Synthesis, protonation, and electrophilic alkylation of CpW(CO)2[η3-2-(phenylethynyl)allyl]

Article abstract of DOI:10.1021/om9507989

CpW(CO)₂[η³-2-(phenylethynyl)allyl] (2) was prepared from the reaction between CpW-(CO)₃Na and 2-methylene-4-phenyl-3-butyn-1-yl tosylate, followed by decarbonylation with Me₃NO. Treatment of 2 with CF₃SO₃H in cold CDCl₃ produced a mixture of [CpW(CO)₂-(η⁴-1-(benzylidene)trimethylenemethane)]X (3a) and CpW(CO)₂(η³-2-CH ₂X-4-phenyl-2,3-butadien-1-yl) (3b) (X = CF₃SO₃), which were characterized with ¹H and ¹³C NMR spectra. Treatment of this mixture (3a,b) with a variety of nucleophiles gave compounds of the type CpW(CO)₂(η³-2-CH ₂X-4-phenyl-2,3-butadien-1-yl) (X = OH (4a), OMe (4b), iBuNH (4c), Me (4d), Ph (4e), CCPh (4f), H (4g)). In the presence of Bu₄NI, protonation of 4d-e with CF₃-SO₃H in cold CH₂Cl₂ produced CpW(CO)I[η⁴-(2-PhCH₂-3-XCH₂)vinylketene] (X = Me (6a), Ph (6b)), the structural identity of which was established from an X-ray diffraction study of the analogous complex CpW(CO)I[η⁴-(2-PhCH₂-3-ICH₂)vinylketene] (6c). Treatment of 2 with a mixture of acetaldehyde and BF₃·Et₂O in cold CH₂Cl₂, followed by reduction of NaBH₃-CN gave CpW(CO)₂(η ³-2-methyl-4-phenyl-5-methyl-2,4-pentadien-1-yl) (7), which was characterized by X-ray structural analysis.

Full text of DOI:10.1021/om9507989

Organometallics 1996, 15, 1565-1571
1565
Syn th esis, P r oton a tion , a n d Electr op h ilic Alk yla tion of
Cp W(CO)2[η3-2-(p h en yleth yn yl)a llyl]
Chi-Yi Cheng,† Chao-Hsieh Hsieh,† Gene-Hsian Lee,‡ Shie-Ming Peng,‡ and
Rai-Shung Liu*,†
Departments of Chemistry, National Tsing Hua University, Hsinchu 30043, Taiwan, Republic
of China, and National Taiwan University, Taipei, Taiwan 10764, Republic of China
Received October 11, 1995X
CpW(CO)2[η3-2-(phenylethynyl)allyl] (2) was prepared from the reaction between CpW-
(CO)3Na and 2-methylene-4-phenyl-3-butyn-1-yl tosylate, followed by decarbonylation with
Me3NO. Treatment of 2 with CF3SO3H in cold CDCl3 produced a mixture of [CpW(CO)2-
(η4-1-(benzylidene)trimethylenemethane)]X (3a ) and CpW(CO)2(η3-2-CH2X-4-phenyl-2,3-
1
butadien-1-yl) (3b) (X ) CF3SO3), which were characterized with H and 13C NMR spectra.
Treatment of this mixture (3a ,b) with a variety of nucleophiles gave compounds of the type
CpW(CO)2(η3-2-CH2X-4-phenyl-2,3-butadien-1-yl) (X ) OH (4a ), OMe (4b), iBuNH (4c), Me
(4d ), Ph (4e), CCPh (4f), H (4g)). In the presence of Bu4NI, protonation of 4d -e with CF3-
SO3H in cold CH2Cl2 produced CpW(CO)I[η4-(2-PhCH2-3-XCH2)vinylketene] (X ) Me (6a ),
Ph (6b)), the structural identity of which was established from an X-ray diffraction study of
the analogous complex CpW(CO)I[η4-(2-PhCH2-3-ICH2)vinylketene] (6c). Treatment of 2
with a mixture of acetaldehyde and BF3‚Et2O in cold CH2Cl2, followed by reduction of NaBH3-
CN gave CpW(CO)2(η3-2-methyl-4-phenyl-5-methyl-2,4-pentadien-1-yl) (7), which was char-
acterized by X-ray structural analysis.
Sch em e 1
In tr od u ction
Protonation1 and electrophilic alkylation2 of CpM-
(CO)2(η3-2-vinylallyl) produced isolable CpM(CO)2(η4-
trimethylenemethane)+ precipitates (M ) Mo, W) which
were reactive toward attack of various nucleophiles to
yield difunctionalized π-allyl complexes2a as depicted in
Scheme 1. Demetalations of these trimethylenemethane
cations with Me3NO gave functionalized 1,3-diene
complexes.2a In organic reactions, electrophilic proto-
nation and alkylation of organic alkynes are more
difficult than those of olefins because the vinyl cation
generated in the former is an energetically unstable
species.3 One can reasonably anticipate that formation
of a η4-1-(methylene)trimethylenemethane (Scheme 1,
eq 2) cation is more difficult than that of a η4-trimeth-
ylenemethane species. In this work, we report proto-
nation of CpW(CO)2[η3-2-(phenylethynyl)allyl] (2) to
yield a tungsten η4-1-(benzylidene)trimethylenemethane
cation, an unprecedented case of η4-1-(methylene)-
trimethylenemethane; the reaction chemistry of this
cation is also described.
Sch em e 2
Resu lts a n d Discu ssion
Syn th esis, Str u ctu r e, a n d P r oton a tion of Com -
p ou n d 2. According to a conventional method,4 the
reaction between CpW(CO)3Na and 2-methylene-4-
phenyl-3-butyn-1-yl tosylate gave air-stable CpW(CO)3-
(η1-2-methylene-4-phenyl-3-butyn-1-yl) (1) as a yellow
oil; the yield was 68%. Further stirring of 1 with
anhydrous Me3NO (2.0 equiv) in CH2Cl2 led to decar-
bonylation5 to produce CpW(CO)2[η3-2-(phenylethynyl)-
allyl] (2) in 60% yield as an air-stable yellow solid. The
molecular structure of 2 is provided in Figure 1; selected
† National Tsing Hua University.
‡ National Taiwan University.
X Abstract published in Advance ACS Abstracts, February 15, 1996.
(1) Allen, S. R.; Barnes, S. G.; Green, M.; Moran, G.; Murrall, N.
M.; Welch, A. J . Chem. Soc., Dalton Trans. 1984, 1175.
