpoint of the C(39)-C(43) Cp ligand.
1H, 31P{1H}, and 13C{1H} NMR spectroscopy, and X-ray
diffraction. A view of the molecular geometry is shown
in Figure 3. Selected bond distances and angles are
listed in Table 2. As for 11, the geometry around the
ruthenium center is close to octahedral with the cyclo-
pentadienyl ligand occupying three sites of a face, and
the angles formed by the triisopropylphosphine, the
carbonyl group, and the unsaturated η1-carbon ligand
are close to 90°.
In solution, the presence of an R,â-unsaturated 2-azaal-
lenyl ligand in 23 is mainly supported by the 13C{1H}
NMR spectrum, which shows a doublet due to C(1) at
207.1 (J (PC) ) 9.0 Hz) ppm.
Transition metal 2-azaallenyl complexes are rare;
(42) Torres, M. R.; Santos, A.; Perales, A.; Ros, J . J . Organomet.
Chem. 1988, 353, 221.
(43) Romero, A.; Santos, A.; Vegas, A. Organometallics 1988, 7, 1988.
(44) Lo´pez, J .; Santos, A.; Romero, A.; Echavarren, A. M. J .
Organomet. Chem. 1993, 443, 221.
(45) Lo´pez, J .; Romero, A.; Santos, A.; Vegas, A.; Echavarren, A.
M.; Noheda, P. J . Organomet. Chem. 1989, 373, 249.
(46) Seitz, F.; Fischer, H.; Riede, J . J . Organomet. Chem. 1985, 287,
87.
(47) Aumann, R.; Althaus, S.; Kru¨ger, C.; Betz, P. Chem. Ber. 1989,
122, 357.
(48) (a) Al-Talib, M.; J ibril, I.; Wu¨rthwein, E.-U.; J ochims, J . C.;
Huttner, G. Chem. Ber. 1984, 117, 3365. (b) J ochims, J . C.; Abu-El-
Halawa, R.; J ibril, I.; Huttner, G. Chem. Ber. 1984, 117, 1900. (c) Al-
Talib, M.; J ochims, J . C. Chem. Ber. 1984, 117, 3222. (d) Al-Talib, M.;
J ibril, I.; Huttner, G.; J ochims, J . C. Chem. Ber. 1985, 118, 1876. (e)
Wu¨rthwein, E.-U.; Kupfer, R.; Allmann, R.; Nagel, M. Chem. Ber. 1985,
118, 3632. (f) Al-Talib, M.; J ochims, J . C.; Zsolnai, L.; Huttner, G.
Chem. Ber. 1985, 118, 1887. (g) Kupfer, R.; Wu¨rthwein, E.-U.; Nagel,
M.; Allmann, R. Chem. Ber. 1985, 118, 643. (h) Krestel, M.; Kupfer,
R.; Allmann, R.; Wu¨rthwein, E.-U. Chem. Ber. 1987, 120, 1271.
(49) Orpen, A. G.; Brammer, L.; Allen, F. H.; Kennard, O.; Watson,
D. G.; Taylor, R. J . Chem. Soc., Dalton Trans. 1989, S1.
The unsaturated η1-carbon ligand can be described
as an R,â-unsaturated-2-azaallenyl unit. Thus, the Ru-
C(1) distance (2.027(7) Å) is similar to those found in
the alkenyl complexes [Ru{C(dCHPh)OC(O)CH3}(CO)-
{η1-OC(CH3)2}(PPri ) ]+ (1.967(8) Å),6 [Ru(η5-C5H5){C-
3 2
(dCHCO2CH3)OC(O)CH3}(PPh3)] (2.002(2) Å),40 [Ru{C-
(dC(CO2CH 3)CH dCH C(CH 3)3)C(O)OCH 3}Cl(CO)-
(PPh3)2] (2.03(1) Å),41 [Ru{(E)-CHdCHC3H7}Cl(CO)(Me2-
Hpz)(PPh3)2] (2.05(1) Å),42 [Ru{(E)-CHdCHCMe3}-
(40) Daniel, T.; Mahr, N.; Braun, T.; Werner, H. Organometallics
1993, 12, 1475.
(41) Torres, M. R.; Vegas, A.; Santos, A.; Ros, J . J . Organomet. Chem.
1987, 326, 413.
+
+

[RuHCl(CO)(PPri )2]
Organometallics, Vol. 15, No. 15, 1996 3431
3
indeed, 23 is the only example for ruthenium. Apart
from 23, the only other 2-azaallenyl examples are the
derivatives [Cr{C(Ph)dNdCR2}(CO)5], [Cr{C(CH3)d
NdCR2}(CO)5],47 and [M{C(OEt)dNdCR2}(CO)5] (M )
Cr, W).46 Complex 23 is also significant because it is
prepared from an allenylidene compound, while the
complexes [Cr{C(Ph)dNdCR2}(CO)5] and [Cr{C(CH3)d
NdCR2}(CO)5] were obtained from aminocarbene com-
pounds by condensation of the NH2 group with organic
carbonyl compounds in the presence of NEt3 and POCl3/
NEt3,47 and the derivatives [M{C(OEt)dNdCR2}(CO)5]
(M ) Cr, W) by successive reaction of M(CO)6 with Na-
[NdCR2] and [Et3O]BF4.46
In addition, it should be pointed out that a difference
in the reactivity exists between the allenylidene frag-
ment of 9 and the vinylidene ligands of [M(η5-C5H5)-
(dCdCHR)(CO)2] (M ) Mn, Re). While 9 reacts with
benzophenone imine to give the 2-azaallenyl complex
23, the reactions of the vinylidene derivatives afford
iminocarbene complexes.50
The iminoallenyl complex 24 was isolated as a yellow
solid in 92% yield. Similarly to the alkoxyallenyl (19
and 20) and the (alkylthio)allenyl (22) derivatives, the
most characteristic spectroscopic features of 24 are the
CdCdC stretching frequency in the IR spectrum, which
is observed at 1888 cm-1, and the three resonances in
the 13C{1H} NMR spectrum at 194.7 (s), 114.9 (d, J (PC)
) 12.9), and 102.3 (s) ppm for the Câ, CR, and Cγ allenyl
carbon atoms, respectively. Complex 24 is also signifi-
cant because, as far as we know, iminoallenyl complexes
have not been previously reported.
The allenylidene ligand of the complex [Ru(η5-C5H5)-
(CdCdCPh2)(CO)(PPri )]BF4 also shows a markedly
3
different reactivity with that observed for the alle-
nylidene ligands stabilized by the fragments [Ru(η5-
C5H5)(PMe3)2]+ and [Ru(η5-C9H7)L2]+ (L2 ) 2 PPh3,
dppm, dppe). While the complex [Ru(η5-C5H5)(Cd
CdCPh2)(CO)(PPri )]BF4 reacts with alcohols to give
3
R,â-unsaturated alkoxycarbene derivatives, the latter
are inert.4b,31a The allenylidene complex [Ru(η5-C5H5)-
(CdCdCPh2)(CO)(PPri )]BF4 also reacts with water,
3
thiols, and benzophenone imine to afford R,â-unsatur-
ated-hydroxycarbene, -alkoxycarbene, and -2-azaallenyl
compounds, respectively. By deprotonation, the hy-
droxycarbene compounds give acyl derivatives, and the
alkoxycarbene, (alkylthio)carbene, and 2-azaallenyl com-
plexes yield allenyl derivatives.
Exp er im en ta l Section
All reactions were carried out with rigorous exclusion of air
using Schlenk tube techniques. Solvents were dried by the
usual procedures and distilled under argon prior to use. The
reagents dimethyl acetylenedicarboxylate (Merk), 1,1-diphen-
yl-2-propyn-1-ol (ABCR), 2-propyn-1-ol (Aldrich), 1-ethynyl-1-
cyclohexanol (Fluka), 1-propanethiol (Fluka), and benzophe-
none imine (Aldrich) were obtained from commercial sources,
as indicated, and used without further purification. The
starting material [RuHCl(CO)(PPri )2] (1) was prepared by a
3
published method.10
NMR spectra were recorded on either a Varian UNITY 300
or a Bruker 300 AXR spectrometer. Chemical shifts are
expressed in ppm upfield from Me4Si (1H and 13C) and 85%
H3PO4 (31P). Coupling constants, J , are given in Hz. The T1
experiments were performed on a Varian UNITY 300 spec-
trophotometer with a standard 180°-τ-90° pulse sequence.
