Functionalised alkenylcarbene metal complexes (M=Ru, W, Cr) by activation of propargyl alcohol derivatives

Article abstract of DOI:10.1016/S0022-328X(00)00038-3

The reaction of arene ruthenium(II) complexes [Ru(η⁶-C₆Me₄R₂)(PMe ₃)Cl₂] (1, R=Me; 1′, R=H) with propargyl alcohol derivatives HCC(H)(OH)(p-C₆H₄-X) (a, X=HCC(H)(OH); c, X=CHO; d, X=CH=CH₂; e, X=CH=CH-CH=CH₂) and methanol gives the (methoxy)-alkenylcarbene ruthenium complexes [Ru(η⁶-C₆Me₄R₂)(PMe ₃)(Cl) (=C(OMe)(CH=CH-p-C₆H₄-X)][PF₆] (2a) and (2′c-e). Similarly, the half-sandwich carbene complexes [Ru(η⁵-C₅H₅)(CO)(PPh ₃)(=C(OMe)(CH=CH-p-C₆H₄-X)][BF₄] (4a and 4d) are obtained from [Ru(η⁵-C₅H₅)(CO)(PPh₃)(Cl)] (3) and propargyl alcohol derivatives a and d, respectively. Treatment of M(CO)₅(THF) (M=W, Cr) with a and HCC(H)(OH)-C₄H₂S-(OH)(H)CCH (b) yields the monometallic complexes (CO)₅M=C(OMe)(=C(OMe)(CH=CH-Ar-(OH)(H)CCH)] (5a) (M=W; -Ar-=-C₆H₄-), 5b (M=W; -Ar-=-C₄H₂S-), and 7a (M=Cr; -Ar-=-C₆H₄-) as the major products, and the bimetallic complexes (CO)₅W=C(OMe)CH=CH-Ar-CH=CH(OMe)C=W(CO)₅ (6a) and (6b) as the minor products. Finally, the reaction of 5a and 5b with amines (ⁱPrNH₂, Me₂NH, Et₂NH), and diamines such as ethylene diamine and piperazine produces the expected amino alkenyl-tungsten complexes 9a-13a and 9b in high yields.

Full text of DOI:10.1016/S0022-328X(00)00038-3

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 601 (2000) 78–86
Functionalised alkenylcarbene metal complexes (M=Ru, W, Cr)
by activation of propargyl alcohol derivatives
Karine Ulrich, Emmanuel Porhiel, Vincent Pe´ron, Vincent Ferrand,
Hubert Le Bozec *
UMR 6509 CNRS-Uni6ersite´ de Rennes 1, Organome´talliques et Catalyse: Chimie et Electrochimie Mole´culaire, Campus de Beaulieu,
F-35042 Rennes, Cedex, France
Received 15 December 1999; accepted 19 January 2000
Abstract
The reaction of arene ruthenium(II) complexes [Ru(h6-C6Me4R2)(PMe3)Cl2] (1, R=Me; 1%, R=H) with propargyl alcohol
derivatives HCꢀC(H)(OH)(p-C6H4ꢁX) (a, X=HCꢀC(H)(OH); c, X=CHO; d, X=CHꢂCH2; e, X=CHꢂCHꢁCHꢂCH2) and
methanol gives the (methoxy)-alkenylcarbene ruthenium complexes [Ru(h6-C6Me4R2)(PMe3)(Cl) (ꢂC(OMe)(CHꢂCH-p-
C6H4ꢁX)][PF6] (2a) and (2%c–e). Similarly, the half-sandwich carbene complexes [Ru(h5-C5H5)(CO)(PPh3)(ꢂC(OMe)(CHꢂCH-p-
C6H4ꢁX)][BF4] (4a and 4d) are obtained from [Ru(h5-C5H5)(CO)(PPh3)(Cl)] (3) and propargyl alcohol derivatives a and d,
respectively. Treatment of M(CO)5(THF) (M=W, Cr) with a and HCꢀC(H)(OH)ꢁC4H2Sꢁ(OH)(H)CꢀCH (b) yields the
monometallic complexes (CO)5MꢂC(OMe)(ꢂC(OMe)(CHꢂCHꢁArꢁ(OH)(H)CꢀCH)] (5a) (M=W; ꢁArꢁ=ꢁC6H4ꢁ), 5b (M=W;
ꢁArꢁ=ꢁC4H2Sꢁ), and 7a (M=Cr; ꢁArꢁ=ꢁC6H4ꢁ) as the major products, and the bimetallic complexes (CO)5WꢂC(OMe)CHꢂ
CHꢁArꢁCHꢂCH(OMe)CꢂW(CO)5 (6a) and (6b) as the minor products. Finally, the reaction of 5a and 5b with amines (iPrNH2,
Me2NH, Et2NH), and diamines such as ethylene diamine and piperazine produces the expected amino alkenyl–tungsten
complexes 9a–13a and 9b in high yields. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Ruthenium; Tungsten; Chromium; Alkenylcarbene; Alkynols
1. Introduction
fragments such as [Ru(h6-C6R6)(PR3)(Cl)]+ [2,3],
[Ru(h5-C5H5)(CO)(PPr3i )]+ [4], [Ru(h5-C9H7)(dppm)]+
[5] and [M(CO)5] (M=Cr, W) [6,7]. The synthesis of
a,b-unsaturated acyl complexes containing the elec-
Propargyl alcohol derivatives are a useful class of
compounds that can be readily activated by transition
metals and allow the preparation of a variety of multi-
ple metal–carbon bond species such as vinylidene, al-
lenylidene and alkenylcarbene complexes. Thus, a wide
range of stable allenylidene complexes of Group 8
metals has been prepared from various substituted 2-
propyn-1-ols and electron-rich and/or bulky metal com-
plexes [1]. On the other hand, the use of more
electron-poor complexes generates very reactive elec-
trophilic allenylidene intermediates, which can be
trapped by addition of nucleophiles, such as alcohols.
This reactivity has offered an easy synthetic route to
(alkoxy)-alkenylcarbene-containing
organometallic
* Corresponding author.
Scheme 1.
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 0 ) 0 0 0 3 8 - 3

K. Ulrich et al. / Journal of Organometallic Chemistry 601 (2000) 78–86
79
trophilic moiety [Fe(h5-C5Me5)(CO)2]+ has also been
recently reported [8]. The success of this stategy to
prepare alkenylcarbene complexes has prompted us to
examine the generalisation of this procedure by using
more sophisticated 2-propyn-1-ols such as a–e (Scheme
1). This study aims at developing access to new a,b-un-
saturated carbene derivatives as building blocks for the
elaboration of bimetallic complexes. Here we report (i)
the preparation of new propargylic alcohol derivatives,
and (ii) the synthesis and characterisation of the corre-
sponding (methoxy)-alkenylcarbene complexes obtained
by activation of these alkynols in methanol with the
half-sandwich precursors [Ru(h6-C6M4R2)(PMe3)Cl2]
(R=Me, H) and [Ru(h5-C5H5)(CO)(PPh3)(Cl)], and
with the chromium and tungsten carbonyl adducts
[M(CO)5(THF)]. In addition, we describe the aminoly-
sis reactions of the (methoxy)-alkenylcarbene–tungsten
complexes [9].
mixture of cis/trans isomers (2/3) which could not be
separated.