(2) (a) Yang, G.- M.; Su, G.-M.; Liu, R.-S. Organometallics 1992, 11,
3444. (b) Yang, G.-M.; Lee, G.-H.; Peng, S.-M.; Liu, R.-S. Organome-
tallics 1991, 10, 2531. (c) Yang, G.-M.; Lee, G.-H.; Peng, S.-M.; Liu,
R.-S. J . Chem. Soc., Chem. Commun. 1991, 478.
(3) Kohler, H. J .; Lischka, H. J . Am. Chem. Soc. 1979, 101, 3479.
(4) King, R. B.; Fronzaglia, A. Inorg. Chem. 1966, 5, 1837.
(5) Lawson, R. J .; Shapley, J . R. J . Am. Chem. Soc. 1976, 98, 7433.
0276-7333/96/2315-1565$12.00/0 © 1996 American Chemical Society

1566 Organometallics, Vol. 15, No. 6, 1996
Cheng et al.
those of the analogous complexes 4a -f, in which OH,
OMe, iBuNH, Ph, and other substituents replace the
CF3CO2 group of 3b (vide infra). 13C NMR signals of
1
the two cations (3a :3b ) 1:3) were assigned from H-
13C NMR correlation spectra. Compared to spectral
data1,9-10 of CpMo(CO)2(η4-trimethylenemethane)BF4
and CpMo(CO)2(η3-2,3-butadienyl) complexes, we as-
signed the two low-field signals at δ 155.8 and 160.6
ppm to the quaternary C3 carbons of 3a ,b, respectively,
and the signals at δ 96.2 and 93.5 ppm to the C2 carbons
of 3a ,b, respectively. The two W-CO carbonyls were
equivalent for 3a but inequivalent for 3b. The CR
carbon of 3b resonated at δ 64.7 ppm. For both 3a and
3b, we could not deduce the orientation of the phenyl
group with respect to the CpW(CO)2 fragment by proton-
NOE difference spectra. Compounds 3a and 3b are
unstable near 23 °C, at which temperature the NMR
signals of 3a and 3b quickly disappear within 1 h
accompanied by formation of an unknown black pre-
cipitate.
Rea ction s of 3a a n d 3b w ith Nu cleop h iles. Com-
plexes 3a ,b were reactive toward various nucleophiles
under ambient conditions. In a typical reaction, a
mixture of 3a and 3b generated in situ was treated with
excess nucleophile in cold diethyl ether (-20 °C); the
reaction mixture was slowly warmed to 23 °C and
aqueous NH4Cl solution added. Scheme 3 summarizes
the types of nucleophiles and the corresponding isolated
yields. Although starting materials consisted of 3a and
3b each in significant composition (3a :3b ) (1:2)-(1:
3)), for every case in Scheme 3, only η3-2,3-butadienyl
complexes6-10 4a -g were obtained in 48-60% yields.
In entry 1, Bu4NOH replaced water because the latter
was not reactive enough at -20 °C to yield the desired
η3-2,3-butadienyl product; in this case CpW(CO)2(η3-2-
benzoylallyl) (5) was obtained in 35% yield after stirring
the water mixture at 23 °C for 6 h (vide infra). NMR
spectral data of 4a -g were consistent with those
expected for a η1-2,3-butadienyl structure. Similar to
CpMo(CO)2(η3-2,3-butadienyl) complexes, the CHPh
protons of 4a -g show signals at δ 7.50-7.70 ppm,
whereas the two C)CHPh olefin carbons show signals
at δ 160-165 and 120-125 ppm, respectively. The cis
or trans relationship between CHPh and CpW(CO)2
fragments was not deducible from proton-NOE differ-
ence spectra. Although 4a ,d ,e were obtained as yellow
solids, the quality of single crystals was poor.
F igu r e 1. ORTEP drawing of compound 2.
Ta ble 1. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for 2
W-C(1)
W-(C2)
W-C(3)
W-C(4)
W-C(5)
C(1)-O(1)
1.965(6)
1.967(5)
2.267(6)
2.286(6)
2.286(6)
1.144(7)
C(2)-O(2)
C(3)-C(4)
C(4)-C(5)
C(4)-C(6)
C(6)-C(7)
C(7)-C(8)
1.155(6)
1.410(9)
1.409(10)
1.443(8)
1.183(8)
1.433(8)
C(1)-W-C(2)
C(1)-W-C(3)
C(1)-W-C(4)
C(2)-W-C(5)
C(2)-W-C(3)
C(2)-W-C(4)
C(2)-W-C(4)
C(2)-W-C(5)
C(3)-W-C(4)
C(3)-W-C(5)
C(4)-W-C(5)
W-C(1)-O(1)
76.85(21)
82.77(23)
88.46(23)
120.69(23)
119.50(21)
86.63(21)
86.63(21)
80.44(22)
36.07(23)
62.8(3)
W-C(2)-O(2)
W-C(3)-C(4)
W-C(4)-C(5)
W-C(4)-C(6)
W-C(4)-C(6)
C(3)-C(4)-C(5)
C(3)-C(4)-C(5)
C(3)-C(4)-C(6)
C(5)-C(4)-C(6)
W-C(5)-C(4)
C(4)-C(6)-C(7)
C(6)-C(7)-C(8)
178.3(5)
72.7(3)
71.2(3)
72.0(4)
122.5(4)
114.6(5)
121.7(6)
121.7(6)
123.6(6)
72.1(3)
35.9(3)
176.0(5)
174.6(6)
175.1(6)
bond distances and angles appear in Table 1. The
molecule clearly possesses a plane of symmetry across
the tungsten-allyl plane. The tungsten-allyl bonding
is symmetric with essentially equal lengths for the
C(3)-C(4) (1.410(9) Å) and C(4)-C(5) (1.409(10) Å)
bonds as well as for the W-C(3) (2.267(6) Å) and
W-C(5) (2.286(6) Å) bonds. The phenyl group is paral-
lel to the C(3)-C(4)-C(5) allyl plane; this orientation
is favorable for π-electron delocalization through the
phenyl, alkyne, and allyl groups.
The reaction between 2 and CF3SO3H was examined
in an NMR experiment in situ. Shortly after 2 was
treated with CF3SO3H (2.0 equiv) in CDCl3 at -10 °C,
the proton NMR spectra, as depicted in Figure 2,
showed signals of the two solution species 3a ,b in 1:3
molar ratio, respectively. When the same sample was
cooled to -60 °C, 3a ,b were observed to be in the molar
ratio 2:3; these two species appear to be in a state of
equilibrium with each other. Figure 2 shows the
assignment of proton NMR signals for the two cations.
