Addition of acetylenes to olefins. Oxidative coupling versus [2+2] cycloaddition to a vinylidene intermediate

Article abstract of DOI:10.1021/om980902x

The reaction of [RuCpOcKP)y-PPh2CH2CH2CH=CH2)(CH3CN)]PF6 (1) with HCCPh in the absence of base results in the formation of the ?/4-butadiene complexes [RiGp(icP),i]4(3Z,5￡)-PPh2CH2CH2CH=CH-CH=CHPh)]PF6 (2a) and [RuCp(1(P),?74-(3Z)-PPh2CH2CH2CH=CH-CPh=CH2)]PF6 (2b). When the reaction is carried out in the presence of base (NaOEt), in addition to 2a and 2b, the ?73-butadienyl complex RuCp(/c1(P),(3,4,5-?/)-PPh2CH2CH2CHCHCCHPh) (2c) is obtained. The C-C coupling reactions take place also with internal alkynes RCR2 (R1 = R2 = Ph, Et; R1 = Ph, R2 = Et) to give the ?;4-butadiene complexes [RuCp(1(P),?;4-(3Z)5Z)-PPh2CH2CH2CH=CH-CR1=CHR2)]PF6 (3-5). In the case of terminal acetylenes two distinct reaction modes are observed proceeding via either metallacyclopentene complexes or the successive intermediacy of vinylidene and metallacyclobutane complexes. With internal alkynes, the metallacyclopentene route is followed. X-ray structures of representative complexes are reported.

Full text of DOI:10.1021/om980902x

Organometallics 1999, 18, 1011-1017
1011
Ad d ition of Acetylen es to Olefin s. Oxid a tive Cou p lin g
ver su s [2+2] Cycloa d d ition to a Vin ylid en e In ter m ed ia te
Christian Slugovc,† Kurt Mereiter,‡ Roland Schmid,† and Karl Kirchner*,†,#
Institute of Inorganic Chemistry and Institute of Mineralogy, Crystallography, and
Structural Chemistry, Vienna University of Technology, Getreidemarkt 9,
A-1060 Vienna, Austria
Received November 3, 1998
The reaction of [RuCp(κ1(P),η2-PPh2CH2CH2CHdCH2)(CH3CN)]PF6 (1) with HCtCPh in
the absence of base results in the formation of the η4-butadiene complexes [RuCp(κ1(P),η4-
(3Z,5E)-PPh2CH2CH2CHdCH-CHdCHPh)]PF6 (2a ) and [RuCp(κ1(P),η4-(3Z)-PPh2CH2CH2-
CHdCH-CPhdCH2)]PF6 (2b). When the reaction is carried out in the presence of base
(NaOEt), in addition to 2a and 2b, the η3-butadienyl complex RuCp(κ1(P),(3,4,5-η)-PPh2-
CH2CH2CHCHCCHPh) (2c) is obtained. The C-C coupling reactions take place also with
internal alkynes R1CtCR2 (R1 ) R2 ) Ph, Et; R1 ) Ph, R2 ) Et) to give the η4-butadiene
complexes [RuCp(κ1(P),η4-(3Z,5Z)-PPh2CH2CH2CHdCH-CR1dCHR2)]PF6 (3-5). In the case
of terminal acetylenes two distinct reaction modes are observed proceeding via either
metallacyclopentene complexes or the successive intermediacy of vinylidene and metalla-
cyclobutane complexes. With internal alkynes, the metallacyclopentene route is followed.
X-ray structures of representative complexes are reported.
Sch em e 1
In tr od u ction
The coupling of unactivated olefins and acetylenes
mediated by transition metal complexes has been the
subject of several recent investigations.1 The most
common mechanism envisaged is the oxidative coupling
via a metallacyclopentene intermediate as illustrated
in Scheme 1, path a . When terminal alkynes are in-
volved, an alternative mechanism may operate via the
successive intermediacy of vinylidene and metallacy-
clobutane complexes (path b). Such a process is not
limited to early transition metal complexes,2 but has
also been shown by us3 to be operative in the reaction
of the late transition metal complexes RuTp(COD)Cl (Tp
) trispyrazolylborate) and RuTp(κ1(P),η2-Ph2PCHdCH-
(Ph)dCH2)Cl with terminal acetylenes. The products
obtained are η2-butadiene or, in the presence of base,
η3-butadienyl complexes. Herein, we extend our previ-
ous studies on carbon-carbon bond formation between
olefins and acetylenes and report on the reaction of
[RuCp(κ1(P),η2-Ph2PCH2CH2CHdCH2)(CH3CN)]PF6 with
terminal and internal acetylenes. It will be demon-
strated that under certain reaction conditions both
modes of reaction (path a and b) occur simultaneously
in competition with one another. X-ray structures of
representative products are included.
Resu lts a n d Discu ssion
† Institute of Inorganic Chemistry.
‡ Institute of Mineralogy, Crystallography, and Structural Chem-
istry.
The cationic complex [RuCp(κ1(P),η2-PPh2CH2CH2-
CHdCH2)(CH3CN)]PF6 (1) has been prepared in 83%
isolated yield by the reaction of [RuCp(CH3CN)3]PF6
with Ph2PCH2CH2CHdCH2 in CH2Cl2 at room temper-
#
E-mail: kkirch@mail.zserv.tuwien.ac.at.
(1) (a) Trost, B. M.; Indolese, A. F.; Mu¨ller, T. J . J .; Treptow, B. J .
Am. Chem. Soc. 1995, 117, 615. (b) Trost, B. M.; Portnoy, M.; Kurihara,
H. J . Am. Chem. Soc. 1997, 119, 836. (c) Kikuchi, H.; Uno, M.;
Takahashi, S. Chem. Lett. 1997, 1273. (d) Derien, S.; Dixneuf, P. H. J .
Chem. Soc., Chem. Commun. 1994, 2551. (e) Trost, B. M.; Flygare, J .
A. J . Am. Chem. Soc. 1992, 114, 5476. (f) Trost, B. M.; Imi, K.; Indolese,
A. F. J . Am. Chem. Soc. 1993, 115, 8831. (g) Trost, B. M.; Dyker, G.;
Kulawiec, R. J . Am. Chem. Soc. 1990, 112, 7809. (h) Bruce, M. I.;
Gardner, R. C. F.; Howard, J . A. K.; Stone, F. G. A.; Welling, M.;
Woodward, P. J . Chem. Soc., Dalton Trans. 1977, 621. (i) Bruce, M. I.;
Gardner, R. C. F.; Stone, F. G. A. J . Chem. Soc., Dalton Trans. 1979,
906.
(2) (a) Beckhaus, R. Angew. Chem. 1997, 109, 695. (b) Beckhaus,
R.; Sang, J .; Wagner, T.; Ganter, B. Organometallics 1996, 15, 1176.
(c) Alt, H. G.; Engelhardt, H. E.; Rausch, M. D.; Kool, L. B. J .
Organomet. Chem. 1987, 329, 61.
(3) Slugovc, C.; Mereiter, K.; Schmid, R.; Kirchner, K. J . Am. Chem.
Soc. 1998, 120, 6175.
1
ature. Characterization was by H, 13C{1H}, and 31P-
{1H} NMR spectroscopies and elemental analysis.
The NMR spectra of 1 bear no unusual features, and
it is sufficient to point out that the proton resonances
of the terminal CH2d moiety of the Ph2PCH2CH2CHd
CH2 ligand give rise to two characteristic doublets
3
centered at 4.49 (H4anti, J HHcis ) 8.5 Hz) and 2.76 ppm
(H4syn, J HHtrans ) 12.6 Hz). As apparent from the 31P-
3
{1H} NMR spectra, only one of the two possible isomers
is formed.4 A structural view of 2a , as determined by
X-ray crystallography, is depicted in Figure 1. Important
10.1021/om980902x CCC: $18.00 © 1999 American Chemical Society
Publication on Web 02/24/1999

1012 Organometallics, Vol. 18, No. 6, 1999
Slugovc et al.