2.2. Synthesis of (methoxy)-alkenylcarbene–ruthenium
complexes
Treatment of a methanol–dichloromethane solution
of 1 with the dialkynol a in the presence of NaPF6 led
slowly to
a dark-red solution, from which the
(methoxy)-alkenylcarbene complex 2a was isolated as a
black powder in 48% yield (Scheme 2). The clean
formation of 2a requires the addition of an excess of a
(three equivalents) to a dilute solution of 1, otherwise a
stoichiometric reaction gives a mixture of intractable
organometallic compounds including 2a along with the
corresponding bimetallic bis-carbene derivative. In a
similar way, complexes 2%c, 2%d and 2%e were isolated in
good yield (60–75%) from alcohols c–e and the te-
tramethylbenzene ruthenium precursor 1% (Scheme 2).
The carbene complex 2%d was also synthesised by react-
ing the free aldehyde group in 2%c with Ph3PꢂCH2, but
could not be fully separated from triphenylphosphine
oxide. The complex 2%e, containing the dienyl sub-
stituent C6H4ꢁCHꢂCHꢁCHꢂCH2 on the alkenylcarbene
moiety, was isolated as cis/trans isomers (:2:3). The
spectroscopic properties of 2a and 2%c–e are similar to
those of the previously synthetised arene (methoxy)-
alkenylcarbene ruthenium complexes [3] (see Section 3).
2. Results and discussion
2.1. Synthesis of the propargyl alcohol deri6ati6es
The dialkynol derivatives a and b were readily pre-
pared in approximately 80% yield upon addition of
LiCꢀCH (two equivalents) to the corresponding dialde-
hydes [10]. A two-step procedure was used for the
synthesis of c in 66% overall yield from terephthalde-
hyde monodiethyl acetal. The preparation of propargyl
alcohol derivatives d and e was achieved by a Wittig
reaction between c and the in situ-prepared ylide
reagents Ph3PꢂCH2 and Ph3PꢂCHꢁCHꢂCH2, respec-
tively (Scheme 1). Compound e was obtained as a
1
In particular, the H-NMR spectra show, besides the
methoxy and aryl resonances, two typical doublets as-
signed to the CH olefinic protons. The high values of
the vicinal coupling constants (3JHH=15–16 Hz)
confirm the E configuration of the CHꢂCH bond. The
presence of the carbene ligand is evidenced by the
Scheme 2.

80
K. Ulrich et al. / Journal of Organometallic Chemistry 601 (2000) 78–86
Scheme 3.
low-field doublet in the 13C-NMR spectra at l:305
ppm (2JCP=19–20 Hz).
fraction contained the violet binuclear biscarbene com-
plexes 6a–8a (9–10%), whereas the second fraction
gave the red monometallic alkenylcarbene complexes
5a–7a (33–41%) (Scheme 4). Similarly, the propargyl
alcohol b containing a thienyl bridge afforded the cor-
responding tungsten carbene and biscarbene derivatives
5b and 6b in yields of 33 and 9%, respectively. The
methoxy-alkenylcarbene tungsten 5d was also formed in
good yield (60%) under the same reaction conditions
from the 2-propyn-1-ol (d) (Scheme 4). The spectro-
scopic data of 5a,b,d and 7a are in accordance with the
presence of the (methoxy)-alkenylcarbene moieties, and
can be compared with those of the related tungsten and
Only one example of a cyclopentadienyl ruthenium
complex containing an (alkoxy)-a,b-unsaturated car-
bene ligand has been previously reported in the litera-
ture [4]. This complex was obtained by nucleophilic
addition of methanol (or ethanol) to the isolated
diphenylallenylidene cations [Ru(h5-C5H5)(CO)(PiPr3)-
(CꢂCꢂCPh2]+, a behaviour which contrasts with the
inertness of the same ligand bonded to the more elec-
tron-rich fragment [Ru(h5-C5H5)(PR3)2]+ (PR3=PPh3,
PMe3) [11,12]. In our case, we used the isoelectronic,
readily available [Ru(h5-C5H5)(CO)(PPh3)(Cl)] (3) [13]
to prepare the corresponding (methoxy)-alkenylcarbene
complexes. Thus, the reaction of 3 with 2-propyn-1-ol
derivatives a (large excess) and d in methanol–
dichloromethane, in the presence of AgBF4, gave the
expected complexes 4a and 4d as orange microcrys-
talline solids in 74 and 51% yield, respectively (Scheme
3). Both complexes were characterised by spectroscopic
means. Typically, the low-field resonances of the car-
benic RuꢂC appear as broad signals at l:300 ppm,
and the strong vicinal coupling constants (3JHH=15.3
1
chromium derivatives [6]. Thus, H-NMR spectra ex-
hibit typical resonances for the alkenyl fragments with
the E configuration; the 13C-NMR spectra show two
resonances each for the cis and trans CO ligands, and
low-field carbene resonances in the range expected for
alkoxy-carbene–tungsten and –chromium complexes
[l(WꢂC):305 ppm and l(CrꢂC):335 ppm]. The
NMR spectra of the bimetallic complexes are more
simple due to their high symmetry; for example, the
1H-NMR spectrum of 6a exhibits only two doublets for
the vinylic protons (3JHH=15.5 Hz), one resonance for
the protons of the phenyl bridge and another one for
the methoxy protons.
(Methoxy)-carbene–tungsten complexes 5 were easily
transformed into the corresponding amino-carbene
complexes by aminolysis with secondary and primary
amines. Thus, low-temperature treatment of 5a,b with
dimethylamine or diethyl amine in diethyl ether af-
forded quantitatively the (dialkylamino)-alkenylcarbene
derivatives 9a,b and 10a in almost quantitative yield as
bright-orange powders (Scheme 5). Upon reacting 5a
1
Hz) observed in the H-NMR spectra are typical of an
E configuration for the alkenyl substituents.
2.3. Synthesis of (methoxy)- and
(amino)-alkenylcarbene–tungsten and chromium
complexes
Treatment of a methanol solution of a with the
photogenerated M(CO)5·THF adducts (M=W, Cr) af-
forded a mixture of products, whatever the amount of
dialkynol used (1.5–3 equivalents). They were readily
separated by chromatographic workup, and the first

K. Ulrich et al. / Journal of Organometallic Chemistry 601 (2000) 78–86
81
Scheme 4.
with iso-propylamine the aminocarbene 11a was formed
as a mixture of E and Z isomers, which could not be sep-
arated by chromatography (E/Z:3/1). Finally, the
aminolysis route was extended to the high-yield synthesis
of the (diamino)-carbene complexes 12a and 13a (E/Z:
9/1) by using piperazine and ethylene diamine, respec-
tively. The 1H- and 13C-NMR data are in good
agreement with those previously reported for other
(amino)-alkenylcarbene–tungsten complexes [6,14,15].