Only three proton NMR signals were observed for the
nonaromatic protons of 3a , consistent with a η4-1-
(benzylidene)trimethylenemethane cation. In contrast,
five NMR signals were observed for the nonaromatic
protons of 3b, and the AB quartet pattern of the CRH2
proton signals suggested an η3-2,3-butadien-1-yl struc-
ture6-10 in which the CF3CO2 group is linked to the CR
carbon. The two low-field signals at δ 8.20 and 7.74
ppm were assigned to the CHPh protons of 3a ,b,
respectively. The 1H NMR pattern of 3b resembles
Compounds 4a ,b undergo an acid-catalyzed hydroly-
sis to the η3-benzoyl complex 5 at 23 °C (Scheme 4).
Stirring of wet THF solutions of 4a ,b at 23 °C with the
catalyst p-toluenesulfonic acid (10 mol %) for 24 h gave
5 in 55% and 52% yields, respectively. In a separate
NMR experiment, treatment of 4a with CF3CO2H (2.0
equiv) in CDCl3 regenerated the two cations 3a ,b in the
a ratio 3a :3b ) 1:3. Formation of 5 was apparently
generated from hydroxy attack at the C3 carbon of 3a
or 3b. In connection with the results in Scheme 3, we
concluded that attack of OR (OR ) OH, OMe) at the CR
carbon of 3a or 3b is kinetically favorable and reversible
in the presence of acid. The attack at the quaternary
(6) (a) Bruce, M. I.; Rogers, J . R.; Snow, M. R.; Swincer, A. G. J .
Chem. Soc., Chem. Commun. 1981, 271. (b) Bruce, M. I.; Hambley, T.
W.; Snow, M. R.; Swincer, A. G. Organometallics 1985, 4, 494.
(7) Nesmeyanov, A. N.; Kolobova, N. E.; Zlotina, I. B.; Lokshin, B.
V.; Lescheva, I. F.; Znobina, G. K.; Anisimov, K. N. J . Organomet.
Chem. 1976, 110, 339.
(9) (a) Benyunes, S. A.; Deeth, R. J .; Fries, A.; Green, M.; Mapartlin,
M.; Nation, C. B. M. J . Chem. Soc., Dalton Trans. 1992, 3453. (b)
Benyunes, S. A.; Green, M.; Deeth, R. J .; Mapartlin, M.; Nation, C. B.
M. J . Chem. Soc., Chem. Commun. 1989, 1998.
(8) Hughes, R. P.; Lambert, J . M. J .; Rheingold, A. L. Organome-
tallics 1985, 4, 2055.
(10) Brisdon, B. J .; Deeth, R. J .; Hodson, A. W. G.; Kemp, C. W.;
Mahon, M. F.; Molloy, K. C. Organometallics 1991, 10, 1107.

CpW(CO)2[η3-2-(phenylethynyl)allyl]
Organometallics, Vol. 15, No. 6, 1996 1567
F igu r e 2. 1H NMR spectra of 3a ,b in CDCl3 at -10 °C.
Sch em e 3
Sch em e 5
column; the yields were 35-40%. IR spectra of 6a ,b
revealed one W-CO terminal absorption band at 2000
cm-1 and a second CO band at 1650 cm-1. In the NMR
spectra, two carbon signals appeared at δ 250 and 210
ppm, respectively, and two sets of NMR signals of
nonequivalent methylene protons were observed in the
region δ 2.50-4.00. The structures of 6a ,b are likely
similar to that of (C5Me5)MoI(CO)[η4-(2-methylvinyl)-
ketene]9a because of close resemblance of their spectra
data. If this is the case, the formation of 6a ,b from 4d ,e
is believed to involve a tungsten-η3-vinylcarbene
intermediate9a generated from protonation at the CHPh
carbon of 4d -4e, as depicted in Scheme 5. Further
insertion of a coordinated carbonyl into the WdC
bond15,16 of this intermediate, followed by capture of
iodide ion, produced the observed products. To ascer-
tain the correct structure, we synthesized the analogue
6c (Scheme 5), which has better crystallinity than 6a ,b
for X-ray structural analysis. Compound 6c was readily
synthesized by treatment of complex 2 with CF3SO3H
Sch em e 4
C3 carbon of 3a or 3b appears to be kinetically slower,
probably because of additional steric hindrance between
the parallel C-OH and C-R bonds (R ) H, Ph) as OH
approaches the C3 carbon opposite CpW(CO)2, as de-
picted in Scheme 4.
Syn th esis a n d Ch a r a cter iza tion of Tu n gsten -
η4-Vin ylk eten e Com p lexes. In the presence of iodide,
compounds 4d ,e were protonated with CF3SO3H to yield
tungsten-η4-vinylketene complexes11-14 6a ,b (Scheme
5). The red products were purified on a short alumina
(12) (a) Newton, M. G.; Pantaleo, N. S.; King, R. B.; Chu, C. K. J .
Chem. Soc., Chem. Commun. 1979, 10. (b) Binger, P.; Cetinkaya, B.;
Kruger, C. J . Organomet. Chem. 1978, 159, 63.
(13) Alcock, N. W.; Danks, T. N.; Richards, C. J .; Thomas, S. E. J .
Chem. Soc., Chem. Commun. 1989, 21.
(14) J ens, K. J .; Weiss, E. Chem. Ber. 1984, 117, 2469.
(15) Mayr, A.; Asaro, M. F.; Glines, T. L. J . Am. Chem. Soc. 1987,
109, 2215.
(11) (a) Wulff, W. D.; Gilberson, S. R.; Springer, J . P. J . Am. Chem.
Soc. 1986, 108, 520. (b) Templeton, J . L.; Herrick, R. S.; Rusik, C. A.;
McKenna, C. E.; McDonald, J . W.; Newton, W. E. Inorg. Chem. 1985,
24, 1383.
(16) Garrett, K. E.; Sheridan, J . B.; Pourreau, D. B.; Feng, W. C.;
Geoffroy, G. L.; Staley, D. L.; Rheingold, A. L. J . Am. Chem. Soc. 1989,
111, 8383.

1568 Organometallics, Vol. 15, No. 6, 1996
Cheng et al.
F igu r e 3. ORTEP drawing of compound 6c.
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for 6c
W-I(1)
2.8498(17)
1.997(9)
2.071(8)
2.381(7)
2.468(7)
2.279(8)
1.140(10)
C(2)-C(3)
C(2)-O(2)
C(3)-C(4)
C(3)-C(6)
C(4)-C(5)
C(6)-C(7)
1.503(12)
1.203(10)
1.386(12)
1.500(12)
1.425(12)
1.522(11)
W-C(1)
W-C(2)
W-C(3)
W-C(4)
W-C(5)
C(1)-C(1)
F igu r e 4. ORTEP drawing of one independent molecule
of compound 7.
C(2) atom; this diastereomer is expected to be more
stable than the other isomer possibly present in the
reaction.