X-ray diffraction. An ORTEP diagram of 2a ‚CH2Cl2 is
depicted in Figure 2, with important bond distances
reported in the caption. 2a ‚CH2Cl2 adopts a three-legged
piano stool conformation with P and the two CdC bonds
of the PPh2CH2CH2CHdCH-CdCHPh ligand as the
legs. The most notable feature, which is consistent with
the NMR data, is the s-cis structure of the butadiene
moiety. The C-C distances within the butadiene frag-
ment are very similar, ranging from 1.426 to 1.431 Å.
The Ru-C distances are slightly shorter by about 0.09
Å for C(21) and C(22) than for C(20) and C(23). The Ru-
P(1) bond distance is 2.335(1) Å.
When the reaction of 1 with HCtCPh (3 equiv) is run
in the absence of base, complexes 2a and 2b are
obtained in 56 and 15% isolated yield. However, NMR
monitoring of the progress of this reaction indicated
complete consumption of 1 after 1 h, giving 2a and 2b
in 3.3:1.0 ratio, with no evidence found for the formation
of 2c but small amounts of polymeric materials (Table
1).6 The coupling reaction turned out to be not restricted
to terminal alkynes. Thus, in similar fashion, 1 was
found to react with 1.5 equiv of internal alkynes R1Ct
CR2 (R1 ) R2 ) Ph, Et; R1 ) Ph, R2 ) Et) to give the
η4-butadiene complexes [RuCp(κ1(P),η4-(3Z,5Z)-PPh2-
CH2CH2CHdCH-CPhdCHPh)]PF6 (3), [RuCp(κ1(P),η4-
(3Z,5E)-PPh2CH2CH2CHdCH-CEtdCHEt)]PF6 (4), and
5 (in the form of the two regioisomers [RuCp(κ1(P),η4-
(3Z,5E)-PPh2CH2CH2CHdCH-CEtdCHPh)]PF6 (5a )
and [RuCp(κ1(P),η4-(3Z,5Z)-PPh2CH2CH2CHdCH-CPhd
CHEt)]PF6 (5b)) in high yields (Table 1). The reactions
with the internal alkynes are drastically slower than
those with HCtCPh as determined by 31P{1H} NMR
spectroscopy (ca. 8 h for PhCtCPh vs 1 h for HCtCPh
under the same reaction conditions). All complexes have
F igu r e 1. Structural view of 1 (PF6- omitted for clarity).
Selected bond lengths (Å) and angles (deg): Ru-P(1) 2.342-
(1), Ru-N 2.061(4), Ru-C(Cp)av 2.206 (7), Ru-C(20) 2.250-
(6), Ru-C(21) 2.217(7), C(20)-C(21) 1.421(12), Ru-N-
C(22) 172.5(5), C(19)-C(20)-C(21) 119.3(9).
bond distances are reported in the caption. Complex 1
adopts the usual three-legged piano stool structure. The
olefin moiety of the Ph2PCH2CH2CHdCH2 ligand is
bonded almost symmetrically to the metal center, with
the Ru-C bonds to the internal and terminal carbon
atoms C(20) and C(21) being 2.250(6) and 2.217(7) Å,
respectively. The CdC double bond is almost perpen-
dicular to the Ru-N bond. The Ru-N and Ru-P(1)
distances are 2.061(4) and 2.342(1) Å, respectively.
Treatment of 1 with HCtCPh in MeOH in the pres-
ence of NaOEt (1 equiv) at 65 °C for 3 h afforded, on
workup, the two isomeric η4-butadiene complexes [RuCp-
(κ1(P),η4-(3Z,5E)-PPh2CH2CH2CHdCH-CHdCHPh)]-
PF6 (2a ) and [RuCp(κ1(P),η4-(3Z)-PPh2CH2CH2CHd
CH-CPhdCH2)]PF6 (2b ) as well as the η3-butadi-
enyl complex RuCp(κ1(P),(3,4,5-η)-PPh2CH2CH2CHCH-
CCHPh) (2c) in 34, 7, and 39% isolated yields, respec-
tively (Scheme 2).
1
been characterized by elemental analysis and H, 13C-
1
{1H}, and 31P{1H} NMR spectroscopies. The H NMR
spectra of all these complexes exhibit resonances for the
H6 proton in the range 2.0-2.4 ppm, indicating that it
is syn to the metal center. In addition, the molecular
structure of the major isomer 5a determined by X-ray
crystallography (Figure 3) confirms that the phenyl
substituent is situated on the C6 carbon atom. Impor-
tant bond distances and angles are given in the caption.
The overall geometry of the complex is very similar to
that of 2a . The bond distances between Ru and the
butadiene fragment, which is adopting a s-cis conforma-
tion, are short for C(21) and C(22), being 2.175(3) and
2.196(3) Å, respectively, and long for C(20) and C(23),
being 2.253(3) and 2.304(3) Å, respectively. The C-C
bond distances within this moiety are relatively uni-
form, varying between 1.418 and 1.431 Å, and do not
exhibit the typical short-long-short pattern, as is the
case for most Ru(II) η4-diene complexes.7 The Ru-P(1)
bond distance is 2.318(1) Å.
Characterization of 2 was again by a combination of
elemental analysis and 1H and 13C{1H} NMR spec-
1
troscopies. The solution H NMR spectroscopic data for
2a include doublets of doublets centered at 6.48 (H5) and
2.65 ppm (H6syn) with a common coupling constant of
3J HH ) 9.7 Hz, consistent with an E-arrangement of the
C5-C6 double bond. The significant upfield shift of the
H6syn proton is characteristic of this type of complexes
(vide infra). In the 1H NMR spectrum of 2b the
resonances of the terminal CH2d moiety of the Ph2-
PCH2CH2CHdCHCPhdCH2 show a doublet centered at
3.61 (H6anti, 2J HH ) 4.9 Hz) and a characteristic doublet
2
of doublets centered at 1.17 ppm (H6syn, J HH ) 4.9 Hz,
3J HP ) 16.4 Hz). In the 13C{1H} NMR spectrum of 2c,
the characteristic resonance of the C5 carbon atom is
observed at 171.6 ppm, in agreement with those for
other η3-butadienyl complexes.5 All other resonances are
unremarkable and are not discussed here.
As we have previously shown,3 the C5 carbon of the
η3-butadienyl complexes is nucleophilic, which offers the
(5) For related η3-butadienyl complexes see: (a) Yi, C. S.; Liu, N.;
Rheingold, A. L.; Liable-Sands, L. M. Organometallics 1997, 16, 3910.
(b) Bruce, M. I.; Duffy, D. N.; Liddell, M. J .; Tiekink, E. R. T.; Nicholson,
B. K. Organometallics 1992, 11, 1527. (c) Bruce, M. I.; Hambly, T. W.;
Liddell, M. J .; Snow, M. R.; Swincer, A. G.; Tiekink, E. R. T.
Organometallics 1990, 9, 96. (d) Bruce, M. I.; Hambly, T. W.; Snow,
M. R.; Swincer, A. G. Organometallics 1985, 4, 501. (e) Bruce, M. I.;
Rodgers, J . R.; Snow, M. R.; Swincer, A. G. J . Chem. Soc., Chem.
Commun. 1981, 271.
In addition to full NMR spectroscopic and analytical
characterizations of the products, the solid-state struc-
ture of 2a ‚CH2Cl2 was determined by single-crystal
(4) (a) Bennett, M. A.; Heath, G. A.; Hockless, D. C. R.; Kovacik, I.;
Willis, A. C. J . Am. Chem. Soc. 1998, 120, 932. (b) Bruce, M. I.;
Hambley, T. W.; Snow, M. R.; Swincer, A. G. J . Organomet. Chem.
1984, 273, 361.
(6) Slugovc, C.; Doberer, D.; Gemel, C.; Schmid, R.; Kirchner, K.;
Winkler, B.; Stelzer, F. Monatsh. Chem. 1998, 129, 221.