The protons and carbons of the alkenyl moieties are typ-
ically shifted upfield relative to those of the methoxy-car-
bene precursor 5a, and the carbene resonances are
usually found at l:245–250 ppm.
access of such dissymmetric p-conjugated bridged car-
bene complexes [9].
3. Experimental
All manipulations were carried out under an argon at-
mosphere with Schlenk techniques. Solvents were dried
and distilled before use by standard techniques. Com-
plexes (h6-C6Me4R2)RuCl2(PMe3) (R=H, Me) [16] and
(h5-C5H5)RuCl(CO)(PPh3) [13] were prepared according
to the literature procedure. NMR spectra were recorded
on Bruker DPX-200 and AM-300 spectrometers. In-
frared spectra were obtained on a Nicolet FTIR spec-
trometer. High-resolution mass spectra were obtained on
Varian MAT 311 and Micromass ZABSpec TOF spec-
trometers at the CRMPO (University of Rennes,
France). Microanalyses were performed by the ‘Centre
de Microanalyse du CNRS’ at Vernaison, France.
In summary, the above results offer a convenient route
to a variety of functionalised (alkoxy)- and (amino)-
alkenylcarbenes of Group
6 and 8 metal com-
plexes. These monometallic species could be used as
building blocks for the preparation of new mixed
bimetalllic complexes, for example, by activation of the
free propargyl alcohol substituents with another
organometallic moiety. We are currently studying the
3.1. 1,4-[HꢁCꢀCꢁCH(OH)]C6H4 (a)
Acetylene (120 mmol) was dissolved in 140 ml THF at
−78°C. After dropwise addition of nBuLi (1.6M, 42 ml,
40 mmol), the solution was stirred at −78°C for 15 min.
A solution of terephthaldehyde (4.02 g, 30 mmol) in 30
ml THF was slowly added and the reaction mixture was
stirred for 20 min at −78°C. Saturated aqueous sodium
carbonate (20 ml) was then slowly added at room tem-
perature (r.t.). After extraction of the organic phase, the
aqueous layer was washed twice with diethyl ether
(2×30 ml). The combined organic phases were
dried over MgSO4 and the solvent was evaporated in
vacuo. Compound a was obtained as a white powder
in 80% yield (4.468 g). M.p. 110°C. IR (KBr): w 3400
Scheme 5.

82
K. Ulrich et al. / Journal of Organometallic Chemistry 601 (2000) 78–86
(br, OH), 2115 (w, CꢀC). 1H-NMR (300.135 MHz,
CDCl3): l 7.55 (s, 4H, C6H4ꢁ), 5.49 (dd, 2H, J=5.9
and 2.2 Hz, CH(OH)), 5.06 (d, 2H, J=6.0 Hz,
CH(OH)), 3.07 (d, 2H, J=2.2 Hz, ꢀCꢁH). Anal. Calc.
for C12H10O2 (186.2): C, 77.42; H, 5.38. Found: C,
77.14; H, 5.65%.
d in 74% yield (0.890 g). IR (KBr): w 3430 (br, OH),
2115 (w, CꢀC), 1602 (s, CꢂC). 1H-NMR (300.135 MHz,
CDCl3): l 7.50 (s, 4H, C6H4ꢁ), 6.71 (dd, 1H, J=17.0
and 11.0 Hz, CHꢂ), 5.73 (dd,1H, J=17.0 and 1.0 Hz,
CH2ꢂ), 5.42 (d, 1H, J=2.3 Hz, CH(OH)), 5.25 (dd,1H,
J=11.0 and 1.0 Hz, CH2ꢂ), 3.1 (d, 1H, J=2.3 Hz,
ꢀCꢁH). Anal. Calc. for C11H10O (158.2): C, 83.52; H,
6.37. Found: C, 82.07; H, 6.36%.
3.2. 2,5-[HꢁCꢀCꢁCH(OH)]C4H2S (b)
By using the same procedure, compound b was ob-
tained as a brown powder in 86% yield (4.950 g) from
thiophene 2,5-carbaldehyde (30 mmol, 4.2 g). IR (KBr):
w 3340 (br, OH), 2119 (w, CꢀC). 1H-NMR (300.135
MHz, CDCl3): l 6.99 (s, 2H, C4H2Sꢁ); 5.66 (d, 2H,
J=2.1 Hz, CH(OH)), 5.31 (br, 2H, CH(OH)), 3.14 (d,
2H, J=2.1 Hz, ꢀCꢁH). Anal. Calc. for C10H8O2S
(192.2): C, 62.48; H, 4.19; S, 16.47. Found: C, 62.56; H,
4.25; S, 16.47%.
3.5. HꢁCꢀCꢁCH(OH)ꢁC6H4ꢁCHꢂCHꢁCHꢂCH2 (e)
The synthesis follows the method outlined for the
synthesis of d. Compound e was obtained as a pale-yel-
low oil in 72% yield (1.061 g) from HꢁCꢀCꢁCH-
(OH)ꢁC6H4ꢁCHO (c) (1.28 g,
8
mmol) and
Ph3PꢂCHꢁCHꢂCH2, and was used in the next step
without further column chromatography purification.
1
IR (KBr): w 3450 (br, OH), 2114 (w, CꢀC). H-NMR
(300.135 MHz, CDCl3), trans/cis: l 7.30 (m, 4H,
C6H4ꢁ), 6.80 (m, 1H, CHꢂ), 6.48 (d, 1H, J=15.9 Hz,
CHꢂ, trans isomer), 6.38 (d, 1H, J=13.5 Hz, CHꢂ, cis
isomer), 5.38 (d, 1H, J=2.2 Hz, CH(OH)), 5.30 (m,
1H, CH2ꢂ), 5.15 (m, 1H, CH2ꢂ), 2.60 (d, 1H, J=2.2
Hz, ꢀCꢁH).
3.3. HꢁCꢀCꢁCH(OH)ꢁC6H4ꢁCHO (c)
By using the same procedure, HꢁCꢀCꢁCH(OH)ꢁ
C6H4ꢁCH(OEt)2 was obtained as a yellow oil in 75%
yield (2.632 g) from terephthaldehyde monodiethyl ac-
etal (15 mmol, 3.1 g). IR (KBr): w 3400 (br, OH), 2115
1
(w, CꢀC). H-NMR (300.135 MHz, CDCl3): l 7.55 (s,
3.6. [(C6Me6)(Cl)(PMe3)RuꢂC(OMe)CHꢂCHꢁ
C6H4ꢁC(H)(OH)(CꢀCH)]PF6 (2a)
4H, C6H4-), 5.45 (s, 1H, CHꢁ), 5.35 (d, 1H, J=2.3 Hz,
CH(OH)), 3.48 (q, 4H, J=7.5 Hz, OCH2ꢁ), 2.57 (d,
1H, J=2.3 Hz, ꢀCꢁH), 1.14 (t, 6H, J=7.5 Hz, CH3).