I(1)-W-C(1)
I(1)-W-C(2)
I(1)-W-C(3)
I(1)-W-C(4)
I(1)-W-C(5)
C(1)-W-C(2)
C(1)-W-C(3)
C(1)-W-C(4)
C(1)-W-C(5)
C(2)-W-C(3)
C(2)-W-C(4)
C(2)-W-C(5)
C(3)-W-C(4)
C(3)-W-C(5)
C(4)-W-C(5)
79.0(3)
136.62(23)
98.04(20)
78.88(20)
86.93(23)
89.1(3)
W-C(1)-O(1)
W-C(2)-C(3)
W-C(2)-O(2)
C(3)-C(2)-O(2)
W-C(3)-C(2)
W-C(3)-C(4)
W-C(3)-C(6)
C(2)-C(3)-C(4)
C(2)-C(3)-C(6)
C(4)-C(3)-C(6)
W-C(4)-C(3)
W-C(4)-C(5)
C(3)-C(4)-C(5)
W-C(5)-C(4)
C(3)-C(6)-C(7)
178.3(7)
81.9(5)
146.7(6)
131.2(7)
59.4(4)
Alk yla tion of 2 w ith Aceta ld eh yd e. We carried
out preliminary tests on the alkylation of 2 with
acetaldehyde in the presence of BF3‚Et2O. Treatment
of 2 with a mixture of BF3‚Et2O (1.2 equiv) and CH3-
CHO (10 equiv) in cold diethyl ether produced a brown-
ish yellow precipitate, and further addition of Bu4NOH
or MeOH led to disappearance of this cation. The
resulting products consisted of three diastereomers for
each case, due to generation of three asymmetric carbon
centers. Separations of the mixtures with fractional
crystallization or column chromatography were unsuc-
cessful. Treatment of this salt with NaBH3CN (5-6
equiv) in acetonitrile produced only one product, 7, in
65% yield after workup. Complex 7 has a η3-pentadi-
enyl structure containing a vinyl PhCdCHMe group,
as indicated by the 1H and 13C NMR data. The
structure of 7 was confirmed with an X-ray diffraction
study to provide the molecular structure in Figure 4 and
the selected bond distances and angles in Table 3. The
ORTEP drawing shows a η3-pentadienyl ligand with a
trans PhCdCH double bond and a methyl group on the
central allyl carbon. The phenyl group is essentially
orthogonal to the allyl plane presumably because of
steric hindrance. The η3-pentadienyl fragment is nearly
planar, as indicated by the dihedral angle 27(4)° be-
tween the C(3a)-C(4a)-C(5a) and C(6a)-C(7a)-C(8a)
planes.
We used NaBD3CN (95% deuterium content) as a
reducing reagent to understand the formation mecha-
nism of 7. In this reaction, 1H NMR spectra of 7 showed
deuterium content at C2 methyl and C3H positions: ca.
30% and 92%, respectively. These data indicate that
intermediate C is likely an alkylated (methylene)-
trimethylenemethane cation that underwent hydride
attack at the C1 position to yield η1-2,3-butadienyl
species D. A second hydride attack at the allyl C3-
carbon of D led to SN2′ displacement of the OBF3- group
to yield 7.
76.8(4)
81.8(3)
129.6(5)
113.9(7)
119.8(7)
126.3(8)
70.0(4)
65.4(4)
117.5(8)
79.9(4)
104.3(3)
138.9(3)
38.7(3)
63.8(3)
75.0(3)
33.2(3)
62.0(3)
34.6(3)
113.8(7)
and Bu4NI (2.3 equiv) in cold CH2Cl2; the yield was 40%.
Here, the η3-2,3-butadienyl complex A is presumably the
reaction intermediate that reacted further with HI to
6c as the final product.
The molecular structure of 6c is shown in Figure 3,
and the selected bond distances and angles are provided
in Table 2. The ORTEP drawing confirms the η4-
vinylketene structure; the coordination geometry about
the tungsten center approximates a piano-stool geom-
etry if vinylketene is considered two-coordinate. The
η4-butadiene moiety is almost planar, as indicated by
the small dihedral angle 1.1(1)° between the C(2)-C(3)-
C(4) and C(3)-C(4)-C(5) planes; however, the O(2)
atom lies 0.72(1) Å from the diene plane. In this η4-
diene moiety, the W-C(2) distance (2.071(8) Å) is much
shorter than the other W-C(3) (2.381(7) Å), W-C(4)
(2.468(7) Å), and W-C(5) (2.279(8) Å) bonds; likewise,
the C(2)-C(3) length (1.503(12) Å) is longer than the
C(3)-C(4) (1.386(12) Å) and C(4)-C(5) (1.425(12) Å)
bonds. According to these structural parameters, the
tungsten-η4-vinylketene moiety is best described by an
σ,η3-acylallyl bonding, represented by B in Scheme 5.
In this formalism, the C(2) atom becomes sp2-hybridized
to distort the ketene O(2)-C(2)-C(3) fragment (131.2(7)°)
from linearity. The long W-C(2) bond reflects the
electronic effect of the C(2)-O(2) carbonyl, which makes
the C(2) atom more significant than the other carbons
in the metal-diene back-bonding. Consequently, the
W-I bond (2.8498(17) Å) is favored to be trans to the
In conclusion, we have demonstrated the existence of
a CpW(CO)2(η4-1-(methylene)trimethylenemethane)+ cat-
ion, which was generated on protonation of CpW(CO)2-

CpW(CO)2[η3-2-(phenylethynyl)allyl]
Organometallics, Vol. 15, No. 6, 1996 1569
Ta ble 3. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for 7
ylacetylene and 2-bromo-2-propen-1-ol according to the pro-
cedures described in the literature.17
1
All H NMR (400 and 300 MHz) and 13C NMR (100 and 75
W(1a)-C(1a)
W(1a)-C(2a)
W(1a)-C(2a)
W(1a)-C(3a)
W(1a)-C(4a)
W(1a)-C(5a)
C(1a)-C(2a)
C(1a)-O(1a)
C(2a)-O(2a)
C(3a)-C(4a)
C(4a)-C(5a)
C(4a)-C(9a)
C(5a)-C(6a)
C(6a)-C(7a)
1.93(3)
1.87(3)
1.87(3)
2.32(3)
2.31(3)
2.351(25)
2.37(4)
1.15(3)
1.18(3)
1.41(4)
1.40(4)
1.45(4)
1.55(4)
1.36(4)
W(1b)-C(1b)
W(1b)-C(1b)
W(1b)-C(2b)
W(1b)-C(3b)
W(1b)-C(4b)
C(1b)-O(1b)
C(2b)-O(2b)
C(3b)-C(4b)
C(4b)-C(5b)
C(4b)-C(9b)
C(5b)-C(6b)
C(6b)-C(7b)
C(6b)-C(10b)
C(7b)-C(8b)
1.83
MHz) spectra were obtained on either a Bruker AM-400 or a
1.83(3)
1.88(3)
2.28(3)
2.26(3)
1.25(3)
1.25(4)
1.42(4)
1.33(4)
1.70(4)
1.44(4)
1.38(4)
1.52(4)
1.47(4)
1
Varian Gemini-300 spectrometer; the chemical shifts in H and
13C NMR spectra are reported relative to tetramethylsilane
(δ 0 ppm). Elemental analyses were performed at National
Cheng Kung University, Tainan, Taiwan. Infrared spectra
were recorded on a Perkin-Elmer 781 spectrometer. High-
resolution mass spectra were recorded on a J EOL HX 110
spectrometer.