Addition of Acetylenes to Olefins
Organometallics, Vol. 18, No. 6, 1999 1013
Sch em e 2
F igu r e 3. Structural view of 5a ‚1/2CH2Cl2 (CH2Cl2 and
-
PF6 omitted for clarity). Selected bond lengths (Å): Ru-
-
F igu r e 2. Structural view of 2a ‚CH2Cl2 (CH2Cl2 and PF6
P(1) 2.318(1), Ru-C(Cp)av 2.216(4), Ru-C(20) 2.228(4),
Ru-C(21) 2.144(4), Ru-C(22) 2.193(3), Ru-C(23) 2.277-
(3), C(20)-C(21) 1.418(5), C(21)-C(22) 1.431(5), C(22)-
C(23) 1.423(4), C(23)-C(24) 1.485(4).
omitted for clarity). Selected bond lengths (Å): Ru-P(1)
2.335(1), Ru-C(Cp)av 2.239(4), Ru-C(20) 2.253(3), Ru-
C(21) 2.175(3), Ru-C(22) 2.196(3), Ru-C(23) 2.304(3),
C(20)-C(21) 1.431(5), C(21)-C(22) 1.426(5), C(22)-C(23)
1.428(5), C(23)-C(24) 1.491(5).
from that of 2a . Thus, the expected upfield resonance
1
of the H6syn proton is no longer present in the H NMR
Ta ble 1. P r od u ct Distr ibu tion of th e Rea ction of 1
w ith Alk yn es
spectrum.
Instead, a doublet centered at 5.82 ppm (H6anti) with
3
a coupling constant of J HH ) 7.6 Hz is observed,
further, consistent with a cis arrangement of the C5-
C6 double bond and either a s-cis or a s-trans geometry
of the butadiene fragment. Unfortunately, attempts to
grow suitable crystals for X-ray diffraction study were
unsuccessful.
The reaction mechanism shown in Scheme 4 repre-
sents our working hypothesis for providing the η4-
butadiene and η3-butadienyl products. First is the
formation of the isomeric η2-alkyne complexes A and A′.
By analogy with the established coupling mechanisms,
proposed by Trost1a and Dixneuf,1d the oxidative cou-
pling of HCtCPh with the double bond of the Ph2PCH2-
CH2CHdCH2 ligand leads to the ruthenacyclopentene
intermediates B and B′, which give the complexes 2a
and 2b , respectively, via a â-elimination/reductive
elimination sequence. Parallel to the oxidative coupling
process, the cationic vinylidene complex C is formed via
a 1,2 hydrogen shift.9 Subsequent [2+2] cycloaddition
at the RudC bond gives the metallacyclobutane complex
D. This reaction needs the presence of a strong base
entry
R1
R2
productsa
1
2
3
4
5
Ph
Ph
Ph
Et
H
D
Ph
Et
Et
76% 2a 23% 2b
78% 2a D 22% 2bD
91% 3b
92% 4b
Ph
85% 5a 15% 5b
Product distribution has been determined by 1H NMR spec-
troscopy. Isolated yield.
a
b
possibility of further functionalizations by treating them
with electrophiles. Accordingly, 2c reacts with CF3-
COOH to yield the new complex [RuCp(κ1(P),η4-(3Z,5Z)-
PPh2CH2CH2CHdCH-CHdCHPh)]CF3COO (2d ) in es-
sentially quantitative yield, as monitored by 1H, 13C{1H},
and 31P{1H}NMR spectroscopies (Scheme 3). From steric
considerations (MM2 calculations indicate unfavorable
repulsive interactions between the phenyl substituents
of the butadiene and the PPh2 moieties), 2d might adopt
the 3Z,5Z-s-trans conformation,7a,8 although the alter-
native s-cis structure cannot definitely be ruled out.
Interestingly, the NMR spectra of 2d differ significantly
(8) For s-trans η4-diene complexes see: (a) Melendez, E.; Arif, A.
M.; Rheingold, A. L.; Ernst, R. D. J . Am. Chem. Soc. 1988, 110, 8703.
(b) Ernst, R. D.; Melendez, E.; Stahl, L. Organometallics 1991, 10, 3635.
(c) Melendez, E.; Ilarraza, R.; Yap, G. P. A.; Rheingold, A. L. J .
Organomet. Chem. 1996, 522, 1. (d) Sugaya, T.; Tomita, A.; Sago, H.;
Sano, M. Inorg. Chem. 1996, 35, 2692. (e) Hunter, A. D.; Legzdins, P.;
Nurse, C. R.; Einstein, F. W. B.; Willis, A. C. J . Am. Chem. Soc. 1985,
107, 1791. (f) Christensen, N. J .; Legzdins, P.; Einstein, F. W. B.; J ones,
R. H. Organometallics 1991, 10, 3070. (g) Carfagna, C.; Deeth, R. J .;
Green, M.; Mahon, M. F.; McInnes, J . M.; Pellegrin, S.; Woolhouse, C.
B. J . Chem. Soc., Dalton Trans. 1995, 3975. (h) Benyunes, S. A.; Day,
J . P.; Green, M.; Al-Saadoon, A. W.; Waring, T. L. Angew. Chem. 1990,
102, 1505.
(7) (a) Fagan, P. J .; Mahoney, W. S.; Calabrese, J . C.; Williams, I.
D. Organometallics 1990, 9, 1843. (b) Gemel, C.; Kalt, D.; Sapunov,
V. N.; Mereiter, K.; Schmid, R.; Kirchner, K. Organometallics 1997,
16, 427. (c) Gemel, C.; Schmid, R.; Kirchner, K.; Mereiter, K. Acta
Crystallogr., in press.

1014 Organometallics, Vol. 18, No. 6, 1999
Slugovc et al.
Sch em e 3
Sch em e 4
with deprotonation of one of the â-hydrogen atoms,
yielding the stable η3-butadienyl complex 2c. In the
absence of base no evidence of 2c is found, suggesting
that C and D are in equilibrium with A (A′) and that
alternative rearrangements (e.g., a 1,2-H shift to give
either 2a or the s-trans isomer 2d ) are unfavorable or
do not take place at all.
via either a ruthenacyclopentene complex or the suc-
cessive intermediacy of a vinylidene and a ruthenacy-
clobutane complex. The latter mode is restricted to
terminal alkynes. It is interesting to note that analogous
reactions on RuTp complexes proceed exclusively via the
vinylidene pathway.3
The following observations may be taken to support
this mechanism. (i) In the absence of base, the reaction
of 1 with DCtCPh gives complexes 2a D and 2bD, where
the deuterium is attached at C5 and C,6 respectively,
and anti to the metal center. This implies that the syn
hydrogen originates exclusively and in all cases from
the olefin. From this labeling experiment and, of course,
from the fact that 2a is actually formed, it is apparent
that no vinylidene but a ruthenacyclopentene interme-
diate is involved in the coupling process. (ii) In the
presence of base, on the other hand, the occurrence of a
vinylidene intermediate was verified by a labeling
experiment. Thus, the η3-butadienyl product 2cD (formed
together with 2a D and 2bD) of the reaction of deuterium-
labeled phenylacetylene DCtCPh with 1 contains deu-
terium exclusively at the olefinic carbon C6 of the
butadienyl moiety, as shown by 1H and 13C NMR
spectroscopy (Scheme 4). The η3-butadienyl complex 2c
did not incorporate deuterium to give 2cD under reflux
in CD3OD in the presence of NaOEt. Likewise, also the
complexes 2a and 2b did not incorporate deuterium to
give 2a D and 2bD under reflux in CD3OD.
Exp er im en ta l Section
Gen er a l In for m a tion . All manipulations were performed
under an inert atmosphere of argon by using Schlenk tech-
niques. All chemicals were standard reagent grade and used
without further purification. The solvents were purified ac-
cording to standard procedures.10 The deuterated solvents were
purchased from Aldrich and dried over 4 Å molecular sieves.
TLC was performed on Riedel-deHaen TLC-sheets silica gel
60 F 254 (layer thickness 0.2 mm). For column chromatogra-
phy silica gel grade 60, 70-230 mesh, 60 Å, purchased from
Merck, or neutral MN-aluminum oxide, purchased from Ma-
cherey-Nagel, was used. [RuCp(CH3CN)3]PF611 and Ph2PCH2-
CH2CHdCH2 were prepared according to the literature. H,
13C{1H}, and 31P{1H} NMR spectra were recorded on a Bruker
AC-250 spectrometer operating at 250.13, 62.86, and 101.26
MHz, respectively, and were referenced to SiMe4 and H3PO4
(85%). Microanalyses were done by Microanalytical Labora-
tories, University of Vienna.