The propargylic alcohol was then dissolved in 40 ml
of dichoromethane, and 40 g of SiO2 and 8 ml of
H2SO4 (3%) were added. The reaction mixture was
stirred at r.t. overnight. After extraction of the organic
phase and evaporation of the solvent in vacuo, the
crude oil was chromatographed on silica gel. Elution
with dichloromethane gave c as a yellow oil in 85%
yield (2.100 g). IR (KBr): w 3450 (br, OH), 2115 (w,
In a Schlenk flask, 1 (1 mmol, 0.41g) was dissolved in
80 ml of a 1:3 methanol–dichloromethane mixture. To
the red solution was added sodium hexaflurophosphate
(1.2 mmol, 0.2 g) and a in excess (3.3 mmol, 0.61 g).
After 18 h of stirring at r.t., the solvent was removed
under vacuum. The black precipitate was washed with
diethyl ether (2×20 ml) and then dissolved in 20 ml of
dichloromethane. The solution was filtered through a
filter paper tipped cannula. Complex 2a was obtained
in 48% yield (0.345 g) by recrystallisation of the precip-
itate by slow diffusion of ether into a CH2Cl2 solution.
1H-NMR (300.135 MHz, acetone-d6): l 8.50 (d, 1H,
J=15.5 Hz, CHꢂ), 7.95 (d, 2H, J=8.3 Hz, C6H4ꢁ),
7.70 (d, 1H, J=15.5 Hz, CHꢂ); 7.60 (d, 2H, J=8.3
Hz, C6H4ꢁ), 5.60 (s, 1H, CH(OH)), 4.70 (s, 3H, OCH3),
3.15 (d, 1H, J=2.3 Hz, ꢀCꢁH), 2.15 (s, 18H, C6Me6),
1.50 (d, 1H, J=10.9 Hz, PMe3). 13C{1H}-NMR (ace-
tone-d6): l 303.4 (d, J=20.6 Hz, RuꢂC), 167.7 (CHꢂ),
147.9 (CHꢂ), 135.4, 131.2, 128.4, 127.6 (C6H4ꢁ), 106.8
(C6Me6), 84.9 (CꢀCꢁH), 75.8 (CꢀCꢁH), 65.8 (OCH3),
63.5 (CH(OH)), 16.4 (C6Me6), 15.8 (d, J=35 Hz,
PMe3). 31P-NMR (acetone-d6): l 17.7 (PMe3), −142.0
(sept, J=709 Hz, PF−6 ). Anal. Calc. for C28H39ClF6-
O2P2Ru (720): C, 46.66; H, 5.41. Found: C, 46.96; H,
5.35%.
1
CꢀC), 1700 (s,CHO). H-NMR (300.135 MHz, CDCl3):
l 9.90 (s, 1H, CHO), 7.73 (m, 4H, C6H4ꢁ), 5.45 (d, 1H,
J=2.5 Hz, CH(OH)), 2.69 (d, 1H, J=2.5 Hz, ꢀCꢁH).
HRMS (EI) Calc. for C10H8O2 [M]+: 160.0524. Found:
160.0522.
3.4. HꢁCꢀCꢁCH(OH)ꢁC6H4ꢁCHꢂCH2 (d)
In a Schlenk flask containing 6 mmol of Ph3PꢂCH2
(obtained from 2.4 g of Ph3PCH+3 I− and 0.67 g of
tBuOK) in 40 ml of THF, was added 900 mg of
HꢁCꢀCꢁCH(OH)ꢁC6H4ꢁCHO (c) (5.6 mmol). The re-
action mixture was stirred at r.t. for 2 h and water (20
ml) was then added. The organic phase was extracted,
dried over MgSO4 and the solvent was evaporated in
vacuo to give a pale-yellow oil, which was purified by
column chromatography on alumina (CH2Cl2) to yield

K. Ulrich et al. / Journal of Organometallic Chemistry 601 (2000) 78–86
83
3.7. [(C6Me4H2)(Cl)(PMe3)RuꢂC(OMe)-
CHꢂCHꢁC6H4ꢁCHO]PF6 (2%c)
J=14.8 Hz, CHꢂ), 7.0 (dd, 1H, J=15.7 and 10.1 Hz,
CHꢂ), 6.60 (d, 1H, J=15.7 Hz, CHꢂ), 6.52 (dd, 1H,
J=14.1 and 10.5 Hz, CHꢂ), 5.79 (s, 2H, C6H2Me4),
5.47 (m, 1H, CH2ꢂ), 5.27 (m, 1H, CH2ꢂ), 4.43 (s, 3H,
OCH3), 2.05 (s, 6H, C6H2Me4), 1.89 (s, 6H, C6H2Me4),
1.48 (d, 1H, J=10.9 Hz, PMe3); cis 8.58 (d, 1H,
J=14.8 Hz, CHꢂ), 7.78 (d, 2H, J=8.3 Hz, C6H4ꢁ),
7.47 (d, 2H, J=8.4 Hz, C6H4ꢁ), 7.40 (d, 1H, J=14.8
Hz, CHꢂ), 6.90 (m, 1H, CHꢂ), 6.45 (m, CHꢂ), 6.41
(d, 1H, J=9.9 Hz, CHꢂ); 5.70 (s, 2H, C6H2Me4), 5.50
(m, 1H, CH2ꢂ), 5.33 (m, 1H, CH2ꢂ), 4.45 (s, 3H,
OCH3), 2.05 (s, 6H, C6H2Me4), 1.89 (s, 6H, C6H2Me4),
1.48 (d, 1H, J=10.9 Hz, PMe3). 31P-NMR (acetone-
d6): l 13.5 (PMe3). Anal. Calc. for C27H37ClF6O2P2Ru
(706.05): C, 46.69; H, 5.33. Found: C, 46.89; H,
5.30%.
The synthesis follows the method outlined for the
synthesis of 2a. Complex 2%c was obtained as brown
microcrystals in 60% yield (0.399 g) from c (0.50 g, 3
mmol), 1% (0.38 g, 1 mmol) and NaPF6 (0,50g, 3
1
mmol). IR (KBr): w 1700 (s, CꢂO). H-NMR (300.135
MHz, CD2Cl2): l 10.05 (s, 1H, CHO), 8.52 (d, 1H,
J=15.1 Hz, CHꢂ), 7.92 (s, 4H, C6H4ꢁ), 7.43 (d, 1H,
J=15.1 Hz, CHꢂ), 5.85 (s, 2H, C6H2Me4), 4.50 (s,
3H, OCH3), 2.10 (s, 6H, C6H2Me4), 1.96 (s, 6H,
C6H2Me4), 1.50 (d, 1H, J=11.0 Hz, PMe3). 13C{1H}-
NMR (CD2Cl2): l 302.8 (d, J=19.1 Hz, RuꢂC),
139.9 (CHꢂ), 139.3 (CHꢂ), 131.4, 131.0, 130.8
(C6H4ꢁ), 106.9, 106.8, 99.8, 99.7 (C6Me4H2), 66.3
(OCH3), 17.4 (d, J=29 Hz, PMe3), 17.1 (C6Me4H2).