(1) Syn t h esis of Cp W(CO)3(η1-2-m et h ylen e-4-p h en yl-
3-bu tyn -1-yl) (1). W(CO)6 (5.00 g, 14.2 mmol) was refluxed
with NaC5H5 (1.17 g, 15.0 mmol) in THF (40 mL) for 72 h,
and to this solution was added 2-methylene-4-phenyl-3-butyn-
1-yl tosylate (4.58 g, 14.2 mmol) at 23 °C. The mixture was
stirred for 4 h, evaporated to dryness, and extracted with
diethyl ether (2 × 20 mL). The extract was concentrated and
eluted through a silica column (diethyl ether/hexane 1/1) to
give 1 as a yellow oil (Rf 0.88, 4.60 g, 9.70 mmol, 68%) IR
(Nujol, cm-1): υ(CO) 2011 (vs), 1916 (vs); υ(CtC) 2004 (m).
1H NMR (300 MHz, CDCl3): δ 7.44-7.28 (5H, m, Ph), 5.52
(5H, s, Cp), 5.12 (2H, s, dCH2), 2.52 (2H, s, WsCH2). 13C NMR
(75 MHz, CDCl3): δ 228.6, 217.1 (2 WsCO), 138.8, 131.2,
128.3, 128.0 (Ph), 123.4 (C2), 116.8 (dCH2), 92.2 (Cp), 92.1,
88.3 (CtC), -7.1 (WsC1). Mass (75 eV, m/e): 474 (M+), 446
(M+ - CO), 390 (M+ - 3CO). Anal. Calcd for C19H14WO3: C,
48.13; H, 2.98. Found: C, 49.28; H, 2.06.
(2) Syn th esis of Cp W(CO)2[η3-2-(p h en yleth yn yl)a llyl)]
(2). To a CH2Cl2 (30 mL) solution of 1 (4.00 g, 8.44 mmol)
was added Me3NO (1.26 g, 16.8 mmol), and the mixture was
stirred at 23 °C for 12 h. To this solution was added H2O,
and the product was extracted with diethyl ether (2 × 20 mL).
The extract was concentrated and eluted through a silica
column (diethyl ether/hexane 1/1, Rf 0.58) to produce a yellow
band that yielded 2 as a yellow solid (2.26 g, 5.06 mmol, 60%).
IR (neat, cm-1): υ(CO) 1951 (s), 1880 (s). 1H NMR (400 MHz,
-30 °C, CDCl3): endo/ exo ) 3/2, endo isomer, δ 7.40-7.19
(5H, m, Ph), 5.32 (5H, s, Cp), 2.88 (2H, s, H1s), 1.77 (2H, s,
C(1a)-W(1a)-C(2a) 77.1(11) W(1a)-C(5a)-C(6a) 119.1(17)
C(1a)-W(1a)-C(3a) 82.3(10) C(4a)-C(5a)-C(6a) 123.2(24)
C(1a)-W(1a)-C(4a) 87.7(11) C(5a)-C(6a)-C(7a) 129 (3)
C(1a)-W(1a)-C(5a) 120.8(11) C(6a)-C(7a)-C(8a) 129 (3)
C(2a)-W(1a)-C(3a) 121.0(11) C(1b)-W(1b)-C(2b)
C(2a)-W(1a)-C(4a) 88.7(11) C(1b)-W(1b)-C(3b)
C(2a)-W(1a)-C(5a) 86.0(10) C(1b)-W(1b)-C(4b)
76.8(12)
81.5(11)
91.9(11)
C(3a)-W(1a)-C(4a) 35.4(9) C(2b)-W(1b)-C(3b) 121.5(11)
C(3a)-W(1a)-C(5a) 59.2(9) C(2b)-W(1b)-C(4b)
C(4a)-W(1a(-C(5a) 35.0(10) C(3b)-W(1b)-C(4b)
W(1a)-C(1a)-C(2a) 50.3(9) W(1b)-C(1b)-O(1b) 174.2(23)
W(1a)-C(1a)-O(1a) 174.7(24) W(1b)-C(2b)-O(2b) 174.0(24)
90.6(11)
36.5(10)
C(2a)-C(1a)-O(1a) 128.6(22) W(1b)-C(3b)-C(4b)
W(1a)-C(2a)-C(1a) 52.5(9) W(1b)-C(4b)-C(3b)
W(1a)-C(2a)-O(2a) 177.8(22) W(1b)-C(4b)-C(5b)
71.3(15)
72.2(16)
75.8(17)
C(1a)-C(2a)-O(2a) 125.8(20) W(1b)-C(4b)-C(9b) 116.7(16)
W(1a)-C(3a)-C(4a) 71.7(16) C(3b)-C(4b)-C(5b) 121 (3)
W(1a)-C(4a)-C(3a) 72.9(16) C(3b)-C(4b)-C(9b) 110.2(23)
W(1a)-C(4a)-C(5)
W(1a)-C(4a)-C(9a) 125.9(20) C(4b)-C(5b)-C(6b) 130(3)
C(3a)-C(4a)-C(5a) 110(3) C(5b)-C(5b)-C(7b) 125(3)
74.3(16) C(5b)-C(4b)-C(9b) 127(3)
C(3a)-C(4a)-C(9a) 119.4(25) C(5b)-C(6b)-C(10b) 113.5(24)
C(5a)-C(4a)-C(9a) 129.5(24) C(7b)-C(6b)-C(10b) 120.4(24)
W(1a)-C(5a)-C(4a) 70.7(15) C(6b)-C(6b)-C(8b) 127(3)
Sch em e 6
H
1a); exo isomer, δ 7.40-7.19 (5H, m, Ph), 5.45 (5H, s, Cp),
2.97 (2H, s, H1s), 1.27 (2H, s, H1a). 13C NMR (100 MHz, -30
°C, CDCl3): endo isomer, δ 225.9 (CO), 132.1, 127.9, 127.8,
122.3 (Ph), 88.4 (Cp), 89.9, 81.8 (CtC), 59.1 (C2), 29.0 (C1);
exo isomer, δ 223.4 (CO), 131.6, 128.3, 122.0 (Ph), 94.3 (Cp),
91.3, 81.5 (CtC), 59.1 (C2), 35.2 (C1). Mass (75 eV, m/e): 446
(M+), 390 (M+ - 2CO). Anal. Calcd for C18H14WO2: C, 48.46;
H, 3.16. Found: C, 48.40; H, 3.16.