12
1
In summary, we have shown that selective coupling
of olefins and acetylenes (internal and terminal) is
feasible in the coordination sphere of the RuCp complex
[RuCp(κ1(P),η2-PPh2CH2CH2CHdCH2)(CH3CN)]PF6. Two
different reaction routes have been identified proceeding
[Ru Cp (K1(P ),η2-P P h 2CH2CH2CHdCH2)(CH3CN)]P F 6 (1).
To a solution of [RuCp(CH3CN)3]PF6 (317 mg, 0.730 mmol) in
(9) (a) Bruce, M. I. Chem. Rev. 1991, 91, 197. (b) Slugovc, C.;
Sapunov, V. N.; Wiede, P.; Mereiter, K.; Schmid, R.; Kirchner, K. J .
Chem. Soc., Dalton Trans. 1997, 4209. (c) de los Rios, I.; Tenorio, M.
J .; Puerta, M. C.; Valerga, P. J . Am. Chem. Soc. 1997, 119, 6529.
(10) Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory
Chemicals, 3rd ed.; Pergamon: New York, 1988.
(11) Gill, T. P.; Mann, K. R. Organometallics 1982, 1, 485.

Addition of Acetylenes to Olefins
Organometallics, Vol. 18, No. 6, 1999 1015
CH2Cl2 (6 mL) was slowly added Ph2PCH2CH2CHdCH2 (175
mg, 0.730 mmol), and the mixture was stirred at room
temperature for 5 h. During that time the color changed from
orange to yellow. The solvent was then removed under reduced
pressure, and the remaining residue was redissolved in CH2-
Cl2 (1 mL). Upon addition of Et2O (3 mL) and n-hexane (1 mL)
a bright yellow precipitate was formed, which was collected
on a glass frit, washed with Et2O (3 × 1 mL) and n-hexane (1
× 1 mL), and dried in vacuo. Yield: 360 mg (83%). Anal. Calcd
for C23H25F6NP2Ru: C, 46.63; H, 4.25; N, 2.36. Found: C,
20 °C): 90.7 (PPh2), -143.3 (1J PF ) 709.5 Hz, PF6). 31P{1H}
NMR (δ, CDCl3, 20 °C): 89.6 (PPh2), -143.2 (1J PF ) 712.1 Hz,
PF6).
[Ru Cp (K1(P ),η4-(3Z)-P P h 2CH2CH2CHdCH-CP h dCH2)]-
P F 6 (2b). The volume of the CHCl3 filtrate from the recrys-
tallization of 2a was reduced to about 1 mL. Upon addition of
Et2O, a white precipitate was formed, which was collected on
a glass frit, washed with Et2O (2 × 2 mL), and dried under
vacuum. Yields: 16 mg (7%) and 21 mg (15%) from methods
a and b, respectively. Anal. Calcd for C29H27F6P2Ru: C, 53.38;
1
1
46.78; H, 4.33; N, 2.44. H NMR (δ, CDCl3, 20 °C): 7.69-7.32
H, 4.17. Found: C, 53.77; H, 4.44. H NMR (δ, CDCl3, 20 °C):
(m, 10H, Ph), 5.03-4.88 (m, 1H, H3), 4.79 (s, 5H, Cp), 4.49 (d,
3J HHcis ) 8.5 Hz, 1H, H4anti), 3.21-3.02 (m, 2H, H1,2), 2.94-
3
7.90-7.31 (m, 15H, PPh2, PhR), 6.37 (d, J HHcis ) 8.4 Hz, 1H,
2
H4), 5.71 (m, 1H, H3), 4.70 (s, 5H, Cp), 3.61 (d, J HH ) 4.9 Hz,
3
2.62 (m, 1H, H1,2), 2.76 (d, J HHtrans ) 12.6 Hz, 1H, H4syn), 1.90
1H, H6anti), 3.56-3.27 (m, 2H, H1,2), 2.54-2.21 (m, 1H, H1,2),
(s, 3H, NtC-CH3), 1.43-1.19 (m, 1H, H1,2). 13C{1H} NMR (δ,
2
3
1.17 (dd, J HH ) 4.9 Hz, J PH ) 16.4 Hz, 1H, H6syn), 1.05-0.82
1
CDCl3, 20 °C): 138.1 (d, J PC ) 45.8 Hz, 1C, Ph1), 134.0
(m, 1H, H1,2). 13C{1H} NMR (δ, CDCl3, 20 °C): 140.5 (d, J PC
1
2
2
(d, J PC ) 9.5 Hz, 2C, Ph2,6), 131.7 (d, J PC ) 10.2 Hz, 2C,
) 46.9 Hz, 1C, Ph1), 138.7 (1C, PhR1), 134.8 (d, J PC ) 10.3
2
Ph2′,6′), 131.7 (d, J PC ) 2.5 Hz, 1C, Ph4), 131.5 (d, J PC ) 2.5
4
4
Hz, 2C, Ph2,6), 132.8 (d, J PC ) 2.2 Hz, 1C, Ph4), 132.0 (d, J PC
4
1
Hz, 1C, Ph4′), 130.2 (d, J PC ) 1.2 Hz, NtC-CH3), 129.9
3
) 39.8 Hz, 1C, Ph1′), 131.5 (d, 2J PC ) 9.8 Hz, 2C, Ph2′,6′), 131.4
3
3
(d, J PC ) 10.2 Hz, 2C, Ph3,5), 129.6 (d, J PC ) 10.2 Hz, 2C,
(d, J PC ) 3.5 Hz, 1C, Ph4′), 130.5 (1C, PhR4), 130.2 (d, J PC
)
4
3
Ph3′,5′), 129.5 (d, J PC ) 42.6 Hz, 1C, Ph1′), 84.0 (d, J PC ) 1.9
1
2
10.9 Hz, 2C, Ph3,5), 130.0 (2C, PhR3,5), 129.8 (d, J PC ) 9.8 Hz,
3
Hz, 5C, Cp), 77.3 (d, J PC ) 2.5 Hz, C3), 52.3 (C4), 40.9 (d, J PC
1
2C, Ph3′,5′), 126.8 (2C, PhR2,6), 103.5 (C5), 89.5 (5C, Cp), 83.6
) 30.5 Hz, C1), 30.6 (d, J PC ) 9.5 Hz, C2), 4.1 (NtC-CH3).
2
(C4), 79.6 (d, J PC ) 3.3 Hz, C3), 46.5 (d, J PC ) 33.2 Hz, C1),
42.9 (d, 2J PC ) 1.0 Hz, C6), 25.5 (d, 2J PC ) 7.8 Hz, C2). 31P{1H}
NMR (δ, CDCl3, 20 °C): 91.8 (PPh2), -143.2 (1J PF ) 712.1 Hz,
PF6).
3
1
31P{1H} NMR (δ, CDCl3, 20 °C): 76.3 (PPh2), -143.5 (1J PF
712.1 Hz, PF6).
)
[R u Cp (K1(P ),η4-(3Z,5E )-P P h 2CH 2CH 2CH dCH -CH d
CHP h )]P F 6 (2a ). Meth od a . A suspension of 1 (202 mg, 0.341
mmol) in MeOH (4 mL) was treated with HCtCPh (131 µL,
1.19 mmol) and NaOMe (23.2 mg, 0.341 mmol) and was then
stirred under reflux for 3 h. After that time the solvent was
removed under reduced pressure. The residue was redissolved
in CH2Cl2 (10 mL), and insoluble materials were removed by
filtration over Na2SO4. The volume of the filtrate was reduced
to about 2 mL, and upon addition of Et2O (15 mL), a white
precipitate was formed, which was collected on a glass frit and
washed with Et2O (5 × 2 mL) (the filtrate is used for the
isolation of 2c). The crude product (145 mg) was purified via
column chromatography (silica gel). The first yellow band was
eluted with CH2Cl2/MeOH (v/v ) 30:1). Recrystallization from
CHCl3 gave 2a in the form of 2a ‚CH2Cl2 as pale yellow crystals
(the CHCl3 filtrate was used for the isolation of 2b). Yield: 85
mg of (34%). Meth od b. A solution of 1 (126 mg, 0.213 mmol)
and HCtCPh (70 µL, 0.638 mmol) in CHCl3 (4 mL) was stirred
under reflux for 2 h. Upon removal of the solvent the resulting
residue was transferred to a glass frit and washed with Et2O
(5 × 1 mL). The crude product was purified by two recrystal-
lizations from CHCl3, yielding yellow crystals of 2a ‚CH2Cl2 (the
CHCl3 solution was used for the isolation of 2b). Yield: 78
mg (56%). Anal. Calcd for C29H27F6P2Ru: C, 53.38; H, 4.17.