31P-NMR (acetone-d6): l 13.7 (PMe3). HRMS (FAB+)
Calc. for C24H33O2PClRu [M−PF6]+: 521.0954.
Found: 521.0959.
3.10. [(C5H5)(CO)(PPh3)RuꢂC(OMe)-
CHꢂCHꢁC6H4ꢁC(H)(OH)(CꢀCH)]BF4 (4a)
In a Schlenk flask, 3 (1 mmol, 0.49 g) was dissolved
in 120 ml of a 1:2 methanol–dichloromethane mixture.
To the orange solution was added silver tetraflurobo-
rate (1.1 mmol, 0.21 g). After 1 h of stirring at r.t., an
excess of a (3 mmol, 0.56 g) was added and the reac-
tion mixture was stirred overnight. The solution was
then decanted and filtered through a filter paper
tipped cannula. The solvent was removed under vac-
uum. Recrystallisation of the precipitate by slow diffu-
sion of ether into a CH2Cl2 solution afforded 4a as
orange microcrystals in 74% yield (0.550 g). IR (KBr):
w 2115 (w, CꢀC), 1972 (s, CO). 1H-NMR (300.135
MHz, CD2Cl2): l 7.60–7.30 (m, 20H, PPh3, C6H4ꢁ
and CHꢂ), 6.91 (d, 1H, J=15.4Hz, CHꢂ), 5.49 (d,
1H, J=2.1 Hz, CH(OH)), 5.34 (s, 5H, C5H5), 4.16 (s,
3H, OCH3), 2.72 (d, 1H, J=2.3 Hz, ꢀCꢁH). 31P-
NMR (acetone-d6): l 50.5 (PPh3). Anal. Calc. for
C37H32BF4O3PRu·0.5Et2O: C, 60.01; H, 4.78; P, 3.97.
Found: C, 60.02; H, 4.47; P, 3.59%.
3.8. [(C6Me4H2)(Cl)(PMe3)RuꢂC(OMe)-
CHꢂCHꢁC6H4ꢁCHꢂCH2]PF6 (2%d)
The synthesis follows the method outlined for the
synthesis of 2a. Complex 2%d was obtained as black
microcrystals in 75% yield (0.510 g) from c (0.32 g, 2
mmol), 1% (0.38 g, 1 mmol) and NaPF6 (0,17g, 1.1
mmol). 1H-NMR (300.135 MHz, acetone-d6): l 8.15
(d, 1H, J=14.9 Hz, CHꢂ), 7.95 (d, 2H, J=8.4 Hz,
C6H4ꢁ), 7.80 (d, 1H, J=14.9 Hz, CHꢂ), 7.65 (d, 2H,
J=8.4 Hz, C6H4ꢁ), 6.85 (dd, 1H, J=17.5 and 10.0
Hz, CHꢂ), 6.35 (s, 2H, C6H2Me4), 6.05 (d, 1H, J=
17.5 Hz, CH2ꢂ), 5.50 (d, 1H, J=11.0 Hz, CH2ꢂ), 4.70
(s, 3H, OCH3), 2.20 (s, 6H, C6H2Me4), 2.0 (s, 6H,
C6H2Me4), 1.55 (d, 1H, J=11.3 Hz, PMe3). 13C{1H}-
NMR (CD2Cl2): l 301.1 (d, J=19.1 Hz, RuꢂC), 170.0
(CHꢂ), 143.0 (CHꢂ), 136.0, 134.0, 131.0 (C6H4ꢁ),
117.0 (CH2ꢂ), 107.1 (C6Me4H2), 65.0 (OCH3), 17.4
(C6Me4H2), 17.0 (d, J=35 Hz, PMe3). 31P-NMR
(acetone-d6):
l
15.3 (PMe3). Anal. Calc. for
C25H35ClF6O2P2Ru (680): C, 45.22; H, 5.31; P, 9.33.
Found: C, 44.92; H, 5.32; P, 9.44%.
3.11. [(C5H5)(CO)(PPh3)RuꢂC(OMe)CHꢂCHꢁ
C6H4ꢁCHꢂCH2)]BF4 (4d)
3.9. [(C6Me4H2)(Cl)(PMe3)RuꢂC(OMe)-
The synthesis follows the method outlined for the
synthesis of 4a. Complex 4d was obtained as orange
microcrystals in 50% yield (0.357 g) from d (0.24 g, 1.5
mmol) and 3 (0.49 g, 1 mmol). IR (KBr): w 1972 (s,
CHꢂCHꢁC6H4ꢁCHꢂCHꢁCHꢂCH2]PF6 (2%e)
The synthesis follows the method outlined for the
synthesis of 2a. Complex 2%e was obtained as black
microcrystals in 73% yield (0.515 g) from c (0.37 g, 2
mmol), 1% (0.38 g, 1 mmol) and NaPF6 (0,17g, 1.1
1
CO), 1588(s, CꢂC). H-NMR (300.135 MHz, acetone-
d6): l 7.50–7.20 (m, 20H, PPh3, C6H4 and CHꢂ), 6.90
(d, 1H, J=15.4 Hz, CHꢂ), 6.70 (dd, 1H, J=17.6 and
10.9 Hz, CHꢂ), 6.0 (d, 1H, J=17.6 Hz, CHꢂ), 5.40
(d, 1H, J=10.9 Hz, CHꢂ), 5.30 (s, 5H, C5H5), 4.15 (s,
3H, OCH3). 13C{1H}-NMR (acetone-d6): l 299.2 (br,
1
mmol). H-NMR (300.135 MHz, CD2Cl2): l trans 8.58
(d, 1H, J=14.8 Hz, CHꢂ), 7.77 (d, 2H, J=8.4 Hz,
C6H4ꢁ), 7.54 (d, 2H, J=8.4 Hz, C6H4ꢁ), 7.40 (d, 1H,

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K. Ulrich et al. / Journal of Organometallic Chemistry 601 (2000) 78–86
RuꢂC), 202.2 (d, J=19.0 Hz, CO), 148.9 (CHꢂ), 142.3
(CHꢂ), 136.0–130.0 (PPh3, CHꢂ, and C6H4ꢁ), 117.3
(CH2ꢂ), 90.2 (C5H5), 66.1 (OCH3). 31P-NMR (acetone-
acetone-d6): l 8.13 (d, 1H, J=15.4 Hz, CHꢂ), 7.81 (d,
2H, J=8.1 Hz, C6H4ꢁ), 7.66 (d, 2H, J=8.1 Hz,
C6H4ꢁ), 7.25 (d, 1H, J=15.4 Hz, CHꢂ), 5.54 (s, 1H,
CH(OH)), 5.21 (s, 1H, CH(OH)), 4.89 (s, 3H, OCH3),
3.12 (s, 1H, ꢀCꢁH). 13C{1H}-NMR (75.47 MHz, ace-
tone-d6): l 334.4 (CrꢂC), 225.7 (CO), 217.8 (CO), 145.9
(C6H4ꢁ), 139.9 (CHꢂ), 134.9 (CHꢂ), 130.5, 128.2
(C6H4ꢁ), 83.2 (CꢀCꢁH), 75.5 (CꢀCꢁH), 67.5 (OCH3),
63.7 (CH(OH)). HRMS (FAB+) Calc. for C18H12O752Cr
[M]+: 391.9988. Found: 391.9999.
d6):
l
48.7 (PPh3). HRMS (FAB+) Calc. for
C36H32O2PRu [M−BF4]+: 629.1194. Found: 629.1192.