(3) Ch a r a cter iza tion of 3a ,b. To compound 2 (22.6 mg,
5.06 × 10-2 mmol) in CDCl3 (0.35 mL) was added CF3SO3H
(8.90 ul, 1.01 × 10-1 mmol) at -10 °C, and the yields of 3a
and 3b (3a /3b )1/3) were ca. 96% according to in situ NMR
spectra. IR (CH2Cl2, cm-1): 2050 (s), 2030 (s), 2001 (s), 1988
(s). 1H NMR (400 MHz, -10 °C, CDCl3): 3a , δ 8.20 (1H, s,
CHPh), 7.41-7.09 (5H, m, Ph), 5.82 (5H, s, Cp), 3.64 (2H, s,
[2-(phenylethynyl)allyl] (2). Nucleophilic attack at this
cation produced a CpW(CO)2(η3-2,3-butadienyl) complex
that in the presence of HI underwent protonation to
yield cations of the type CpW(CO)I(η4-vinylketene)+.
Electrophilic alkylation of 2 with acetaldehyde/BF3‚Et2O
yielded the corresponding CpW(CO)2(η4-1-(methylene)-
trimethylenemethane)+ precipitate that upon NaBH3-
CN reduction gave an η3-pentadienyl derivative.
H
1s), 3.13 (2H, s, H1a); 3b, δ 7.74 (1H, s, CHPh), 7.41-7.09
(5H, m, Ph), 5.50 (5H, s, Cp), 3.47 (1H, s, H1s), 3.11 (1H, d, J
) 6.5 Hz, CRHH′), 3.02 (1H, d, J ) 6.5 Hz, CRHH′), 2.89 (1H,
s, H1a). 13C NMR (100 MHz, -10 °C, CDCl3): 3a , 198.8 (W-
CO), 155.8 (C3), 134.7, 129.8, 128.8, 127.2 (Ph), 122.1 (CHPh),
96.2 (C2), 86.7 (C5H5), 56.3 (C1); 3b, 200.3, 197.9 (2 W-CO),
160.6 (C3), 134.0, 130.8, 128.4, 127.0 (Ph), 122.2 (CHPh), 93.5
(C2), 87.7 (C5H5), 64.7 (CR), 56.2 (C1). Both 3a and 3b were
not stable at 23 °C in solid form, and elemental analyses of
the two samples were not successful.
(4) Syn th esis of Cp W(CO)2[η3-2-(h yd r oxym eth yl)-4-
p h en yl-2,3-bu ta d ien -1-yl] (4a ). To a diethyl ether solution
(10 mL) of 2 (0.20 g, 0.45 mmol) was added CF3SO3H (0.040
mL, 0.90 mmol) at -20 °C, and the mixture was stirred for 1
h to produce dark yellow precipitates of 3a and 3b. To the
Exp er im en ta l Section
All operations were carried out under argon in a Schlenk
apparatus or in a glove box. The solvents benzene, diethyl
ether, tetrahydrofuran, and hexane were dried with sodium
benzophenone and distilled before use. Dichloromethane was
dried over calcium hydride and distilled. W(CO)6, phenyl-
acetylene, and cyclopentadiene were obtained commercially
and used without purification. Anhydrous Me3NO was ob-
tained by sublimation of its dihydrate form at 110 °C. 2-Meth-
ylene-4-phenyl-3-butyn-1-yl tosylate was prepared from phen-
(17) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett.
1975, 4467.

1570 Organometallics, Vol. 15, No. 6, 1996
Cheng et al.
precipitate at -20 °C were added a THF solution of 20% Bu4-
NOH (1.17 mL, 0.90 mmol) and then H2O (4 mL); the mixture
was stirred for 2 h before addition of an aqueous NH4OH (5
mL) solution. The solution was extracted with diethyl ether
(2 × 20 mL), concentrated and eluted through a silica column
(diethyl ether/hexane ) 1/1) to produce a yellow band (Rf 0.40)
that gave 4a as a yellow solid (0.11 g, 0.24 mmol, 53%). IR
(CH2Cl2, cm-1): υ(CO) 1954 (s), 1881 (s). 1H NMR (300 MHz,
CDCl3): δ 7.61 (1H, s, CHPh), 7.50-7.18 (5H, m, Ph), 5.26
(5H, s, Cp), 4.24 (1H, d, J ) 12.3 Hz, CRHH′), 4.12 (1H, d, J
) 12.3 Hz, CRHH′), 2.93 (1H, s, H1s), 2.59 (1H, s, H1a). 13C
NMR (75 MHz, CDCl3): δ 225.1, 224.4 (2 WsCO), 159.5 (C3),
139.7, 128.2, 127.5, 126.6 (Ph), 122.7 (CHPh), 89.8 (Cp), 80.6
(C2), 67.5 (CR), 28.2 (C1). Mass (75 eV, m/e): 464 (M+ - CO),
408 (M+ - 2CO). Anal. Calcd for C18H16WO3: C, 46.58; H,
3.47. Found: C, 46.36; H, 3.35.
that lithium phenylacetylide (5.0 equiv) was used; the yield
was 60%. IR (Nujol, cm-1): υ(CO) 1955 (s), 1884 (s). 1H NMR
(400 MHz, CDCl3): δ 7.62 (1H, s, CHPh), 7.31-7.17 (10H, m,
Ph), 5.27 (5H, s, Cp), 3.86 (1H, d, J ) 17.6 Hz, CHH′), 3.27
(1H, d, J ) 17.6Hz, CHH′), 3.16 (1H, s, H1s), 2.68 (1H, s, H1a).
13C NMR (100 MHz, CDCl3): δ 225.1, 224.4 (2 WsCO), 160.5
(C3), 141.0, 138.5, 132.0, 131.0, 129.0, 128.0, 127.6, 126.9, 123.2
(2 Ph + C4), 89.7 (Cp), 87.0, 83.4 (CtC), 79.1 (C2), 28.8 (CR),
27.8 (C1). Mass (75 eV, m/e): 548 (M+), 492 (M+ - 2CO). Anal.