Found: C, 48.99; H, 4.08, which is consistent with C29H27F6P2-
Ru‚CH2Cl2. 1H NMR (δ, MeNO2-d3/CDCl3 (1:3), 20 °C): 7.77-
7.33 (m, 10H, PPh2), 7.21 (t, 1H, PhR4), 7.08 (t, 2H, PhR3,5),
R u Cp (K1(P ),(3,4,5-η)-(3E ,5E /Z)-P P h 2CH 2CH 2CH CH -
CCHP h ) (2c). The volume of the filtrate of 2a was reduced
to about 2 mL, and insoluble materials were removed by
filtration. Evaporation of the remaining solvent gave an orange
oil (80 mg). The crude product was dissolved in CH2Cl2 (1 mL)
and purified via column chromatography (neutral Al2O3, 5 g).
The first yellow band was eluted with CH2Cl2 and evaporated
to dryness, affording 2c as an orange oil. Yield: 67 mg (39%).
Anal. Calcd for C29H26PRu: C, 68.76; H, 5.17. Found: C, 68.91;
H, 5.22. 1H NMR (δ, CDCl3, 20 °C): 7.65-7.01 (m, 13H, PPh2,
H6, PhR), 6.80 (m, 3H, PhR), 4.94 (s, 5H, Cp), 4.47 (m, 1H, H3),
3.57 (m, 1H, H4), 2.36-2.07 (m, 1H, H1,2), 2.01-1.86 (m, 1H,
H1,2), 1.74-1.57 (m, 1H, H1,2), 1.43-0.88 (m, 1H, H1,2). 13C-
3
{1H} NMR (δ, CDCl3, 20 °C): 171.6 (d, J PC ) 15.8 Hz, 1C,
4
1
C5), 140.7 (d, J PC ) 2.2 Hz, PhR1), 140.2 (d, J PC ) 35.4 Hz,
1C, Ph1), 138.9 (d, J PC ) 46.3 Hz, 1C, Ph1′), 134.4 (d, J PC
)
1
2
11.4 Hz, 2C, Ph2,6), 132.0 (d, J PC ) 9.8 Hz, 2C, Ph2′,6′), 130.0
2
(d, J PC ) 2.2 Hz, 1C, Ph4), 129.6 (d, J PC ) 2.7 Hz, 1C, Ph4′),
4
4
128.3 (d, 3J PC ) 9.3 Hz, 2C, Ph3,5), 128.8 (d, 3J PC ) 9.8 Hz, 2C,
Ph3′,5′), 127.7 (2C, PhR3,5), 125.8 (d, J PC ) 1.1 Hz, 2C, PhR2,6),
5
124.7 (PhR4), 118.3 (d, J PC ) 4.9 Hz, C6), 82.1 (d, J PC ) 2.2
3
2
Hz, 5C, Cp), 61.5 (C4), 40.7 (d, J PC ) 1.1 Hz, 1C, C3), 29.4 (d,
2
1J PC ) 32.7 Hz, C1), 26.8 (d, 2J PC ) 14.2 Hz, C2). 31P{1H} NMR
(δ, CDCl3, 20 °C): 84.3 (PPh2).
[R u Cp (K1(P ),η4-(3Z,5E )-P P h 2CH 2CH 2CH dCH -CDd
CHP h )]P F 6 (2a D). This complex was prepared analogously
to 2a (method a) in MeOH-d4 (3 mL), with 1 (100 mg, 0.169
mmol) and DCtCPh (56 µL, 0.507 mmol) as the starting
materials. Yield: 40 mg (36%). Anal. Calcd for C29H26DF6P2-
3
3
6.62 (d, 2H, PhR2,6), 6.48 (dd, J HHtrans ) 9.7 Hz, J HHcis ) 6.1
3
3
Hz, 1H, H5), 6.03 (dd, J HHtcis ) 7.9 Hz, J HHcis ) 6.1 Hz, 1H,
H4), 5.52-5.42 (m, 1H, H3), 4.95 (s, 5H, Cp), 3.71-3.50 (m,
2H, H1,2), 2.68-2.38 (m, 1H, H1,2), 2.65 (dd, 3J HHtrans ) 9.7 Hz,
3J PH ) 12.5 Hz, 1H, H6syn), 1.22-1.05 (m, 1H, H1,2). 13C{1H}
1
Ru: C, 53.30; H, 4.32. Found: C, 53.42; H, 4.29. H NMR (δ,
MeNO2-d3/CDCl3 (1:3), 20 °C): 7.77-7.33 (m, 10H, PPh2), 7.21
(t, 1H, PhR4), 7.08 (t, 2H, PhR3,5), 6.62 (d, 2H, PhR2,6), 6.03 (d,
3J HHtcis ) 7.9 Hz, 1H, H4), 5.52-5.42 (m, 1H, H3), 4.95 (s, 5H,
Cp), 3.71-3.50 (m, 2H, H1,2), 2.68-2.38 (m, 1H, H1,2), 2.65 (d,
3J PH ) 12.5 Hz, 1H, H6syn), 1.22-1.05 (m, 1H, H1,2). 13C{1H}
1
NMR (δ, CD3NO2/CDCl3 (1:3), 20 °C): 140.6 (d, J PC ) 49.1
3
2
Hz, 1C, Ph1), 139.6 (d, J PC ) 1.0 Hz, 1C, PhR1), 134.1 (d, J PC
) 10.0 Hz, 2C, Ph2,6), 132.0 (d, J PC ) 2.4 Hz, 1C, Ph4), 131.0
4
(d, 4J PC ) 2.9 Hz, 1C, Ph4′), 131.0 (d, 2J PC ) 10.0 Hz, 2C, Ph2′,6′),
129.8 (d, J PC ) 40.5 Hz, 1C, Ph1′), 129.5 (d, J PC ) 10.5 Hz,
1
3
1
NMR (δ, MeNO2-d3/CDCl3 (1:3), 20 °C): 140.6 (d, J PC ) 49.1
2C, Ph3,5), 129.3 (d, J PC ) 10.5 Hz, 2C, Ph3′,5′), 128.7 (2C,
3
3
2
Hz, 1C, Ph1), 139.6 (d, J PC ) 1.0 Hz, 1C, PhR1), 134.1 (d, J PC
PhR3,5), 127.7 (1C, PhR4), 127.4 (2C, PhR2,6), 87.1 (d, J PC ) 1.0
2
) 10.0 Hz, 2C, Ph2,6), 132.0 (d, J PC ) 2.4 Hz, 1C, Ph4), 131.0
4
Hz, 5C, Cp), 83.8 (C5), 82.1 (C4), 80.2 (d, J PC ) 3.8 Hz, C3),
3
(d, 4J PC ) 2.9 Hz, 1C, Ph4′), 131.0 (d, 2J PC ) 10.0 Hz, 2C, Ph2′,6′),
64.9 (d, J PC ) 1.9 Hz, C6), 45.2 (d, J PC ) 33.9 Hz, C1), 24.8
2
1
129.8 (d, J PC ) 40.5 Hz, 1C, Ph1′), 129.5 (d, J PC ) 10.5 Hz,
1
3
(d, J PC ) 7.6 Hz, C2). 31P{1H} NMR (δ, CD3NO2/CDCl3 (1:3),
2
2C, Ph3,5), 129.3 (d, J PC ) 10.5 Hz, 2C, Ph3′,5′), 128.7 (2C,
3
PhR3,5), 127.7 (1C, PhR4), 127.4 (2C, PhR2,6), 87.1 (d, J PC ) 1.0
2
Hz, 5C, Cp), 83.9 (t, J CD ) 23 Hz, C5), 82.3 (C4), 80.2 (d, J PC
1
3
(12) Clark, P. W.; Curtis, J . L. S.; Garrou, P. E.; Hartwell, G. E.