IR spectra were run on a Perkin-Elmer 883 or a Nicolet 550
spectrophotometer (Nujol mulls on polyethylene sheets). Ele-
mental analyses were carried out on a Perkin-Elmer 2400
CHNS/O analyzer. MS data were recorded on a VG Autospec
double-focusing mass spectrometer operating in the positive
mode; ions were produced with the standard Cs+ gun at ca.
30 kV, and 3-nitrobenzyl alcohol (NBA) was used as the
matrix.
Con clu d in g Rem a r k s
This study has revealed that the five-coordinate
complex [RuHCl(CO)(PPri ) ] is a useful starting mate-
3 2
rial for the preparation of new cyclopentadienylruthe-
nium compounds containing unsaturated η1-carbon
ligands, which includes allenylidene and R,â-unsatur-
ated-hydroxycarbene, -acyl, -alkoxycarbene, -(alkylthio)-
carbene, -2-azaallenyl, alkoxyallenyl, (alkylthio)allenyl,
and iminoallenyl derivatives. Thus, it reacts with
cyclopentadiene to give [RuH(η5-C5H5)(CO)(PPri3)]. Ace-
tone solutions of this complex react with HBF4‚Et2O to
afford the solvated compound [Ru(η5-C5H5)(CO){η1-OC-
P r ep a r a tion of [Ru H(η5-C5H5)(CO)(P P r i3)] (2). An ex-
cess of freshly distilled cyclopentadiene (3 mL, 44.48 mmol)
was added to a suspension of 1 (1.0 g, 2.06 mmol) in 20 mL of
methanol. The mixture was stirred at reflux temperature for
4 h, undergoing a color change of orange to yellow. The
solution was filtered and evaporated to dryness. The residue
was treated with 20 mL of n-pentane, and the mixture was
(CH3)2}(PPri )]BF4, which is a novel precursor for the
3
preparation of the unsaturated η1-carbon complexes.
The chemical behavior of the fragment [Ru(η5-C5H5)-
filtered to eliminate [HPPri ]Cl. The yellow solution was
3
(CO)(PPri )]+ has some characteristics in common with
concentrated to about 3 mL and cooled to 195 K. A cream
colored solid precipitated, which was separated by decantation,
washed with cold hexane, and dried in vacuo. The solid was
recrystallized from methanol to give white crystals which were
separated by decantation, washed with cold methanol, and
3
the arene systems [RuCl(η6-arene)(PR3)]+ but marked
differences with the chemical behavior of the related
osmium fragment [Os(η5-C5H5) (CO)(PPri )]+ and the
3
more electron-rich half-sandwich ruthenium units [Ru-
(η5-C5H5)(PMe3)2]+ and [Ru(η5-C9H7)(PR3)2]+. Thus, the
acetone complex [Ru(η5-C5H5){η1-OC(CH3)2}(CO)(PPri3)]-
BF4 reacts with alkyn-1-ols to afford R,â-unsaturated-
hydroxycarbene compounds via allenylidene interme-
diates, whereas, under similar experimental conditions,
dried in vacuo. Yield: 630 mg (86%). Anal. Calcd for C15
-
H
27OPRu: C, 50.69; H, 7.66. Found: C, 51.08; H, 7.94. IR
(Nujol, cm-1): ν(RuH) 1985 m, ν(CO) 1920 vs, br. 1H NMR
(300 MHz, 293 K, C6D6) δ 4.87 (s, 5H, Cp), 1.73 (m, 3H,
PCHCH3), 1.01 (dd, 9H, J (HH) ) 7.1, J (PH) ) 10.1, PCHCH3),
0.96 (dd, 9H, J (HH) ) 7.1, J (PH) ) 9.8, PCHCH3), -12.05 (d,
1H, J (PH) ) 30.7, RuH). 31P{1H} NMR (121.4 MHz, 293 K,
C6D6): δ 91.6 s.
the fragments [Os(η5-C5H5)(CO)(PPri )]+ and [Ru(η5-
3
C5H5)(PMe3)2]+ afford allenylidene derivatives or vi-
nylvinylidene compounds when the alkyn-1-ols have
hydrogen atoms adjacent to the hydroxy group.
P r ep a r a tion of [Ru (η5-C5H5)(η2-H2)(CO)(P P r i3)]BF 4 (3)
a n d [Ru H2(η5-C5H5)(CO)(P P r i3)]BF 4 (4). A solution of 2 (15
mg, 0.042 mmol) in 0.5 mL of CD2Cl2 in an NMR tube was
treated with a stoichiometric amount of tetrafluoroboric acid
(5.7 µL, 0.042 mmol, 54% in diethyl ether). The NMR tube
was sealed under argon and measurements initiated im-
(50) Terry, M. R.; Mercando, L. A.; Kelley, C.; Geoffroy, G. L.;
Nombel, P.; Lugan, N.; Mathieu, R.; Ostrander, R. L.; Owens-
Waltermire, B. E.; Rheingold, A. L. Organometallics 1994, 13, 843.
+
+

3432 Organometallics, Vol. 15, No. 15, 1996
Esteruelas et al.
mediately. Spectroscopic data for 3: 1H NMR (300 MHz, 293
K, CD2Cl2) δ 5.67 (s, 5H, Cp), 2.40 (m, 3H, PCHCH3), 1.35 (dd,
9H, J (HH) ) 4.4, J (PH) ) 7.1, PCHCH3), 1.30 (dd, 9H, J (HH)
) 4.7, J (PH) ) 7.1, PCHCH3), -7.95 (br, 2H, Ru(η2-H2)); T1
(Ru(η2-H2), 300 MHz, CD2Cl2) ) 34 ms (253 K), 22 ms (233
K), 13 ms (213 K), 6 ms (193 K); 31P{1H} NMR (121.4 MHz,
293 K, CD2Cl2) δ 81.4 (br). Spectroscopic data for 4: 1H NMR
(300 MHz, 293 K, CD2Cl2) δ 5.80 (s, 5H, Cp), -7.17 (d, 2H,
J (PH) ) 19.8, RuH2); 31P{1H} NMR (121.4 MHz, 293 K, CD2-
Cl2) δ 86.7 (s).
5.57. IR (Nujol, cm-1): ν(CO) 2025 vs, ν(CtC) 1869 s, ν(CdO)
1717, 1705 both s, ν(C-O) 1248 s, ν(BF4) 1056 vs, br. 1H NMR
(300 MHz, 293 K, CDCl3) δ 5.91 (s, 5H, Cp), 3.96, 3.89 (both
br s, 6H, CO2CH3), 2.52 (m, 3H, PCHCH3), 1.26 (dd, 9H, J (HH)
) 6.9, J (PH) ) 15.4, PCHCH3), 1.18 (dd, 9H, J (HH) ) 6.9,
J (PH) ) 15.9, PCHCH3); 31P{1H} NMR (121.4 MHz, 293 K,
CDCl3) δ 65.2 s; 13C{1H} NMR (75.4 MHz, 293 K, CDCl3, plus
APT) δ 199.0 (-, d, J (PC) ) 17.5, CO), 161.9, 158.2 (-, both
br s, CO2CH3), 92.3 (+, s, Cp), 73.4, 72.5 (-, both br s, CtC),
54.4, 54.3 (+, both s, CO2CH3), 28.0 (+, d, J (PC) ) 24.4,
PCHCH3), 19.7 (+, s, PCHCH3), 19.4 (+, d, J (PC) ) 1.9,
PCHCH3). MS (FAB+): m/z ) 497 (M+).