Calcd for C26H20WO2: C, 56.96; H, 3.68. Found: C, 57.12; H,
3.02.
(10) Syn th esis of Cp W(CO)2(η3-2-m eth yl-4-p h en yl-2,3-
bu ta d ien -1-yl) (4g). This compound was similarly prepared
according to the procedure for synthesis of 4a , except that
NaBH3CN (3.0 equiv) was used; the yield was 52%. IR (Nujol,
cm-1): υ(CO) 1955 (s), 1884 (s). 1H NMR (400 MHz, CDCl3):
δ 7.53 (1H, s, CHPh), 7.50 (2H, d, J ) 5.0 Hz, Ph), 7.38 (2H,
t, J ) 5.0 Hz, Ph), 7.16 (1H, J ) 5.0 Hz, Ph), 5.25 (5H, s, Cp),
2.84 (1H, s, H1s), 2.64 (1H, s, H1a), 2.27 (3H, s, Me). 13C NMR
(75 MHz, CDCl3): 226.8, 223.7 (2 WsCO), 162.5 (C3), 140.1,
127.9, 127.2, 126.1 (Ph), 121.9 (C4), 89.8 (Cp), 81.4 (C2), 31.3
(C1), 22.5 (Me). Mass (75 eV, m/e): 448 (M+). Anal. Calcd
for C18H16WO2: C, 48.24; H, 3.60. Found: C, 48.04; H, 3.55.
(11) Syn th esis of Cp W(CO)2(η3-2-ben zoyla llyl) (5). To
(5) Syn th esis of Cp W(CO)2[η3-2-(m eth oxym eth yl)-4-
p h en yl-2,3-bu ta d ien -1-yl] (4b). This compound was simi-
larly prepared according to the procedure for synthesis of 4a ,
except that excess MeOH (5 mL) was used; the yield was 55%.
IR (neat, cm-1): υ(CO) 1955 (s), 1884 (s). 1H NMR (400 MHz,
CDCl3): δ 7.63 (1H, s, CHPh), 7.48-7.14 (5H, m, Ph), 5.25
(5H, s, Cp), 3.95 (1H, d, J ) 10.6 Hz, CRHH′), 3.60 (1H, d, J )
10.6 Hz, CRHH′), 3.45 (3H, s, OMe), 2.90 (1H, s, H1s), 2.59
(1H, s, H1a). 13C NMR (100 MHz, CDCl3): δ 224.4, 221.9 (2
WsCO), 160.7 (C3), 139.8, 128.0, 127.4, 126.3 (Ph), 122.1
(CHPh), 89.6 (Cp), 78.0 (C2), 76.4 (OMe), 58.6 (CR), 29.6 (C1).
Mass (75 eV, m/e): 478 (M+), 422 (M+ - 2CO). Anal. Calcd
for C19H18WO3: C, 47.72; H, 3.79. Found: C, 48.15; H, 3.41.
(6) Syn t h esis of Cp W(CO)2[η3-2-((isob u t yla m in o)-
m eth yl)-4-p h en yl-2,3-bu ta d ien -1-yl] (4c). This compound
was prepared according to the procedure for synthesis of 4a ,
except that excess isobutylamine (2 mL) was used; the yield
was 48%. IR (Nujol, cm-1): υ(CO) 1953 (s), 1882 (s). 1H NMR
(400 MHz, CDCl3): δ 7.55 (1H, s, CHPh), 7.50-7.17 (5H, m,
Ph), 5.23 (5H, s, Cp), 3.30 (1H, d, J ) 13.1 Hz, CRHH′), 3.02
(1H, d, J ) 13.1 Hz, CRHH′), 2.88 (1H, s, H1s), 2.64 (1H, s,
a THF/H2O solution (1/1, 5 mL) of 3a (0.22 g, 0.48 mmol) was
-2
added p-toluenesulfonic acid (4.1 mg, 2.4 × 10
mmol), and
the mixture was stirred for 6 h at 23 °C. To this solution was
added an aqueous NaHCO3 solution (5 mL), and the product
was extracted with ether, concentrated, and eluted through a
silica column (diethyl ether/hexane) to yield a yellow band (Rf
0.54) that gave 5 (0.12 g, 0.26 mmol, 55%). IR (cm-1): υ(CO)
1962 (s), 1887 (s), 1658 (vs). 1H NMR (400 MHz, -10 °C,
CDCl3): δ 7.32-7.22 (5H, m, Ph), 5.34 (5H, s, Cp), 3.69 (2H,
s, COCH2), 3.12 (2H, s, H1s), 1.59 (2H, s, H1a). 13C NMR (100
MHz, -10 °C, CDCl3): δ 222.3 (2 WsCO), 198.1 (PhCOCH2),
135.1, 129.5, 128.4, 126.6 (Ph), 87.9 (Cp), 86.7 (C2), 42.6 (CH2),
25.4 (C1). Mass (75 eV, m/e): 464 (M+), 436 (M+ - CO), 408
(M+ - 2CO). Anal. Calcd for C18H16WO3: C, 46.58; H, 3.47.
Found: C, 46.36; H, 3.35.
H
1a), 2.59 (2H, m, NCH2), 1.77 (1H, m, CHMe2), 0.93 (6H, d, J
) 6.6 Hz, Me). 13C NMR (75 MHz, CDCl3): δ 222.8, 222.0 (2
WsCO), 161.4 (C3), 139.8, 127.9, 127.4, 126.3 (Ph), 121.6
(CHPh), 89.7 (Cp), 57.1 (C2), 56.6 (CR), 30.2 (C1), 28.3 (NCH2),
20.6 (CH), 20.4 (Me). Mass (75 eV, m/e): 519 (M+), 463 (M+
- 2CO). Anal. Calcd for C22H25WO2N: C, 50.88; H, 4.85.
Found: C, 51.16; H, 4.67.
(12) Syn th esis of Cp W(CO)I[η4-2-ben zyl-3-(eth ylvin yl)-
k eten e] (6a ). To a dichloromethane (10 mL) solution of 4d
(0.10 g, 0.22 mmol) and Bu4NI (0.11 g, 0.30 mmol) was added
CF3SO3H (0.011 mL, 0.11 mmol) at -60 °C; the mixture was
stirred for 2 h before addition of an aqueous NaHCO3 solution
(10 mL). The product was extracted with diethyl ether (2 ×
10 mL), concentrated, and eluted through a short alumina
column (dichloromethane/diethyl ether ) 1/1) to produce a red
band that yielded 6a as a red solid (Rf 0.45, 40 mg, 0.080 mmol,
35%). IR (Nujol, cm-1): υ(CO) 1999 (s), 1942 (s), 1650 (vs).