Can. J . Chem. 1974, 52, 1714.
2
1
) 3.8 Hz, C3), 65.1 (d, J PC ) 1.8 Hz, C6), 45.2 (d, J PC ) 33.9

1016 Organometallics, Vol. 18, No. 6, 1999
Slugovc et al.
2
Hz, C1), 24.8 (d, J PC ) 7.6 Hz, C2). 31P{1H} NMR (δ, MeNO2-
[R u Cp (K1(P ),η4-(3Z,5Z)-P P h 2CH 2CH 2CH dCH -CP h d
CHP h )]P F 6 (3). A solution of 1 (108 mg, 0.182 mmol) and
PhCtCPh (48.7 mg, 0.273 mmol) in CHCl3 (4 mL) was heated
under reflux for 17 h. The volume of the solution was reduced
to 0.5 mL, and upon addition of Et2O (1 mL), a white
precipitate was formed, which was collected on a glass frit,
washed with Et2O (3 × 2 mL), and dried in vacuo. Yield: 121
mg (91%). Anal. Calcd for C35H31F6P2Ru: C, 57.69; H, 4.29.
d3/CDCl3 (1:3), 20 °C): 90.7 (PPh2), -143.3 (1J PF ) 709.5 Hz,
PF6).
[R u Cp (K1(P ),η4-(3Z,5E )-P P h 2CH 2CH 2CH dCH -CDd
CHPh)]PF6(2aD)and [RuCp(K1(P),η4-(3Z,5Z)-PPh2CH2CH2CHd
CH-CP h dCHD)]P F 6 (2bD). A sealed NMR tube, charged
with 1 (20 mg, 0.034 mmol) and DCtCPh (9.6 µL, 0.101 mmol),
was heated at 57 °C with CDCl3 as the solvent. The sample
was transferred to a NMR probe, and 1H and 31P{1H}NMR
spectra were recorded. The conversion was complete after 1 h
10 min, resulting in a mixture of 2a D (78%) and 2bD (22%).
The 1H NMR spectra of these complexes are consistent with
those of 2a and 2b, respectively, excepting the following
signals. 2a D: The signal at 6.48 ppm is no longer observed
1
Found: C, 57.92; H, 4.42. H NMR (δ, CDCl3, 20 °C): 7.48-
7.43 (m, 6H, PPh2, PhR′), 7.32-7.20 (m, 9H, PPh2, PhR′), 7.03
(t, 1H, PhR4), 6.82 (t, 2H, PhR3,5), 6.37 (d, 2H, PhR2,6), 6.33 (m,
1H, H4), 5.61 (m, 1H, H3), 4.98 (s, 5H, Cp), 3.60-3.41 (m, 2H,
3
H1,2), 2.75-2.43 (m, 1H, H1,2), 2.35 (d, J PH ) 15.3 Hz, 1H,
H6syn), 1.54-1.30 (m, 1H, H1,2). 13C{1H} NMR (δ, CDCl3, 20
1
°C): 141.1 (d, J PC ) 48.0 Hz, 1C, Ph1), 139.6 (PhR1), 137.0
3
(PhCHdCD-CHdCH-CH2), 6.03 (d J HHtcis ) 7.9 Hz, 1H,
2
4
(PhR′1), 134.1 (d, J PC ) 9.8 Hz, 2C, Ph2,6), 132.1 (d, J PC ) 2.2
3
PhCHdCD-CHdCH-CH2), 2.65 (d, J PH ) 12.5 Hz, 1H,
Hz, 1C, Ph4), 131.6 (2C, PhR′), 131.4 (d, 4J PC ) 2.8 Hz, 1C, Ph4′),
PhCHsyndCD-CHdCH-CH2). 31P{1H} NMR (δ, CDCl3, 20
°C): 89.6 (PPh2), -143.2 (1J PF ) 712.1 Hz, PF6). 2bD: The
signal at 3.61 ppm is no longer observed (DantiCHdCPh-CHd
131.2 (d, J PC ) 9.8 Hz, 2C, Ph2′,6′), 130.5 (2C, PhR′), 130.01
2
(PhR′4), 130.02 (d, J PC ) 10.4 Hz, 2C, Ph3,5), 130.03 (d, J PC
)
3
1
41.4 Hz, 1C, Ph1′), 129.7 (d, J PC ) 10.4 Hz, 2C, Ph3′,5′), 129.3
3
CH-CH2), 1.17 (d, J PH ) 16.4 Hz, 1H, DCHsyndCPh-CHd
3
(2C, PhR3,5), 128.4 (1C, PhR4), 127.2 (2C, PhR2,6), 105.5 (C5), 90.0
CH-CH2). 31P{1H} NMR (δ, CDCl3, 20 °C): 91.8 (PPh2), -143.2
(1J PF ) 712.1 Hz, PF6).
(5C, Cp), 84.8 (C4), 76.8 (d, J PC ) 3.8 Hz, C3), 61.7 (d, J PC
)
3
2
1.9 Hz, C6), 45.5 (d, 1J PC ) 34.9 Hz, C1), 24.9 (d, 2J PC ) 8.7 Hz,
C2). 31P{1H} NMR (δ, CDCl3, 20 °C): 92.1 (PPh2), -143.4 (1J PF
) 713.4 Hz, PF6).
Ru Cp (K1(P ),(3,4,5-η)-P P h 2CH2CH2CHCHCCDP h ) (2cD).
This complex was prepared analogously to 2a (method a) in
MeOH-d4 (3 mL), with 1 (100 mg, 0.169 mmol) and DCtCPh
(56 µL, 0.507 mmol) as the starting materials. Yield: 24 mg
(28%). Anal. Calcd for C29H25DPRu: C, 68.62; H, 5.36. Found:
[R u Cp (K1(P ),η4-(3Z,5Z)-P P h 2CH 2CH 2CH dCH -CP h d
CHP h )]P F 6 (3). A sealed NMR tube, charged with a solution
of 1 (20 mg, 0.034 mmol) and PhCtCPh (18.2 mg, 0.102 mmol)
in CDCl3 (0.5 mL), was heated at 57 °C. The reaction was
1
C, 68.88; H, 5.44. H NMR (δ, CDCl3, 20 °C): 7.65-7.01 (m,
12H, PPh2, PhR), 6.80 (m, 3H, PhR), 4.94 (s, 5H, Cp), 4.47 (m,
1H, H3), 3.57 (m, 1H, H4), 2.36-2.07 (m, 1H, H1,2), 2.01-1.86
(m, 1H, H1,2), 1.74-1.57 (m, 1H, H1,2), 1.43-0.88 (m, 1H, H1,2).
monitored by H and 31P{1H} NMR spectroscopies, indicating
1
complete conversion after 8 h.
13C{1H} NMR (δ, CDCl3, 20 °C): 171.6 (d, J PC ) 15.8 Hz, 1C,
3
[R u Cp (K1(P ),η4-(3Z,5E )-P P h 2CH 2CH 2CH dCH -CE t d
CHEt)]P F 6 (4). A solution of 1 (100 mg, 0.169 mmol) and
EtCtCEt (29.0 µL, 0.254 mmol) in CHCl3 (4 mL) was heated
at reflux for 17 h. The solution was reduced to about 0.5 mL,
and upon addition of Et2O (1 mL), a bright yellow precipitate
was formed, which was collected on a glass frit, washed with
Et2O (3 × 2 mL), and dried in a vacuum. Yield: 98 mg (92%).