P r ep a r a tion of [Ru D(η5-C5H5)(CO)(P P r i3)] (2d ) a n d
[Ru (η5-C5H5)(η2-HD)(CO)(P P r i3)]BF 4 (3d ). A solution of 2
(11 mg, 0.031 mmol) in 0.5 mL of CD3OD in an NMR tube
sealed under argon was heated at 338 K for 24 h. Spectro-
scopic data for 2d : 1H NMR (300 MHz, 293 K, CD3OD) δ 4.95
(s, Cp), 1.95 (m, 3H, PCHCH3), 1.06 (dd, 18H, J (HH) ) 7.2,
J (PH) ) 13.9, PCHCH3); 31P{1H} NMR (121.4 MHz, 293 K,
CD3OD) δ 91.9 (1:1:1 t, J (PD) ) 4.4). The solvent was removed
in vacuo, and the residue was dissolved in 0.5 mL of CDCl3,
followed by treatment with the stoichiometric amount of
tetrafluoroboric acid (4.2 µL, 0.031 mmol, 54% in diethyl ether).
The NMR tube was sealed under argon, and measurements
were made immediately. Spectroscopic data for 3d : 1H NMR
(300 MHz, 213 K, CDCl3) δ 5.63 (s, Cp), 2.32 (m, 3H, PCHCH3),
1.34 (dd, 9H, J (HH) ) 4.9, J (PH) ) 7.1, PCHCH3), 1.29 (dd,
9H, J (HH) ) 4.9, J (PH) ) 7.1, PCHCH3), -7.87 (1:1:1 t, 1H,
1J (HD) ) 28.5, Ru(η2-HD); 31P{1H} NMR (121.4 MHz, 293 K,
CDCl3) δ 78.6 (br s).
P r ep a r a tion of [Ru (η5-C5H5)Cl(CO)(P P r i3)] (8). A solu-
tion of 5 (300 mg, 0.60 mmol) in 5 mL of methanol was treated
with NaCl (35 mg, 1.20 mmol). The solution was stirred at
room temperature for 5 h, and the solvent was removed in
vacuo. The residue was treated with 10 mL of dichlo-
romethane, and the mixture was filtered to eliminate the
NaBF4 and excess of NaCl. The solvent was evaporated to
dryness, and the residue was washed with n-pentane to afford
a yellow solid which was dried under vacuum. Yield: 190 mg
(81%). Anal. Calcd for C15H26ClOPRu: C, 46.21; H, 6.72.
Found: C, 45.82; H, 6.38. IR (Nujol, cm-1): ν(CO) 1927 vs,
ν(RuCl) 295 s. 1H NMR (300 MHz, 293 K, CDCl3) δ 5.08 (s,
5H, Cp), 2.47 (m, 3H, PCHCH3), 1.27 (dd, 9H, J (HH) ) 7.1,
J (PH) ) 14.5, PCHCH3), 1.20 (dd, 9H, J (HH) ) 7.1, J (PH) )
13.2, PCHCH3); 31P{1H} NMR (121.4 MHz, 293 K, CDCl3) δ
66.4 s. MS (FAB+): m/z ) 390 (M+).
Reaction of [Ru (η5-C5H5)(η2-H2)(CO)(P P r i )]BF4 (3) with
P r ep a r a tion of [Ru (η5-C5H5)(CdCdCP h 2)(CO)(P P r i3)]-
BF 4 (9). A solution of 5 (100 mg, 0.20 mmol) in 5 mL of
dichloromethane was treated with 1,1-diphenyl-2-propyn-1-
ol (50.0 mg, 0.24 mmol). Immediately, the color turned from
orange to dark red, and the solution was concentrated almost
to dryness. By slow addition of diethyl ether a dark red solid
precipitated. The solid was washed with diethyl ether and
3
NEt3. Addition of a stoichiometric amount of NEt3 to a
chloroform-d1 solution of 3 in an NMR tube afforded 2
immediately, as shown by 1H and 31P{1H} NMR spectroscopy.
1
i
5
P r ep a r a tion of [Ru (η -C5H5)(CO){η -OC(CH3)2}(P P r 3)]-
BF 4 (5). A solution of 2 (600 mg, 1.69 mmol) in 5 mL of acetone
was treated with tetrafluoroboric acid (253.7 µL, 1.86 mmol,
54% in diethyl ether). Immediately the color turned from pale
yellow to orange, and the solution was concentrated almost to
dryness. By addition of diethyl ether an orange solid precipi-
tated. The solid was washed with diethyl ether and dried in
vacuo. Yield: 838 mg (99%). Anal. Calcd for C18H32BF4O2-
PRu: C, 43.30; H, 6.46. Found: C, 43.29; H, 6.59. IR (Nujol,
cm-1): ν(CO) 1958 vs, ν(CdO) 1652 s, ν(BF4) 1053 vs, br. 1H
NMR (300 MHz, 293 K, CD2Cl2) δ 5.28 (s, 5H, Cp), 2.44 (s,
{η1-OC(CH3)2}), 2.42 (m, 3H, PCHCH3), 1.26 (dd, 9H, J (HH)
) 7.1, J (PH) ) 14.7, PCHCH3), 1.24 (dd, 9H, J (HH) ) 7.1,
J (PH) ) 13.9, PCHCH3); 31P{1H} NMR (121.4 MHz, 293 K,
CD2Cl2) δ 64.6 s; 13C{1H} NMR (75.4 MHz, 293 K, CDCl3) δ
230.4 (s, {η1-OC(CH3)2}), 203.8 (d, J (PC) ) 18.4, CO), 83.7 (s,
Cp), 32.7 (s, {η1-OC(CH3)2}), 26.5 (d, J (PC) ) 22.6, PCHCH3),
19.6, (s, PCHCH3), 19.4 (d, J (PC) ) 1.0, PCHCH3).
dried in vacuo. Yield: 132 mg (87%). Anal. Calcd for C30
-
H
36BF4OPRu: C, 57.06; H, 5.74. Found: C, 57.02; H, 5.65.
IR (Nujol, cm-1): ν(CdCdC) 2002 s, ν(CO) 1953 vs, ν(Ph) 1587
m, ν(BF4) 1076 vs, br. 1H NMR (300 MHz, 293 K, CDCl3) δ
7.77 (m, 4H, o-Ph), 7.70 (m, 2H, p-Ph), 7.51 (m, 4H, m-Ph),
5.81 (s, 5H, Cp), 2.34 (m, 3H, PCHCH3), 1.22 (dd, 9H, J (HH)
) 7.1, J (PH) ) 10.4, PCHCH3), 1.17 (dd, 9H, J (HH) ) 7.1,
J (PH) ) 9.6, PCHCH3); 31P{1H} NMR (121.4 MHz, 293 K,
CDCl3) δ 79.8 s; 13C{1H} NMR (75.4 MHz, 293 K, CDCl3) δ
288.3 (d, J (PC) ) 13.8, CR), 199.9 (d, J (PC) ) 15.2, CO), 188.5
(d, J (PC) ) 2.3, Câ), 164.4 (s, Cγ), 141.7 (s, Cipso), 133.8 (s, p-Ph),
132.1, 129.4 (both s, o-Ph, m-Ph), 91.4 (s, Cp), 28.8 (d, J (PC)
) 25.3, PCHCH3), 19.9 (s, PCHCH3), 19.5 (d, J (PC) ) 0.9,
PCHCH3). MS (FAB+): m/z ) 545 (M+).
P r ep a r a tion of [Ru (η5-C5H5){C(OH)CH dCP h 2}(CO)-
(P P r i3)]BF 4 (10). Rou te a . A solution of 9 (150 mg, 0.24
mmol) in 5 mL of tetrahydrofuran was treated with water (120
µL, 6.67 mmol). After the solution was stirred for 2 h, the
color turned from dark red to orange and the solvent was
removed in vacuo. The residue was washed with diethyl ether
to give a yellow solid, the solvent was decanted, and the
product was dried in vacuo. Yield: 120 mg (78%).