3.12. General procedure for the synthesis of
(methoxy)-alkenyl carbene–tungsten and chromium
complexes
A solution of W(CO)6 or Cr(CO)6 (1 mmol) in 60 ml
of THF was irradiated for 6 h at r.t. by using a
Rayonet and a Pyrex photochemical reactor. The yel-
low solution of M(CO)5(THF) was then transferred
into a Schlenk flask containing a solution of the di-
alkynol derivative a or b (1.5 mmol) in 30 ml of
methanol. The reaction mixture was then stirred for 18
h at r.t. After evaporation of the solvent under vacuum,
the red residue was chromatographed on silica gel.
Elution with 1:3 dichloromethane–pentane gave first
the violet bimetallic complexes and then the red
monometallic complexes as solids or oils.
3.16. (CO)5CrꢂC(OMe)CHꢂCHꢁC6H4ꢁ
CHꢂCH(MeO)CꢂCr(CO)5 (8a)
Yield: 10% (0.060 g). IR (KBr): w 2055 (m, CO), 1944
1
(s, CO). H-NMR (200.135 MHz, CDCl3): l 7.95 (d,
2H, J=15.3 Hz, CHꢂ), 7.60 (s, 4H, J=8.3 Hz,
C6H4ꢁ), 6.90 (d, 1H, J=15.3 Hz, CHꢂ), 4.85 (s, 6H,
OCH3). 13C{1H}-NMR (CDCl3): l 333.4 (CrꢂC), 222.0
(CO), 216.6 (CO), 140.0 (CHꢂ), 136.9 (C6H4ꢁ), 129.9
(C6H4ꢁ), 127.4 (CHꢂ), 66.6 (OCH3).
3.17. (CO)5WꢂC(OMe)CHꢂCHꢁC4H2Sꢁ
C(H)(OH)(CꢀCH) (5b)
3.13. (CO)5WꢂC(OMe)CHꢂCHꢁC6H4ꢁ
C(H)(OH)(CꢀCH) (5a)
Yield: 33% (0.175 g). IR (KBr): w 2124 (w, CꢀC),
1
Yield: 41% (0.214 g). IR (KBr): w 2130 (w, CꢀC),
2065 (m, CO), 1929 (s, CO). H-NMR (300.135 MHz,
1
2059 (m, CO), 1940 (s, CO). H-NMR (300.135 MHz,
acetone-d6): l 7.70 (d, 1H, J=15.1 Hz, CHꢂ), 7.50 (dd,
1H, J=15.5 and 0.6 Hz, CHꢂ), 7.45 (d, 1H, J=3.8
Hz, C4H2Sꢁ), 7.14 (dd, 1H, J=3.8 and 0.6 Hz,
C4H2Sꢁ), 5.70 (d, 1H, J=2.1 Hz, CH(OH)), 5.50 (s,
1H, CH(OH)), 4.65 (s, 3H, OCH3), 3.15 (d, 1H, J=2.3
Hz, ꢀCꢁH). 13C{1H}-NMR (75.47 MHz, acetone-d6): l
304.9 (WꢂC), 205.1 (CO), 198.6 (CO), 153.7 (C4H2Sꢁ),
142.4 (CHꢂ), 140.5 (C4H2Sꢁ), 136.3 (C4H2Sꢁ), 131.0
(CHꢂ), 127.9 (C4H2Sꢁ), 84.1 (CꢀCꢁH), 75.6 (CꢀCꢁH),
70.0 (OCH3), 60.5 (CH(OH)). Anal. Calc. for
C16H10O7SW (530.2): C, 36.20; H, 1.90; S, 6.03. Found:
C, 35.60; H, 2.20; S, 6.10%.
acetone-d6): l 8.10 (d, 1H, J=15.5 Hz, CHꢂ), 7.84 (d,
2H, J=8.3 Hz, C6H4ꢁ), 7.65 (d, 2H, J=8.3 Hz,
C6H4ꢁ), 7.43 (d, 1H, J=15.5 Hz, CHꢂ), 5.53 (dd, 1H,
J=5.8 and 2.1 Hz, CH(OH)), 5.21 (d, 1H, J=5.9 Hz,
CH(OH)), 4.76 (s, 3H, OCH3), 3.12 (d, 1H, J=2.1 Hz,
ꢀCꢁH). 13C{1H}-NMR (acetone-d6): l 307.4 (WꢂC),
203.8 (CO), 195.5 (CO), 143.8 (CHꢂ), 142.8, 134.8
(C6H4ꢁ), 133.2 (CHꢂ), 129.5, 127.1 (C6H4ꢁ), 83.0
(CꢀCꢁH), 75.2 (CꢀCꢁH), 69.1 (OCH3), 63.9
(CH(OH)). HRMS (FAB+) Calc. for C18H12O1784
W
[M]+: 524.0093. Found: 524.0095.
3.14. (CO)5WꢂC(OMe)CHꢂCHꢁC6H4ꢁ
CHꢂCH(MeO)CꢂW(CO)5 (6a)
3.18. (CO)5WꢂC(OMe)CHꢂCHꢁC4H2Sꢁ
CHꢂCH(MeO)CꢂW(CO)5 (7b)
Yield: 10% (0.090 g). IR (KBr): w 2065 (m, CO), 1941
(s, CO). H-NMR (300.135 MHz, CDCl3): l 7.85 (d,
Yield: 9% (0.080 g). IR (KBr): w 2063 (m, CO), 1946
(s, CO). 1H-NMR (200.13 MHz, CDCl3): l 7.68 (d, 2H,
J=15.1 Hz, CHꢂ), 7.32 (s, 2H, C4H2Sꢁ), 7.22 (d, 1H,
J=15.1 Hz, CHꢂ), 4.58 (s, 6H, OCH3). 13C{1H}-NMR
(CDCl3): l 304.2 (WꢂC), 203.9 (CO), 197.4 (CO), 144.6
(C4H2Sꢁ), 143.6 (CHꢂ), 134.7 (CHꢂ), 125.4 (C4H2Sꢁ),
68.9 (OCH3).