Anal. Calcd for C27H31F6P2Ru: C, 51.27; H, 4.94. Found: C,
51.44; H, 5.09. 1H NMR (δ, CDCl3/CD3NO2 (4:1), 20 °C): 7.65-
7.62 (m, 5H, PPh2), 7.46-7.42 (m, 3H, PPh2), 7.38-7.30 (m,
C5), 140.7 (d, J PC ) 2.2 Hz, PhR1), 140.2 (d, J PC ) 35.4 Hz,
4
1
1C, Ph1), 138.9 (d, J PC ) 46.3 Hz, 1C, Ph1′), 134.4 (d, J PC
)
1
2
11.4 Hz, 2C, Ph2,6), 132.0 (d, J PC ) 9.8 Hz, 2C, Ph2′,6′), 130.0
2
(d, J PC ) 2.2 Hz, 1C, Ph4), 129.6 (d, J PC ) 2.7 Hz, 1C, Ph4′),
128.3 (d, 3J PC ) 9.3 Hz, 2C, Ph3,5), 128.8 (d, 3J PC ) 9.8 Hz, 2C,
Ph3′,5′), 127.7 (2C, PhR3,5), 125.7 (2C, PhR2,6), 124.7 (PhR4), C6
4
4
not observed, 82.1 (d, J PC ) 2.1 Hz, 5C, Cp), 61.5 (C4), 40.7
2
(d, 2J PC ) 1.1 Hz, 1C, C3), 29.4 (d, 1J PC ) 32.7 Hz, C1), 26.8 (d,
2J PC ) 14.2 Hz, C2). 31P{1H} NMR (δ, CDCl3, 20 °C): 84.3
(PPh2).
3
2H, PPh2), 5.60 (d, J HH ) 8.0 Hz, 1H, H4), 5.23 (m, 1H, H3),
4.83 (s, 5H, Cp.), 3.45-3.02 (m, 2H, H1,2), 2.66-2.04 (m, 3H,
CH2CH3, H1,2, H6syn), 1.66-1.47 (m, 1H, CH2CCH3), 1.36 (m,
4H, H,1,2 CH2CH3), 1.05-0.85 (m, 2H, CH2CH3), 0.60 (VT, 3H,
CH2CH3). 13C{1H} NMR (δ, CDCl3/CD3NO2 (4:1), 20 °C): 140.7
(d, 1J PC ) 47.4 Hz, 1C, Ph1), 133.2 (d, 2J PC ) 9.3 Hz, 2C, Ph2,6),
132.3 (d, 4J PC ) 2.7 Hz, 1C, Ph4), 131.4 (d, 2J PC ) 10.4 Hz, 2C,
[R u Cp (K1(P ),η4-(3Z,5E )-P P h 2CH 2CH 2CH dCH -CH d
CHP h )]P F6 (2a) an d [Ru Cp(K1(P ),η4-(3Z)-P P h 2CH2CH2CHd
CH-CP h dCH2)]P F 6 (2b). A sealed NMR tube, charged with
a solution of 1 (20 mg, 0.034 mmol) and HCtCPh (9.6 µL,
0.101 mmol) in CDCl3 (0.5 mL), was heated at 57 °C. The
reaction was monitored by 1H and 31P{1H} NMR spec-
troscopies, indicating complete conversion after 1 h to give a
mixture of 2a (76%) and 2b (23%).
4
3
Ph2′,6′), 131.2 (d, J PC ) 2.7 Hz, 1C, Ph4′), 129.9 (d, J PC ) 10.4
Hz, 2C, Ph3,5), 129.7 (d, J PC ) 10.4 Hz, 2C, Ph3′,5′), 129.1 (d,
3
1J PC ) 47.4 Hz, 1C, Ph1′), 108.9 (C5), 87.1 (d, J PC ) 1.1 Hz,
2
[R u Cp (K1(P ),η4-(3Z,5Z)-P P h 2CH 2CH 2CH dCH -CH d
CHP h )]CF 3COO (2d ). A 5 mm NMR tube was charged with
1c (20 mg, 0.039 mmol) and was capped with a septum. A
solution of CF3COOH (20 µL) in CDCl3 (0.3 mL) was added
by syringe, and the mixture was transferred to the probe head.
NMR spectra were immediately recorded, indicating the
quantitative formation of 2d .1H NMR (δ, CDCl3, 20 °C): 7.66-
5C, Cp.), 83.6 (C4), 77.6 (d, J PC ) 2.7 Hz, C3), 65.7 (d, J PC
)
3
2
2.7 Hz, C6), 44.9 (d, J PC ) 34.3 Hz, C1), 29.5 (CH2CH3), 25.6
1
(CH2CH3), 24.7 (d, J PC ) 7.6 Hz, C2), 18.6 (CH2CH3), 16.5
2
(CH2CH3). 31P{1H} NMR (δ, CDCl3/CD3NO2 (4:1), 20 °C): 86.8
(PPh2), -143.8 (1J PF ) 709.8 Hz, PF6).
[R u Cp (K1(P ),η4-(3Z,5E )-P P h 2CH 2CH 2CH dCH -CE t d
CHP h)]P F6(5a)and [RuCp(K1(P ),η4-(3Z,5Z)-P P h2CH2CH2CHd
CH-CP h dCHEt)]P F 6 (5b). A solution of 1 (144 mg, 0.243
mmol) and EtCtCPh (52 µL, 0.364 mmol) in CHCl3 (4 mL)
was heated under reflux for 17 h. The solution was reduced
to 0.5 mL, and upon addition of Et2O (1 mL), a white
precipitate was formed, which was collected on a glass frit,
washed with Et2O (3 × 2 mL), and dried in vaccuo. Yield: 159
mg (96%) as a regioisomeric mixture of 5a and 5b in a 7:1
ratio (determined by 1H and 31P{1H} NMR spectroscopies). 5a
could be obtained in pure form after purification by column
chromatography (silica gel). The first yellow band was eluted
with CH2Cl2/MeOH (v/v ) 30:1). Recrystallization of the crude
product from CHCl3 yielded analytically pure 5a in the form
of yellow crystals. Yield: 78 mg (47%). 5b could not be obtained
7.24 (m, 15H, PPh2, PhR), 5.82 (d, J HHcis ) 7.6 Hz, 1H, H6),
3
5.58 (m, 2H, H4, H3), 4.52 (s, 5H, Cp), 3.23-3.08 (m, 3H, H5,
H1,2), 2.86-2.60 (m, 1H, H1,2), 2.38-2.10 (m, 1H, H1,2). 13C-
{1H} NMR (δ, CDCl3, 20 °C): 160.7 (q, J FC ) 38.3 Hz, 1C,
3
CF3COO), 138.4 (PhR1), 136.1 (d, J PC ) 47.4 Hz, 1C, Ph1),
1
132.9 (d, 2J PC ) 8.1 Hz, 2C, Ph2,6), 132.6 (d, 4J PC ) 2.2 Hz, 1C,
Ph4), 131.5 (d, J PC ) 2.8 Hz, 1C, Ph4′), 130.3 (d, J PC ) 10.4
4
3
Hz, 2C, Ph3,5), 130.2 (d, J PC ) 9.8 Hz, 2C, Ph3′,5′), 129.92 (4C,
3
PhR2,3,5,6), 129.9 (d, J PC ) 10.4 Hz, 2C, Ph2′,6′), 127.9 (PhR4),
2
127.7 (d, J PC ) 43.6 Hz, 1C, Ph1′), 116.4 (q, J FC ) 289.6 Hz,
1
2
1C, CF3COO), 90.9 (C5), 90.2 (d, J PC ) 1.6 Hz, 5C, Cp), 87.9
2
(C4), 82.7 (d, J PC ) 2.7 Hz, C3), 74.5 (C6), 41.1 (d, J PC ) 32.2
3
1
2
Hz, C1), 25.3 (d, J PC ) 9.9 Hz, C2). 31P{1H} NMR (δ, CDCl3,
20 °C): 73.4 (PPh2).