P r ep a r a tion of [Ru (η5-C5H5)(CO)2(P P r i3)]BF 4 (6). CO
was bubbled through a stirred solution of 5 (100 mg, 0.2 mmol)
in 10 mL of dichloromethane for 35 min. The color turned
from orange to pale yellow, and the solution was concentrated
almost to dryness. By slow addition of diethyl ether a white
solid precipitated. The solid was washed with diethyl ether
and dried in vacuo. Yield: 60 mg (64%). Anal. Calcd for
C
16H26BF4O2PRu: C, 40.95; H, 5.58. Found: C, 40.92; H, 5.50.
Rou te b. A solution of 11 (100 mg, 0.18 mmol) in 5 mL of
diethyl ether was treated with tetrafluoroboric acid (25 µL,
0.18 mmol, 54% in diethyl ether). A yellow solid immediately
precipitated. The solid was washed with diethyl ether and
IR (Nujol, cm-1): ν(CO) 2050, 1993 both vs, ν(BF4) 1050 vs,
br. 1H NMR (300 MHz, 293 K, CDCl3) δ 5.82 (s, 5H, Cp), 2.43
(m, 3H, PCHCH3), 1.27 (dd, 18H, J (HH) ) 7.2, J (PH) ) 15.9,
PCHCH3); 31P{1H} NMR (121.4 MHz, 293 K, CDCl3) δ 73.8 s.
MS (FAB+): m/z ) 383 (M+).
dried in vacuo. Yield: 95 mg (82%). Anal. Calcd for C30H38
-
BF4O2PRu: C, 55.47; H, 5.89. Found: C, 54.43; H, 5.63. IR
(Nujol, cm-1): ν(OH) 3050 br, ν(CO) 1969 vs, ν(Ph) 1580 w,
ν(CdC) 1560 m, ν(C-O) 1296 s, ν(BF4) 1093, 1032, 976 all vs.
1H NMR (300 MHz, 293 K, CDCl3) δ 12.8 (br, 1H, OH), 7.42-
7.19 (m, 10H, Ph), 7.09 (s, 1H, CHd), 5.31 (s, 5H, Cp), 2.32
(m, 3H, PCHCH3), 1.28 (dd, 9H, J (HH) ) 7.1, J (PH) ) 15.4,
PCHCH3), 1.23 (dd, 9H, J (HH) ) 7.1, J (PH) ) 15.1, PCHCH3);
31P{1H} NMR (121.4 MHz, 293 K, CDCl3) δ 66.5 s; 13C{1H}
NMR (75.4 MHz, 293 K, CDCl3, plus APT) δ 298.7 (-, d, J (PC)
) 9.8, RudC), 202.9 (-, d, J (PC) ) 15.1, CO), 145.3 (-, s,
P r ep a r a t ion of [R u (η5-C5H 5){η2-C2(CO2CH 3)2}(CO)-
(P P r i3)]BF 4 (7). A solution of 5 (80 mg, 0.16 mmol) in 5 mL
of dichloromethane was treated with dimethyl acetylenedi-
carboxylate (60 µL, 0.49 mmol). Immediately the color turned
from orange to yellow, and the solution was concentrated
almost to dryness. By slow addition of diethyl ether a pale
yellow solid precipitated. The solid was washed with diethyl
ether and dried in vacuo. Yield: 88 mg (94%). Anal. Calcd
for C21H32BF4O5PRu: C, 43.23; H, 5.53. Found: C, 43.12; H,
+
+

[RuHCl(CO)(PPri )2]
Organometallics, Vol. 15, No. 15, 1996 3433
3
dCPh2), 140.5, 137.7 (-, both s, Cipso), 140.0 (+, s, CHd), 130.8,
130.2, 129.8, 129.2, 129.0, 128.8 (+, all s, Ph), 90.1 (+, s, Cp),
29.3 (+, d, J (PC) ) 24.5, PCHCH3), 19.9, 19.8 (+, both s,
PCHCH3).
113.2 (both s, CHdCH2), 87.4 (s, Cp), 27.2 (d, J (PC) ) 22.6,
PCHCH3), 19.9, 19.6 (both s, PCHCH3).
P r ep a r a tion of [Ru (η5-C5H5){C(OH)CHdC(CH2)4CH2}-
(CO)(P P r i3)]BF 4 (14). A solution of 15 (290 mg, 0.61 mmol)
in 5 mL of diethyl ether was treated with tetrafluoroboric acid
(83 µL, 0.61 mmol, 54% in diethyl ether). Immediately, a
yellow solid precipitated, which was washed with diethyl ether
and dried in vacuo. Yield: 288 mg (84%). Anal. Calcd for
P r ep a r a t ion of [R u (η5-C5H 5){C(O)CH dCP h 2}(CO)-
(P P r i3)] (11). A solution of 9 (190 mg, 0.30 mmol) in 6 mL of
tetrahydrofuran was treated with water (120 µL, 6.67 mmol).
After the solution was stirred for 2 h, the color turned from
dark red to orange and the solvent was removed in vacuo.
Chromatography of the products on a 10 cm alumina (neutral,
activity grade V) column (eluent: dichloromethane/tetrahy-
drofuran, 15:1) afforded complex 11. The solvent was removed
in vacuo, and the white solid was washed with cold n-pentane
and dried in vacuo. Yield: 144 mg (85%). Anal. Calcd for
C
23H38BF4O2PRu: C, 48.85; H, 6.77. Found: C, 48.43; H, 6.95.
IR (Nujol, cm-1): ν(OH) 3331 br, ν(CO) 1953 vs, ν(CdC) 1586
s, ν(CsO) 1244 s, ν(BF4) 1094, 968 vs, br. 1H NMR (300 MHz,
293 K, CDCl3) δ 13.2 (br, 1H, OH), 6.94 (s, 1H, CHd), 5.56 (s,
5H, Cp), 2.56 (m, 2H, Cy), 2.35 (m, 3H, PCHCH3), 2.37 (m,
2H, Cy), 1.88-1.42 (m, 6H, Cy), 1.30 (dd, 9H, J (HH) ) 7.1,
J (PH) ) 11.2, PCHCH3), 1.26 (dd, 9H, J (HH) ) 7.1, J (PH) )
11.3, PCHCH3); 31P{1H} NMR (121.4 MHz, 293 K, CDCl3) δ
66.7 s; 13C{1H} NMR (75.4 MHz, 293 K, CDCl3, plus APT) δ
295.6 (-, d, J (PC) ) 8.7, RudC), 203.2 (d, J (PC) ) 16.1, CO),
155.3 (-, s, dC), 138.6 (+, s, CHd), 89.2 (+, s, Cp), 37.9, 31.6,
28.6, 27.7, 25.6 (-, all s, Cy), 28.6 (+, d, J (PC) ) 24.4,
PCHCH3), 19.3, 19.2 (+, both s, PCHCH3).
C
30H37O2PRu: C, 64.15; H, 5.38. Found: C, 64.42; H, 5.81.
IR (Nujol, cm-1): ν(CO) 1918 vs, ν(Ph) 1595 m, ν(CdO) 1581
s. 1H NMR (300 MHz, 293 K, C6D6) δ 7.63 (m, 4H, Ph), 7.1
(m, 7H, Ph, CHd), 4.71 (s, 5H, Cp), 1.93 (m, 3H, PCHCH3),
1.00 (dd, 9H, J (HH) ) 7.1, J (PH) ) 13.7, PCHCH3), 0.87 (dd,
9H, J (HH) ) 6.9, J (PH) ) 12.9, PCHCH3); 31P{1H} NMR (121.4
MHz, 293 K, C6D6) δ 71.3 s; 13C{1H} NMR (75.4 MHz, 293 K,
C6D6, plus DEPT) δ 249.5 (Cquat, d, J (PC) ) 10.1, Ru-C), 208.7
(Cquat, d, J (PC) ) 18.4, CO), 144.5 (+, br s, CHd), 144.1, 140.2
(Cquat, both s, Cipso), 131.8, 128.9, 128.5, 127.5, 127.4 (+, all s,
Ph), 130.6 (Cquat, s, dCPh2), 87.5 (+, s, Cp), 27.6 (+, d, J (PC)
) 22.6, PCHCH3), 19.9, 19.5 (+, both s, PCHCH3).