1
2H, J=15.5 Hz, CHꢂ), 7.50 (s, 4H, C6H4ꢁ), 7.10 (d,
1H, J=15.5 Hz, CHꢂ), 4.55 (s, 6H, OCH3). 13C{1H}-
NMR (CDCl3): l 307.0 (WꢂC), 203.8 (CO), 197.4
(CO), 144.2 (CHꢂ), 137.1 (C6H4ꢁ), 131.8 (CHꢂ), 129.0
(C6H4ꢁ), 69.1 (OCH3).
3.15. (CO)5CrꢂC(OMe)CHꢂCHꢁC6H4ꢁ
C(H)(OH)(CꢀCH) (7a)
3.19. (CO)5WꢂC(OMe)CHꢂCHꢁC6H4ꢁCHꢂCH2) (5d)
The synthesis follows the method outlined for the
synthesis of 5a. Complex 5d was obtained as orange
powder in 60% yield (0.300 g) from c (0.24 g, 1.5
Yield: 33% (0.130 g). IR (KBr): w 2123 (w, CꢀC),
1
2059 (m, CO), 1940 (s, CO). H-NMR (300.135 MHz,

K. Ulrich et al. / Journal of Organometallic Chemistry 601 (2000) 78–86
85
mmol). IR (KBr): w 2066 (m, CO), 1942 (s, CO).
1H-NMR (300.135 MHz, CDCl3): l 8.85 (d, 1H, J=
15.5 Hz, CHꢂ), 7.55 (d, 2H, J=8.4 Hz, C6H4ꢁ), 7.45
(d, 2H, J=8.4 Hz, C6H4ꢁ), 7.20 (d, 1H, J=15.5 Hz,
CHꢂ), 6.70 (d, 1H, J=17.6 and 9.9 Hz, CHꢂ), 5.85 (d,
1H, J=17.6 Hz, CH2ꢂ), 5.85 (d, 1H, J=9.9 Hz,
CH2ꢂ), 4.65 (s, 3H, OCH3). 13C{1H}-NMR (CDCl3): l
306.10 (WꢂC), 203.8 (CO), 197.6 (CO), 143.2 (CHꢂ),
140.3 (C6H4ꢁ), 136.4 (CHꢂ), 134.0 (C6H4ꢁ), 133.8
(CHꢂ), 129.6, 127.0 (C6H4ꢁ), 115.9 (CH2ꢂ), 69.0
(OCH3). Anal. Calc. for C17H12O6W (496.1): C, 41.14;
H, 2.42. Found: C, 41.20; H, 2.59%.
142.0 (C4H2Sꢁ), 139.1 (CHꢂ), 127.8, 126.4 (C4H2Sꢁ),
119.7 (CHꢂ), 84.6 (CꢀCꢁH), 75.0 (CꢀCꢁH), 60.2
(CH(OH)), 54.4, 45.1 (NCH3). Anal. Calc. for
C17H13NO6SW (543.2): C, 37.57; H, 2.41; N, 2.58; S,
5.89. Found: C, 37.40; H, 2.64; N, 2.57; S, 6.01%.
3.23. (CO)5WꢂC(NEt2)CHꢂCHꢁC6H4ꢁ
C(H)(OH)(CꢀCH) (10a)
Yield: 95% (0.536 g). IR (KBr): w 2115 (w, CꢀC),
1
2059 (m, CO), 1918 (s, CO). H-NMR (300.135 MHz,
acetone-d6): l 7.55 (m, 4H, C6H4ꢁ), 7.40 (d, 1H, J=
16.8 Hz, CHꢂ), 6.14 (d, 1H, J=16.8 Hz, CHꢂ), 5.49 (s,
1H, CH(OH)), 5.05 (s, 1H, CH(OH)), 4.28 (q, 2H,
J=7.2 Hz, NCH2), 3.96 (q, 2H, J=7.2 Hz, NCH2),
3.07 (d, 1H, J=2.2 Hz, ꢀCꢁH), 1.50 (t, 3H, J=7.2 Hz,
CH3), 1.33 (t, 3H, J=7.2 Hz, CH3). 13C{1H}-NMR
(75.47 MHz, acetone-d6): l 248.9 (WꢂC), 204.6 (CO),
199.4 (CO), 142.3 (C6H4ꢁ), 140.3 (CHꢂ), 136.8, 127.9,
127.4 (C6H4ꢁ), 123.2 (CHꢂ), 85.7 (CꢀCꢁH), 75.1
(CꢀCꢁH), 63.9 (CH(OH)), 58.3, 48.7 (NCH2ꢁ), 14.5,
3.20. General procedure for the synthesis of
(amino)-alkenyl carbene–tungsten and chromium
complexes
To a solution of methoxyalkenyl carbene complexes
(1 mmol) in 20 ml of diethyl ether at −80°C was added
five equivalents of amine. The colour rapidly changed
from red to orange. After stirring for 15 min at
−80°C, the solvant was removed in vacuo at 0°C and
the crude product was chromatographed on silica gel
using 1:2 pentane–dichloromethane as eluent. Evapora-
tion of the solvent gave the amino carbene complexes
as orange to red solids or oils.
14.3 (CH3). HRMS (FAB+) Calc. for C20H19NO1584
[M−CO]+: 537.0776. Found: 537.0775.
W
3.24. (CO)5WꢂC(NHiPr)CHꢂCHꢁC6H4ꢁ
C(H)(OH)(CꢀCH) (11a)
3.21. (CO)5WꢂC(NMe2)CHꢂCHꢁC6H4ꢁ
C(H)(OH)(CꢀCH) (9a)
Yield: 88% (0.490 g). IR (KBr): w 2119 (w, CꢀC),
2059 (m, CO), 1912 (s, CO). E 1H-NMR (300.135
MHz, acetone-d6): l 10.20 (s broad, 1H, NHꢁ), 7.64
(m, 4H, C6H4ꢁ), 7.52 (d, 1H, J=16.0 Hz, CHꢂ), 7.09
(d, 1H, J=16.0 Hz, CHꢂ), 5.51 (m, 1H, CH(OH)),
5.11 (d, 1H, J=6.0 Hz, CH(OH)), 4.51 (m, 1H,
NCHꢁ), 3.09 (d, 1H, J=2.1 Hz, ꢀCꢁH), 1.40 (d, 6H,
J=6.5 Hz, CH3. 13C{1H}-NMR (75.47 MHz, CDCl3):
l 248.0 (WꢂC), 203.0 (CO), 199.1 (CO), 143.3 (CHꢂ),
133.2 (CHꢂ), 83.4 (CꢀCꢁH), 74.9 (CꢀCꢁH), 64.0
(CH(OH)), 51.7 (NCHꢁ), 22.7 (CH3). Z 1H-NMR
(acetone-d6): l 10.20 (s broad, 1H, NHꢁ), 7.70 (m, 5H,
CHꢂ and C6H4ꢁ), 6.81 (d, 1H, J=15.7 Hz, CHꢂ), 5.52
(m, 1H, CH(OH)), 5.06 (d, 1H, J=5.9 Hz, CH(OH)),
4.51 (m, 1H, NCHꢁ), 3.07 (d, 1H, J=2.3 Hz, ꢀCꢁH),
1.49 (d, 6H, J=6.5 Hz, CH3. 13C{1H}-NMR (CDCl3):