Addition of Acetylenes to Olefins
Organometallics, Vol. 18, No. 6, 1999 1017
Ta ble 2. Cr ysta llogr a p h ic Da ta for 1, 2a ‚CH2Cl2, a n d 5a ‚1/2CH2Cl2
1
2a ‚CH2Cl2
5a ‚1/2CH2Cl2
formula
fw
C23H25F6NP2Ru
592.45
C30H30Cl2F6P2Ru
738.45
C31.5H33ClF6P2Ru
724.04
cryst size, mm
space group
a, Å
b, Å
c, Å
0.55 × 0.28 × 0.06
P21/c (No. 14)
7.813(2)
20.403(5)
15.866(6)
101.63(2)
2477(1)
0.65 × 0.12 × 0.12
P21/c (No. 14)
10.333(4)
16.974(6)
18.054(6)
106.84(2)
3031(1)
0.50 × 0.35 × 0.25
P21/n (No. 14)
16.349(4)
17.377(6)
22.709(8)
106.72(2)
6179(3)
â, deg
V, Å3
Z
4
4
8
F
calc, g cm-3
T, K
1.589
298(2)
0.818
empirical
1192
1.618
298(2)
0.856
empirical
1488
1.557
295(2)
0.755
multiscan
2936
µ, mm-1 (Mo KR)
abs corr
F(000)
transmiss fact.
min/max
0.93-0.84
0.93-0.87
0.80-0.74
θ
max, deg
index ranges
25
25
25
-9 e h e 9
-24 e k e 24
-18 e l e 18
24 641
4300
3435
307
0.048
0.063
-12 e h e 12
-20 e k e 20
-21 e l e 21
30 458
5331
4235
410
0.033
0.051
0.080
-19 e h e 19
-20 e k e 20
-26 e l e 27
59 464
10 835
8935
812
0.042
0.053
0.109
no. of rflns measd
no. of unique rflns
no. of rflns I > 2σ(I)
no. of params
R1 (I > 2σ(I))a
R1 (all data)
wR2 (all data)b
diff Fourier peaks
min/max, e Å-3
0.139
-0.56/0.69
-0.31/0.49
-0.56/0.53
R1 ) ∑||Fo| - |Fc||/∑|Fo|. wR2 ) [∑(w(Fo - Fc2)2)/∑(w(Fo2)2)]1/2
.
a
b
2
in pure form. Anal. Calcd for C31H31F6P2Ru: C, 54.71; H, 4.59.
Found: C, 55.00; H, 4.74. 5a : 1H NMR (δ, CDCl3/CD3NO2 (4:
1), 20 °C): 7.42-7.40 (m, 4H, PPh2), 7.29-6.92 (m, 9H, PPh2,
PhR), 6.67 (d, 1H, PhR2,6), 5.66 (d, 3J HH ) 8.2 Hz, 1H, H4), 5.27
(m, 1H, H3), 4.91 (s, 5H, Cp), 3.46-3.35 (m, 3H, CH2CH3, H1,2),
3.12-2.98 (m, 1H, CH2CH3), 2.60-2.47 (m, 1H, H1,2), 2.20 (d,
3J PH ) 14.4 Hz, 1H, H6syn), 1.38-1.18 (m, 1H, H1,2), 1.06 (t,
3H, CH2CH3). 13C{1H} NMR (δ, CDCl3/CD3NO2 (4:1), 20 °C):
X-r a y Str u ctu r e Deter m in a tion for 1, 2a ‚CH2Cl2, a n d
5a ‚1/2CH2Cl2. Crystals of 1, 2a ‚CH2Cl2, and 5a ‚1/2CH2Cl2 were
obtained by diffusion of Et2O into CH2Cl2 solutions. Crystal
data and experimental details are given in Table 2. X-ray data
were collected on a Siemens Smart CCD area detector diffrac-
tometer (graphite monochromated Mo KR radiation, λ )
0.710 73 Å, a nominal crystal-to-detector distance of 4.45 cm,
0.3° ω-scan frames). Corrections for Lorentz and polarization
effects, for crystal decay, and for absorption were applied
(multiscan method, program SADABS13 was used). The struc-
tures of 1 and 5a ‚1/2CH2Cl2 were solved by direct methods,
whereas the structure of 2a ‚CH2Cl2 was solved by the Patter-
son method, using the program SHELXS97.14 Structure refine-
ment on F2 was carried out with the program SHELXL97.15
All non-hydrogen atoms were refined anisotropically. Hydro-
gen atoms were inserted in idealized positions and were
refined riding with the atoms to which they were bonded.
1
2
140.7 (d, J PC ) 48.0 Hz, 1C, Ph1), 137.4 (PhR), 133.8 (d, J PC
4
) 10.4 Hz, 2C, Ph2,6), 131.6 (d, J PC ) 2.7 Hz, 1C, Ph4), 131.2
(d, 4J PC ) 2.7 Hz, 1C, Ph4′), 130.9 (d, 2J PC ) 9.8 Hz, 2C, Ph2′,6′),
3
130.2 (2C, PhR3,5), 129.5 (d, J PC ) 10.4 Hz, 2C, Ph3,5), 128.9
(d, 3J PC ) 10.4 Hz, 2C, Ph3′,5′), 128.5 (2C, PhR2,6), 127.5 (d, 1J PC
2
) 49.6 Hz, 1C, Ph1), 127.4 (1C, PhR4), 108.7 (C5), 87.8 (d, J PC
3
) 1.1 Hz, 5C, Cp), 81.1 (C4), 76.9 (d, J PC ) 3.3 Hz, C3), 66.0
2
1
(d, J PC ) 3.3 Hz, C6), 45.2 (d, J PC ) 34.9 Hz, C1), 29.6 (CH2-
CH3), 24.4 (d, J PC ) 7.6 Hz, C2), 17.0 (CH2CH3). 31P{1H} (δ,
2
CDCl3/CD3NO2 (4:1), 20 °C): 90.2 (PPh2), -143.8 (1J PF ) 709.5
Hz, PF6). NMR spectra of 5b were taken from the mixture of
Ack n ow led gm en t. Financial support by the “Fonds
zur Fo¨rderung der wissenschaftlichen Forschung” is
gratefully acknowledged (Project No. 11896).
1
regioisomers. H NMR (δ, CDCl3/CD3NO2 (4/1), 20 °C) (reso-
nances in aromatic region could not be assigned): 5.79 (d, 3J HH
) 8.8 Hz, 1H, H4), 5.10 (m, 1H, H3), 4.82 (s, 5H, Cp), 0.25 (t,
3H, CH2CH3); the resonances of all other protons were not
assignable. 13C{1H} NMR (δ, CDCl3/CD3NO2 (4:1), 20 °C):
Su p p or tin g In for m a tion Ava ila ble: Listings of atomic
coordinates, anisotropic temperature factors, bond lengths and
angles, and least-squares planes for 1, 2a ‚CH2Cl2, and 5a ‚
1/2CH2Cl2. This material is available free of charge via the
Internet at http://pubs.acs.org.
140.8 (d, J PC ) 48.0 Hz, 1C, Ph1), 138.1 (PhR), 133.9 (d, J PC
1
2
) 9.8 Hz, 2C, Ph2,6), 132.6 (d, J PC ) 2.7 Hz, 1C, Ph4), 131.2
4
(d, 4J PC ) 2.7 Hz, 1C, Ph4′), 131.0 (d, 2J PC ) 9.8 Hz, 2C, Ph2′,6′),
130.3 (2C, PhR3,5), 129.9 (d, J PC ) 10.4 Hz, 2C, Ph3,5), 129.6
3
3
1
(d, J PC ) 10.4 Hz, 2C, Ph3′,5′), 129.0 (d, J PC ) 36.5 Hz, 1C,
OM980902X
Ph1), 128.9 (2C, PhR2,6) (PhR4 was not observed due to coupling
with the deuterium atom), 108.7 (C5), 88.0 (d, J PC ) 1.1 Hz,
(13) Sheldrick, G. M. SADABS: Program for Absorption Correction;
University of Go¨ttingen: Germany, 1996.
(14) Sheldrick, G. M. SHELXS97: Program for the Solution of
Crystal Structures; University of Go¨ttingen: Germany, 1997.
(15) Sheldrick, G. M. SHELXL97: Program for Crystal Structure
Refinement; University of Go¨ttingen: Germany, 1997.
2
5C, Cp), 83.3 (C4) (C3 was not observed), 66.0 (d, J PC ) 3.2
2
Hz, C6), 44.7 (d, J PC ) 35.4 Hz, C1), 25.6 (CH2CH3), 24.4 (d,
1
2J PC ) 7.6 Hz, C2), 15.3 (CH2CH3). 31P{1H} (δ, CDCl3/CD3NO2
(4:1), 20 °C): 90.4 (PPh2), -143.8 (1J PF ) 709.5 Hz, PF6).