P r ep a r a tion of [Ru (η5-C5H5){C(O)CHdC(CH2)4CH2}-
(CO)(P P r i )] (15) an d [Ru (η5-C5H5){CtC-CdCH(CH2)3CH2}-
3
(CO)(P P r i3)] (16). A solution of 5 (538 mg, 1.08 mmol) in 5
mL of dichloromethane was treated with 1-ethynyl-1-cyclo-
hexanol (136.54 mg, 1.08 mmol). The mixture was stirred for
6 h, and the color turned from orange to brown. The solution
was concentrated to ca. 1 mL and chromatographed on
alumina. Dichloromethane eluted a yellow fraction from which
the solvent was removed in vacuo affording a yellow oil. The
oil was chromatographed on a silica gel column. A diethyl
ether/n-pentane mixture (1:5) first eluted a pale yellow fraction
followed by a yellow fraction. Solvents were removed in vacuo
from both fractions affording 15 as a yellow solid from the
P r ep a r a t ion of [R u (η5-C5H 5){C(OH )CH dCH 2}(CO)-
(P P r i3)]BF 4 (12). Rou te a . A solution of 5 (110 mg, 0.22
mmol) in 2 mL of dichloromethane at 263 K was treated with
2-propyn-1-ol (15.4 µL, 0.26 mmol). The solution was stirred
for 2 min, and the color turned from orange to yellow. The
mixture was rapidly cooled to 195 K, and slow addition of
diethyl ether precipitated a yellow solid. The solid was washed
several times with cold diethyl ether and dried in vacuo.
Yield: 99 mg (90%).
Rou te b. A solution of 13 (80 mg, 0.20 mmol) in 5 mL of
diethyl ether was treated with tetrafluoroboric acid (28 µL,
0.20 mmol, 54% in diethyl ether), and immediately a yellow
solid precipitated. The solid was washed with diethyl ether
and dried in vacuo. Yield: 74 mg (76%). Anal. Calcd for
second fraction. Yield: 310 mg (60%). Anal. Calcd for C23H37
-
O2PRu: C, 57.84; H, 7.81. Found: C, 57.64; H, 7.82. IR
(Nujol, cm-1): ν(CO) 1912 vs, ν(CdC) 1612 m, ν(CdO) 1557 s.
1H NMR (300 MHz, 293 K, C6D6) δ 6.85 (s, 1H, CHd), 4.94 (s,
5H, Cp), 2.71 (m, 2H, Cy), 2.07 (m, 3H, PCHCH3), 2.00 (m,
2H, Cy), 1.52 (m, 4H, Cy), 1.38 (m, 2H, Cy), 1.09 (dd, 9H, J (HH)
) 7.2, J (PH) ) 13.8, PCHCH3), 0.95 (dd, 9H, J (HH) ) 7.2,
J (PH) ) 13.2, PCHCH3); 31P{1H} NMR (121.4 MHz, 293 K,
C6D6) δ 72.7 s; 13C{1H} NMR (75.4 MHz, 293 K, C6D6, plus
APT) δ 247.8 (-, d, J (PC) ) 9.6, Ru-C), 208.8 (-, d, J (PC) )
18.4, CO), 141.0 (+, s, CHd), 137.7 (-, s, dC), 87.6 (+, s, Cp),
36.9, 30.0, 29.3, 28.5, 27.0 (-, all s, Cy), 27.1 (+, d, J (PC) )
22.6, PCHCH3), 19.9, 19.7 (+, both s, PCHCH3). 16 was
obtained as a white solid from the pale yellow fraction.
Yield: 25 mg (5%). Anal. Calcd for C23H35OPRu: C, 60.11;
H, 7.68. Found: C, 60.12; H, 8.04. IR (Nujol, cm-1): ν(CtC)
2088 m, ν(CO) 1930 vs, ν(CdC) 1618 w. 1H NMR (300 MHz,
293 K, C6D6) δ 5.99 (m, 1H, CHd), 4.77 (s, 5H, Cp), 2.37 (m,
2H, Cy), 2.05 (m, 5H, PCHCH3 + Cy), 1.53 (m, 4H, Cy), 1.17
(dd, 9H, J (HH) ) 7.1, J (PH) ) 14.4, PCHCH3), 0.90 (dd, 9H,
J (HH) ) 7.1, J (PH) ) 12.9, PCHCH3); 31P{1H} NMR (121.4
MHz, 293 K, C6D6) δ 74.7 s; 13C{1H} NMR (75.4 MHz, 293 K,
C6D6, plus APT) δ 206.4 (-, d, J (PC) ) 17.9, CO), 126.1 (-, d,
J (PC) ) 0.9, tC-), 125.2 (+, s, CHd), 113.3 (-, s, dC), 92.4
(-, d, J (PC) ) 23.0, Ru-Ct), 87.6 (+, s, Cp), 31.9, 25.6, 23.5,
22.7 (-, all s, Cy), 27.5 (+, d, J (PC) ) 23.9, PCHCH3), 20.3
(+, s, PCHCH3), 19.6 (+, d, J (PC) ) 1.4, PCHCH3).
C
18H30BF4O2PRu: C, 43.47; H, 6.08. Found: C, 43.21; H, 6.23.
IR (Nujol, cm-1): ν(OH) 3400-3050 br, ν(CO) 1975 vs, ν(CdC)
1595 m, ν(CsO) 1297 m, ν(BF4) 1091, 1002 vs, br. 1H NMR
(300 MHz, 293 K, CD2Cl2) δ 13.1 (br, 1H, OH), 7.24 (dd, 1H,
J trans ) 17.0, J cis ) 10.7, CHdCHH), 5.94 (d, 1H, J trans ) 17.0,
CHdCHH), 5.57 (s, 5H, Cp), 5.45 (d, 1H, J cis ) 10.7, CHdCHH),
2.33 (m, 3H, PCHCH3), 1.28 (dd, 9H, J (HH) ) 7.1, J (PH) )
14.9, PCHCH3), 1.20 (dd, 9H, J (HH) ) 7.1, J (PH) ) 14.9,
PCHCH3); 31P{1H} NMR (121.4 MHz, 293 K, CD2Cl2) δ 68.2 s;
13C{1H} NMR (75.4 MHz, 293 K, CD2Cl2) δ 296.3 (d, J (PC) )
9.9, RudC), 202.9 (d, J (PC) ) 15.6, CO), 150.0, 121.2 (both s,
CHdCH2), 90.2 (s, Cp), 29.4 (d, J (PC) ) 24.7, PCHCH3), 19.7,
19.6 (both s, PCHCH3).
P r epar ation of [Ru (η5-C5H5){C(O)CHdCH2}(CO)(P P r i )]
3
(13). Complex 12 (277 mg, 0.56 mmol) was chromatographed
on
a 10 cm alumina (neutral, activity grade V) column
(eluent: dichloromethane/tetrahydrofuran, 20:1), affording
complex 13. The solvent was removed in vacuo, and the solid
was recrystallized from cold n-pentane to give a yellow
microcrystalline solid. The solvent was decanted and the
product dried in vacuo. Yield: 97 mg (42%). Anal. Calcd for
C
18H29O2PRu: C, 52.80; H, 7.14. Found: C, 52.94; H, 7.63.