l 242.0 (WꢂC), 203.3 (CO), 198.1 (CO), 140.4 (CHꢂ),
126.8 (CHꢂ), 83.2 (CꢀCꢁH), 75.1 (CꢀCꢁH), 63.9
(CH(OH)), 57.5 (NCHꢁ), 22.5 (CH3). Anal. Calc. for
C20H17NO6W. 0.5 Et2O (588.3): C,44.92; H, 3.77; N,
2.38. Found: C, 45.66; H, 3.83; N, 2.38%.
Yield: 97% (0.520 g). IR (KBr): w 2130 (w, CꢀC),
1
2059 (m, CO), 1919 (s, CO). H-NMR (300.135 MHz,
acetone-d6): l 7.50 (m, 4H, C6H4ꢁ), 7.20 (d, 1H, J=
16.8 Hz, CHꢂ), 6.10 (d, 1H, J=16.8 Hz, CHꢂ), 5.40
(dd, 1H, J=5.5 and 2.2 Hz, CH(OH)), 5.10 (s, 1H,
CH(OH)), 3.85 (s, 3H, NCH3), 3.57 (s, 3H, NCH3), 3.0
(d, 1H, J=2.2 Hz, ꢀCꢁH). 13C{1H}-NMR (75.47
MHz, acetone-d6): l 248.6 (WꢂC), 204.6 (CO), 199.5
(CO), 142.6 (C6H4ꢁ), 140.4 (CHꢂ), 136.7, 127.9, 127.5
(C6H4ꢁ), 124.4 (CHꢂ), 85.6 (CꢀCꢁH), 75.1 (CꢀCꢁH),
63.9 (CH(OH)), 54.3, 45.0 (NCH3). HRMS (FAB+)
Calc. for C19H15NO1684W [M]+: 537.0412. Found:
537.0423.
3.22. (CO)5WꢂC(NMe2)CHꢂCHꢁC4H2Sꢁ
C(H)(OH)(CꢀCH) (9b)
Yield: 82% (0.445 g). IR (KBr): w 2116 (w, CꢀC),
2061 (m, CO), 1899 (s, CO). 1H-NMR (300.135
MHz,CD2Cl2): l 7.04 (dd, 1H, J=3.7 and 0.8 Hz,
C4H2Sꢁ), 6.89 (d, 1H, J=3.7 Hz, C4H2Sꢁ), 6.88 (d, 1H,
J=16.3 Hz, CHꢂ), 6.14 (dd, 1H, J=16.3 and 0.6 Hz,
CHꢂ), 5.61 (s, 1H, CH(OH)), 5.30 (s, 1H, CH(OH)),
3.78 (s, 3H, NCH3), 3.37 (s, 3H, NCH3), 2.73 (d, 1H,
J=2.3 Hz, ꢀCꢁH). 13C{1H}-NMR (75.47 MHz, ace-
tone-d6): l 246.6 (WꢂC), 204.4 (CO), 199.4 (CO), 146.8,
3.25. (CO)5WꢂC(N(CH2CH2)2NH)CHꢂCHꢁ
C6H4ꢁC(H)(OH)(CꢀCH) (12a)
Yield: 93% (0.537 g). IR (KBr): w 2115 (w, CꢀC),
1
2061 (m, CO), 1902 (s, CO). H-NMR (300.135 MHz,
acetone-d6): l 7.54 (m, 4H, C6H4ꢁ), 7.30 (d, 1H, J=
16.7 Hz, CHꢂ), 6.09 (d, 1H, J=16.7 Hz, CHꢂ), 5.48

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K. Ulrich et al. / Journal of Organometallic Chemistry 601 (2000) 78–86
(d, 1H, J=2.1 Hz, CH(OH)), 4.37 (m, 2H, NCH2),
4.11 (m, 2H, NCH2), 3.19 (m, 2H, NCH2), 3.08 (d, 1H,
J=2.3 Hz, ꢀCꢁH), 3.01 (m, 2H, NCH2). 13C{1H}-
NMR (75.47 MHz, acetone-d6): l 245.1 (WꢂC), 204.6
(CO), 199.2 (CO), 142.2 (C6H4ꢁ), 139.3 (CHꢂ), 136.6,
127.7, 127.5 (C6H4ꢁ), 122.9 (CHꢂ), 85.5 (CꢀCꢁH), 74.9
(CꢀCꢁH), 65.1 (NCH2ꢁ), 63.6 (CH(OH)), 56.1, 48.3,
48.0 (NCH2ꢁ). HRMS (FAB+) Calc. for C20H18N2-
O1584W [M−CO]+: 550.0728. Found: 550.0723.
References
[1] For a recent review see: M.I. Bruce, Chem. Rev. 98 (1998) 2797
[2] D. Pilette, K. Ouzzine, H. Le Bozec, P.H. Dixneuf, C.E.F.
Rickard, W.R. Roper, Organometallics 11 (1992) 809.
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Soc. Chem. Commun. (1992) 1220.
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Organometallics 15 (1996) 2137.
3.26. (CO)5WꢂC(NH(CH2CH2NH2))CHꢂCHꢁ
C6H4ꢁC(H)(OH)(CꢀCH) (13a)
[6] C. Cosset, I. Del Rio, H. Le Bozec, Organometallics 14 (1996)
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[7] C. Cosset, I. Del Rio, V. Pe´ron, B. Windmu¨ller, H. Le Bozec,
Synlett. (1996) 435.
Yield: 65% (0.358 g). IR (KBr): w 2116 (w, CꢀC),
2062 (m, CO), 1898 (s, CO). E 1H-NMR (300.135
MHz, CD2Cl2): l 9.60 (s broad, 1H, NHꢁ), 7.46 (d, 2H,
J=8.5 Hz, C6H4ꢁ), 7.38 (d, 2H, J=8.5 Hz, C6H4ꢁ),
7.36 (d, 1H, J=15.8 Hz, CHꢂ), 6.63 (d, 1H, J=15.8
Hz, CHꢂ), 5.45 (d, 1H, J=2.3 Hz, CH(OH)), 3.90 (t,
2H, J=5.6 Hz, NCH2ꢁ), 3.15 (t, 2H, J=5.6 Hz,
NCH2ꢁ), 2.69 (d, 1H, J=2.1 Hz, ꢀCꢁH), 2.1 (s broad,
2H, NH2ꢁ). 13C{1H}-NMR (75.47 MHz, CD2Cl2): l
245.7 (WꢂC), 203.9 (CO), 199.1 (CO), 142.4 (CHꢂ),
131.5 (CHꢂ), 84.3 (CꢀCꢁH), 74.9 (CꢀCꢁH), 63.5
(CH(OH)), 56.8 (NCH2ꢁ), 41.2(NCH2ꢁ). Anal. Calc.
for C19H16N2O6W. (552.2): C,41.30; H, 2.92; N, 5.07.
Found: C, 41.32; H, 3.01; N, 4.69%.
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