IR (Nujol, cm-1): ν(CO) 1922 vs, ν(CdC) 1606 m, ν(CdO) 1562
P r ep a r a tion of [Ru (η5-C5H5){C(OMe)CHdCP h 2}(CO)-
(P P r i3)] BF 4 (17). A solution of 9 (90 mg, 0.14 mmol) in 5
mL of methanol was stirred for 15 min, and the color turned
from dark red to yellow. The solution was concentrated almost
to dryness, and slow addition of diethyl ether precipitated a
yellow solid. The solid was washed with diethyl ether and
dried in vacuo. Yield: 80 mg (85%). Anal. Calcd for
s. 1H NMR (300 MHz, 293 K, C6D6) δ 6.94 (dd, 1H, J trans
16.9, J cis ) 9.7, CHdCHH), 5.63 (dd, 1H, J trans ) 16.9, J gem
)
)
2.3, CHdCHH), 4.86 (s, 5H, Cp), 4.73 (dd, 1H, J cis ) 9.7, J gem
) 2.3, CHdCHH), 1.99 (m, 3H, PCHCH3), 1.02 (dd, 9H, J (HH)
) 7.2, J (PH) ) 13.9, PCHCH3), 0.89 (dd, 9H, J (HH) ) 7.2,
J (PH) ) 13.6, PCHCH3); 31P{1H} NMR (121.4 MHz, 293 K,
C6D6) δ 72.4 s; 13C{1H} NMR (75.4 MHz, 293 K, C6D6) δ 247.2
(d, J (PC) ) 10.6, Ru-C), 208.7 (d, J (PC) ) 18.1, CO), 152.6,
C
31H40BF4O2PRu: C, 56.11; H, 6.07. Found: C, 56.14; H, 6.45.
IR (Nujol, cm-1): ν(CO) 1953 vs, ν(CdC) 1593 m, ν(Ph) 1570
+
+

3434 Organometallics, Vol. 15, No. 15, 1996
Esteruelas et al.
m, ν(CsO) 1275 s, ν(BF4) 1050 vs, br. 1H NMR (300 MHz,
293 K, CDCl3) δ 7.4-7.0 (m, 10H, Ph), 6.47 (s, 1H, CHd), 4.94
(s, 5H, Cp), 4.26 (s, 3H, OCH3), 2.20 (m, 3H, PCHCH3), 1.20
(dd, 9H, J (HH) ) 6.9, J (PH) ) 15.4, PCHCH3), 1.13 (dd, 9H,
J (HH) ) 6.6, J (PH) ) 14.8, PCHCH3); 31P{1H} NMR (121.4
MHz, 293 K, CDCl3) δ 65.9 s; 13C{1H} NMR (75.4 MHz, 293
K, CDCl3) δ 305.0 (br, RudC), 202.8 (d, J (PC) ) 16.0, CO),
139.6, 137.8 (both s, Cipso + dCPh2), 136.7 (br s, CHd), 131.0,
129.7, 129.5, 128.7, 128.6, 128.4 (all s, Ph), 89.5 (s, Cp), 66.8
(s, OCH3), 29.3 (d, J (PC) ) 24.2, PCHCH3), 19.6, 19.3 (both s,
PCHCH3). MS (FAB+): m/z ) 577 (M+).
P r ep a r a tion of [Ru (η5-C5H5){C(OEt)CHdCP h 2}(CO)-
(P P r i3)]BF 4 (18). A solution of 9 (100 mg, 0.16 mmol) in 5
mL of ethanol was stirred for 45 min, and the color turned
from dark red to yellow. The solution was concentrated almost
to dryness, and slow addition of diethyl ether precipitated a
yellow solid. The solid was washed with diethyl ether and
dried in vacuo. Yield: 90 mg (84%). Anal. Calcd for
NMR (121.4 MHz, 293 K, C6D6) δ 72.2 s; 13C{1H} NMR (75.4
MHz, 293 K, C6D6, plus APT) δ 206.8 (-, d, J (PC) ) 18.9, CO),
197.6 (-, s, Câ), 142.3, 142.0 (-, both s, Cipso), 135.7 (-, d, J (PC)
) 13.3, CR), 129.2, 128.7, 128.2, 128.2, 125.8, 125.7 (+, all s,
Ph), 106.6 (-, s, Cγ), 86.0 (+, s, Cp), 66.5 (-, s, OCH2CH3),
27.8 (+, d, J (PC) ) 22.6, PCHCH3), 20.1, 19.6 (+, both s,
PCHCH3), 15.5 (+, s, OCH2CH3).
P r ep a r a tion of [Ru (η5-C5H5){C(SP r n )CHdCP h 2}(CO)-
(P P r i3)]BF 4 (21). A solution of 9 (150 mg, 0.24 mmol) in 5
mL of dichloromethane was treated with 1-propanethiol (23
µL, 0.25 mmol). After the solution was stirred for 5 h, the
color turned dark orange, and the solution was concentrated
almost to dryness. Slow addition of diethyl ether precipitated
an orange solid. The solid was washed with diethyl ether and
dried in vacuo. Yield: 165 mg (98%). Anal. Calcd for
C
33H44BF4OPRuS: C, 56.01; H, 6.27; S, 4.53. Found: C, 55.94;
H, 6.45; S, 3.34. IR (Nujol, cm-1): ν(CO) 1964 vs, ν(Ph) 1585
w, ν(CdC) 1561 m, ν(BF4) 1074, 1051, 1030, all s. 1H NMR
(300 MHz, 293 K, CDCl3) δ 7.46-7.08 (m, 10H, Ph), 6.91 (s,
1H, CHd), 5.10 (s, 5H, Cp), 3.34 (m, 2H, SCH2CH2CH3), 2.42
(m, 3H, PCHCH3), 1.76 (m, 2H, SCH2CH2CH3), 1.32 (dd, 9H,
J (HH) ) 6.9, J (PH) ) 12.0, PCHCH3), 1.27 (dd, 9H, J (HH) )
6.9, J (PH) ) 11.4, PCHCH3), 1.01 (t, 3H, J (HH) ) 7.2, SCH2-
CH2CH3); 31P{1H} NMR (121.4 MHz, 293 K, CDCl3) δ 60.6 s;
13C{1H} NMR (75.4 MHz, 293 K, CDCl3, plus DEPT) δ 311.6
(Cquat, d, J (PC) ) 6.8, RudC), 202.6 (Cquat, d, J (PC) ) 17.3,
CO), 142.9 (+, br s, CHd), 140.9, 140.6 (Cquat, both s, Cipso),
138.1 (Cquat, s, dCPh2), 131.1, 129.3, 129.0, 128.7, 128.6, 128.3
(+, all s, Ph), 90.4 (+, s, Cp), 48.4 (-, s, SCH2CH2CH3), 29.3
(+, d, J (PC) ) 24.1, PCHCH3), 20.5 (-, s, SCH2CH2CH3), 20.1
(+, s, PCHCH3), 19.6 (+, d, J (PC) ) 1.5, PCHCH3), 13.3 (+, s,
SCH2CH2CH3).
C
32H42BF4O2PRu: C, 56.72; H, 6.24. Found: C, 56.84; H, 5.91.
IR (Nujol, cm-1): ν(CO) 1952 vs, ν(Ph) 1585 w, ν(CdC) 1566
m, ν(CsO) 1261 s, ν(BF4) 1057 vs, br. 1H NMR (300 MHz,
293 K, CDCl3) δ 7.5-7.1 (m, 10H, Ph), 6.56 (s, 1H, CHd), 4.99
(s, 5H, Cp), 4.73 (q, 2H, J (HH) ) 7.0, OCH2CH3), 2.31 (m, 3H,
PCHCH3), 1.52 (t, 3H, J (HH) ) 7.0, OCH2CH3), 1.30 (dd, 9H,
J (HH) ) 7.1, J (PH) ) 15.1, PCHCH3), 1.24 (dd, 9H, J (HH) )
7.1, J (PH) ) 14.4, PCHCH3); 31P{1H} NMR (121.4 MHz, 293
K, CDCl3) δ 65.9 s; 13C{1H} NMR (75.4 MHz, 293 K, CDCl3) δ
303.8 (br, RudC), 203.0 (d, J (PC) ) 15.8, CO), 139.8, 137.9
(both s, Cipso + dCPh2), 137.0 (br s, CHd), 131.2, 129.7,129.6,
128.7, 128.7, 128.5 (all s, Ph), 89.5 (s, Cp), 77.2 (s, OCH2CH3),
29.5 (d, J (PC) ) 24.3, PCHCH3), 19.8 (s, PCHCH3), 19.5 (d,
J (PC) ) 1.4, PCHCH3), 14.6 (s, OCH2CH3).
P r ep a r a tion of [Ru (η5-C5H5){C(OMe)dCdCP h 2}(CO)-
(P P r i3)] (19). A solution of 17 (250 mg, 0.38 mmol) in 5 mL
of tetrahydrofuran was treated with sodium methoxide (22 mg,
0.41 mmol), and the mixture was stirred for 2 h. The color
turned from yellow to pale yellow, and the solvent was removed
in vacuo. A 12 mL volume of toluene was added and the
mixture filtered to eliminate NaBF4. The solvent was removed
in vacuo, and the residue was washed with cold n-pentane to
afford a pale yellow solid. The solvent was decanted and the
product dried by vacuum. Yield: 173 mg (80%). Anal. Calcd
for C31H39O2PRu: C, 64.68; H, 6.83. Found: C, 64.37; H, 6.56.
IR (Nujol, cm-1): ν(CO) 1913 vs, ν(CdCdC) 1871 m, ν(Ph) 1595
m, ν(CsO) 1049 s. 1H NMR (300 MHz, 293 K, C6D6) δ 7.75
(m, 4H, Ph), 7.31 (m, 4H, Ph), 7.17 (m, 2H, Ph), 4.99 (s, 5H,
Cp), 3.55 (s, 3H, OCH3), 1.99 (m, 3H, PCHCH3), 1.03 (dd, 9H,
J (HH) ) 7.2, J (PH) ) 13.7, PCHCH3), 0.91 (dd, 9H, J (HH) )
7.2, J (PH) ) 13.7, PCHCH3); 31P{1H} NMR (121.4 MHz, 293
K, C6D6) δ 70.4 s; 13C{1H} NMR (75.4 MHz, 293 K, C6D6) δ
206.9 (d, J (PC) ) 18.9, CO), 197.8 (s, Câ), 142.2, 141.9 (both s,
P r ep a r a tion of [Ru (η5-C5H5){C(SP r n )dCdCP h 2}(CO)-
(P P r i3)] (22). A solution of 21 (159 mg, 0.22 mmol) in 5 mL
of tetrahydrofuran was treated with sodium methoxide (13.5
mg, 0.24 mmol) and the mixture stirred for 1.5 h. The color
turned from dark orange to pale yellow, and the solvent was
removed in vacuo. A 12 mL volume of toluene was added, and
the mixture was filtered to eliminate NaBF4. The solvent was
removed in vacuo and the residue washed with cold n-pentane
to afford a yellow solid dried by vacuum. Yield: 94 mg (68%).
Anal. Calcd for C33H43OPRuS: C, 63.95; H, 6.99; S, 5.17.
Found: C, 63.72; H, 7.10; S, 5.20. IR (Nujol, cm-1): ν(CO)
1930 vs, ν(CdCdC) 1887 m, ν(Ph) 1595 m. 1H NMR (300 MHz,
293 K, C6D6) δ 7.63 (m, 4H, Ph), 7.27 (m, 4H, Ph), 7.14 (m,
2H, Ph), 5.04 (s, 5H, Cp), 2.85 (m, 2H, SCH2CH2CH3), 2.00
(m, 3H, PCHCH3), 1.57 (m, 2H, SCH2CH2CH3), 1.05 (dd, 9H,
J (HH) ) 7.2, J (PH) ) 14.3, PCHCH3), 0.81 (dd, 9H, J (HH) )
7.2, J (PH) ) 12.6, PCHCH3), 0.81 (t, 3H, J (HH) ) 7.2, SCH2-
CH2CH3); 31P{1H} NMR (121.4 MHz, 293 K, C6D6) δ 71.1 s;
13C{1H} NMR (75.4 MHz, 293 K, C6D6) δ 206.4 (d, J (PC) )
19.8, CO), 195.9 (s, Câ), 141.0, 140.6 (both s, Cipso), 128.2-125.2,
(all s, Ph), 103.4 (s, Cγ), 90.1 (d, J (PC) ) 11.3, CR), 85.7 (s,
Cp), 39.0 (s, SCH2CH2CH3), 26.8 (d, J (PC) ) 22.6, PCHCH3),
22.7 (s, SCH2CH2CH3), 19.9, 18.8 (both s, PCHCH3), 13.4 (s,
SCH2CH2CH3).
P r ep a r a tion of [Ru (η5-C5H5){C(CHdCP h 2)dNdCP h 2}-
(CO)(P P r i3)]BF 4 (23). A solution of 9 (125 mg, 0.20 mmol)
in 5 mL of tetrahydrofuran was treated with benzophenone
imine (37 µL, 0.21 mmol). After the solution was stirred for 6
h, the color turned to orange, and the solution was concen-
trated almost to dryness. By slow addition of diethyl ether
an orange solid precipitated. The solid was washed with
diethyl ether and dried in vacuo. Yield: 147 mg (91%). Anal.
Calcd for C43H47BF4NOPRu: C, 63.55; H, 5.83; N, 1.72.
Found: C, 63.20; H, 5.97; N, 1.82. IR (Nujol, cm-1): ν(CO)
1942 vs, ν(CdNdC) 1813 m, ν(Ph) 1593, 1577 both w, ν(CdC)
1550 s, ν(BF4) 1055 vs, br. 1H NMR (300 MHz, 293 K, CDCl3)
δ 7.66-6.60 (m, 21H, Ph + CHd), 5.29 (s, 5H, Cp), 2.26 (m,
3H, PCHCH3), 1.20 (dd, 9H, J (HH) ) 7.2, J (PH) ) 14.5,
PCHCH3), 1.18 (dd, 9H, J (HH) ) 7.2, J (PH) ) 14.3, PCHCH3);
31P{1H} NMR (121.4 MHz, 293 K, C6D6, plus DEPT) δ 67.0 s;
C
ipso), 138.1 (d, J (PC) ) 13.6, CR), 129.1, 128.8, 128.2, 128.2,
125.9, 125.9 (all s, Ph), 107.7 (s, Cγ), 86.0 (s, Cp), 58.2 (s,
OCH3), 27.8 (d, J (PC) ) 22.6, PCHCH3), 20.0, 19.6 (both s,
PCHCH3).
P r ep a r a tion of [Ru (η5-C5H5){C(OEt)dCdCP h 2}(CO)-
(P P r i3)] (20). A solution of 18 (253 mg, 0.37 mmol) in 5 mL
of tetrahydrofuran was treated with sodium methoxide (22 mg,
0.41 mmol), and the mixture was stirred for 2.5 h. The color
turned from yellow to pale yellow, and the solvent was removed
in vacuo. A 12 mL volume of toluene was added and the
mixture filtered to eliminate NaBF4. The solvent was removed
in vacuo, and the residue was washed with cold n-pentane to
afford an oily pale yellow solid, which was separated by
decantation and dried by vacuum. At room temperature the
product exists as a yellow oil. Yield: 205 mg (93%). IR (Nujol,
cm-1): ν(CO) 1932 vs, ν(CdCdC) 1890 m, ν(Ph) 1595 m, ν-
(CsO) 1047 s. 1H NMR (300 MHz, 293 K, C6D6) δ 7.61 (m,
4H, Ph), 7.10 (m, 6H, Ph), 4.85 (s, 5H, Cp), 3.68 (m, 2H, OCH2-
CH3), 1.89 (m, 3H, PCHCH3), 1.05 (t, 3H, J (HH) ) 7.1,
OCH2CH3), 0.91 (dd, 9H, J (HH) ) 7.2, J (PH) ) 13.7, PCHCH3),
0.80 (dd, 9H, J (HH) ) 6.9, J (PH) ) 12.6, PCHCH3); 31P{1H}
+
+

[RuHCl(CO)(PPri )2]
Organometallics, Vol. 15, No. 15, 1996 3435
3
Ta ble 3. Cr ysta l Da ta a n d Da ta Collection a n d
Refin em en t P a r a m eter s for
9H, J (HH) ) 7.1, J (PH) ) 13.9, PCHCH3), 0.84 (dd, 9H, J (HH)
) 7.1, J (PH) ) 13.2, PCHCH3); 31P{1H} NMR (121.4 MHz, 293
K, CDCl3) δ 71.8 s; 13C{1H} NMR (75.4 MHz, 293 K, CDCl3,
plus APT) δ 207.5 (-, d, J (PC) ) 19.8, CO), 194.7 (-, s, Câ),
155.0 (-, s, NdCPh2), 142.8, 141.8, 141.6, 138.1 (-, all s, Cipso),
130.2, 130.0, 129.1, 128.9, 128.8, 128.1, 128.0, 127.7, 127.6,
125.9, 125.3 (+, all s, Ph), 114.9 (-, d, J (PC) ) 12.9, CR), 102.3
(-, s, Cγ), 85.6 (+, s, Cp), 27.5 (+, d, J (PC) ) 22.6, PCHCH3),
20.0, 19.5 (+, both s, PCHCH3).
[Ru (η5-C5H5){C(O)CHdCP h 2}(CO)(P P r 3i)] (11) a n d
[Ru (η5-C5H5){C(CHdCP h 2)dNdCP h 2}(CO)(P P r i3)]BF 4
(23)
11
23
Crystal Data
C30H37O2PRu
561.665
formula
mol wt
C43H47BNOF4PRu
812.698
X-r ay Str u ctu r e An alysis of [Ru (η5-C5H5){C(O)CHCP h 2}-
(CO)(P P r i3)] (11) a n d [R u (η5-C5H 5){C(CHdCP h 2)dNd
CP h 2}(CO)(P P r i3)]BF 4 (23). Crystals suitable for X-ray
diffraction were obtained by slow diffusion of hexane into a
concentrated solution of 11 in toluene or by diffusion of Et2O
into a concentrated solution of 23 in CH2Cl2. A summary of
crystal data, intensity collection procedure, and refinement is
reported in Table 3 (11 and 23). The crystals were glued on a
glass fiber and mounted on a Siemens-Stoe AED-4 (11) or a
Siemens-P4 (23) diffractometer. Cell constants were obtained
from the least-squares fit of the setting angles of 58 reflections
in the range 20 e 2θ e 42° (11) (60 reflections in the range 20
e 2θ e 30° for 23). The recorded reflections were corrected
for Lorentz and polarization effects. Three orientation and
intensity standards were monitored, and no significant varia-
tion was observed. Reflections were also corrected for absorp-
tion by a semiempirical (Ψ-scan) method.51 The structures
were solved by Patterson (Ru atoms) and conventional Fourier
techniques. Refinements were carried out by full-matrix least-
squares methods with initial isotropic thermal parameters.
Anisotropic thermal parameters were used in the last cycles
of refinement for all non-hydrogen atoms. Hydrogen atoms
were observed or calculated (C-H ) 0.96 Å) and included in
the refinement riding on carbon atoms with common isotropic
thermal values. Atomic scattering factors, corrected for
anomalous dispersion for Ru and P atoms, were taken from
ref 52. All calculations were performed using SHELXTL-
PLUS53 and SHELXL93.54
color and habit
yellow, irregular
prism
0.29 × 0.17 × 0.35
monoclinic
P21/c
17.932(4)
9.442(2)
18.311(3)
118.68(1)
2720(1)
orange, irregular
prism
0.40 × 0.38 × 0.20
monoclinic
P21/n
15.039(3)
14.620(3)
18.825(4)
109.651(7)
3898(1)
cryst size, mm
cryst syst
space group
a, Å
b, Å
c, Å
â, deg
V, Å3
Z
4
4
D(calcd), g cm-3
temp, K
1.3716
293
1.3848
293
Data Collection and Refinement
diffractometer
λ(Mo KR) radiation,
Å; technique
monochomator
µ, mm-1
scan type
2θ range, deg
no. of data collect
no. of unique data
Siemens-STOE AED-2 Siemens-P4
0.710 73; bisecting geometry
graphite oriented
0.66
ω/2θ
3 e 2θ e 50
7354
4756
0.50
θ/2θ
2 e 2θ e 50
8650
6822
470
0.1452
0.0592
no. of params refined 308
wR2(F2, all data)
R1(F, Fo > 4.0σF)
0.0724
0.0256
a
2
b
wR2(F2) ) {∑[w(Fo - Fc2)2]/∑[w(Fo2)2]}1/2
.
R1(F) ) ∑||Fo| -
|Fc||/∑|Fo|.
13C{1H} NMR (75.4 MHz, 293 K, C6D6) δ 207.1 (Cquat, d, J (PC)
) 9.0, RusCdN), 203.2 (Cquat, d, J (PC) ) 16.6, CO), 145.7,
139.6, 136.9, 134.1, 131.0, 130.0 (Cquat, all s, NdCPh2 + Cipso
+ CHdCPh2), 131.9, 131.7, 130.3, 129.9, 129.8, 128.8, 128.7,
128.5, 128.3, 127.5, 127.5 (+, all s, Ph + CHd), 87.4 (+, s,
Cp), 28.8 (+, d, J (PC) ) 24.1, PCHCH3), 19.7, 19.5 (+, both s,
PCHCH3).
Ack n ow led gm en t. We thank the DGICYT (Project
PB-95-0806, Programa de Promocio´n General del Cono-
cimiento) and the EU (European Union) (Project: Selec-
tive Processes and Catalysis Involving Small Molecules)
for financial support.
P r ep a r a tion of [Ru (η5-C5H5){C(NdCP h 2)dCdCP h 2}-
(CO)(P P r i3)] (24). A solution of 23 (200 mg, 0.25 mmol) in 5
mL of tetrahydrofuran was treated with sodium methoxide
(14.0 mg, 0.26 mmol) and the mixture stirred for 1.5 h. The
color turned from orange to yellow, and the solvent was
removed in vacuo. A 12 mL volume of toluene was added, and
the mixture was filtered to eliminate NaBF4. The solvent was
removed in vacuo and the residue was washed with n-pentane
to afford a yellow solid dried by vacuum. Yield: 164 mg (92%).
Anal. Calcd for C43H46NOPRu: C, 71.24; H, 6.39; N, 1.93.
Found: C, 70.81; H, 6.59; N, 1.78. IR (Nujol, cm-1): ν(CO)
1935 vs, ν(CdCdC) 1888 m, ν(Ph) 1607 w, 1574 w, ν(CdN)
1594 m. 1H NMR (300 MHz, 293 K, C6D6) δ 8.05-6.92 (m,
20H, Ph), 4.57 (s, 5H, Cp), 2.03 (m, 3H, PCHCH3), 1.16 (dd,
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates, anisotropic and isotropic thermal parameters,
experimental details of the X-ray study, and bond distances
and angles (32 pages). Ordering information is given on any
current masthead page.
OM960124D
(51) North, A. C. T.; Phillips, D. C.; Mathews, F. S. Acta Crystallogr.,
Sect. A 1969, 24, 351.
(52) International Tables for Crystallography; Kluwer Academic
Publishers: Dordrecht, The Netherlands, 1992; Vol. C.
(53) Sheldrick, G. M. SHELXTL PLUS; Siemens Analytical X-ray
Instruments: Madison, WI, 1990.
(54) Sheldrick, G. M. SHELX93, Program for Crystal Structure,
Univ. of Go¨ttingen, 1993.
+
+