1H NMR (400 MHz, CDCl3): δ 7.39-7.21 (5H, m, Ph), 5.27
(5H, s, Cp), 3.64 (2H, ABq, J ) 4.0 Hz, PhCH2), 3.61 (1H, d, J
) 3.4 Hz, C4Hs), 2.77 (1H, m, CHH′Me), 2.72 (1H, d, J ) 3.4
Hz, C4Ha), 2.65 (1H, m, CHH′Me), 0.73 (3H, t, J ) 7.6 Hz,
Me). 13C NMR (100 MHz, CDCl3): δ 259.4 (C1dO), 219.7 (CO),
147.4 (C3), 139.0, 128.7, 128.6, 126.6 (Ph), 90.4 (Cp), 74.3 (C2),
39.2 (C4), 33.6 (PhCH2), 29.4 (CH2Me), 14.7 (Me). Mass (75
eV, m/e): 562 (M+ - CO). Anal. Calcd for C19H19WO2I: C,
38.67; H, 3.25. Found: C, 38.21; H, 3.15.
(7) Syn t h esis of Cp W(CO)2(η3-2-et h yl-4-p h en yl-2,3-
bu ta d ien -1-yl) (4d ). This compound was similarly prepared
according to the procedure for synthesis of 4a , except that Me2-
CuLi (5.0 equiv) was used; the yield was 55%. IR (Nujol, cm-1):
υ(CO) 1953 (s), 1883 (s). 1H NMR (300 MHz, CDCl3): δ 7.55
(1H, s, CHPh), 7.54-7.19 (5H, m, Ph), 5.52 (5H, s, Cp), 2.85
(1H, s, H1s), 2.61 (1H, s, H1a), 2.23 (2H, m, CRHH′), 1.19 (3H,
t, J ) 7.5Hz, CH2). 13C NMR (75 MHz, CDCl3): δ 224.3, 226.9
(2 WsCO), 161.8 (C3), 140.1, 127.9, 127.4, 126.1 (Ph), 121.5
(CHPh), 89.8 (Cp), 86.3 (C2), 30.8 (C1), 29.6 (CR), 15.5 (Me).
Mass (75 eV, m/e): 462 (M+), 406 (M+ - 2CO). Anal. Calcd
for C19H18WO2: C, 49.37, H, 3.93. Found: C, 49.66; H, 3.88.
(8) Syn th esis of Cp W(CO)2(η3-2-ben zyl-4-p h en yl-2,3-
bu ta d ien -1-yl) (4e). This compound was prepared according
to the procedure for synthesis of 4a except that PhLi (5.0 equiv)
was used; the yield was 58%. IR (Nujol, cm-1): υ(CO) 1955
(s), 1886 (s). 1H NMR (400 MHz, CDCl3): δ 7.60-7.17 (11H,
m, Ph+ CHPh), 5.26 (5H, s, Cp), 3.39 (1H, d, J ) 13.8 Hz,
CHH′), 3.26 (1H, d, J ) 13.8, CHH′), 2.91 (1H, s, H1s), 2.62
(1H, s, H1a). 13C NMR (100 MHz, CDCl3): δ 226.2, 223.5 (2
WsCO), 161.6 (C3), 141.5, 139.5, 132.3, 130.0, 129.0, 128.4,
127.1, 126.5, 122.2 (2 Ph + C4), 89.8 (Cp), 81.8 (C2), 44.3 (CR),
30.1 (C1). Mass (75 eV, m/e): 524 (M+), 468 (M+ - 2CO). Anal.
Calcd for C24H20WO2: C, 54.98; H, 3.85. Found: C, 55.32; H,
3.64.
(13) Syn th esis of Cp W(CO)I[η4-2-ben zyl-3-(ben zylvi-
n yl)k eten e] (6b). This compound was prepared according to
the procedure for synthesis of 6a , except that compound 4e
was used; the yield was 38%. IR (neat, cm-1): υ(CO) 2002
(s). 1H NMR (400 MHz, CDCl3): δ 7.30-6.79 (10H, m, Ph),
5.26 (5H, s, Cp), 4.25 (1H, d, J ) 15.5 Hz, CHH′Ph), 4.02 (1H,
d, J ) 15.5 Hz, CHH′Ph), 3.78 (1H, d, J ) 14.9 Hz, CHH′Ph),
3.71 (1H, d, J ) 14.9 Hz, CHH′Ph), 3.61 (1H, d, J ) 3.2 Hz,
H
4s), 2.73 (1H, d, J ) 3.2 Hz, H4a). 13C NMR (100 MHz,
CDCl3): δ 253.7 (C1dO), 210.0 (WsCO), 143.9 (C3), 138.7,
138.4, 129.4, 128.9, 128.6, 128.2, 126.7, 126.4 (Ph), 90.4 (Cp),
76.4 (C2), 41.1, 40.7, 33.7 (C4 + 2 CH2Ph). Mass (75 eV, m/e)
624: (M+ - CO). Anal. Calcd for C24H21WO2I: C, 44.20; H,
3.25. Found: C, 43.98; H, 3.11.
(9) Syn t h esis of Cp W(CO)2[η3-2-(p h en ylet h yn yl)-4-
p h en yl-2,3-bu ta d ien -1-yl] (4f). This compound was pre-
pared according to the procedure for synthesis of 4a , except

CpW(CO)2[η3-2-(phenylethynyl)allyl]
Ta ble 4. Cr ysta l Da ta a n d Con d ition s for Cr ysta llogr a p h ic Da ta Collection a n d Str u ctu r e Refin em en ta
6c
W12O2C18H16
Organometallics, Vol. 15, No. 6, 1996 1571
2
7
formula
fw
WC18H14O2
446.15
WC20H21O2
477.23
701.97
diffractometer used
nonius
nonius
nonius
space group
a (Å)
b (Å)
monoclinic, P21/c
17.047(5)
6.1126(20)
14.755(3)
100.952(20)
1509.5(7)
4
monoclinic, P21/c
8.1337(18)
11.173(6)
21.306(4)
91.327(16)
1935.8(12)
4
orthorhombic, Pca21
18.169(6)
8.964(3)
21.553(6)
3510.3(19)
c (Å)
â (deg)
V (Å3)
Z
8
D
calc (g cm-3
)
1.963
2.409
1.806
λ (Å)
F(000)
0.7107
844.
0.7107
1270.
0.7107
1840.
unit cell detn: no; 2θ range (deg)
25; 19.66-32.00
25; 28.60-39.65
25; 15.18-19.00
scan type
θ/2θ
θ/2θ
θ/2θ
scan width (deg)
scan speed (deg/min)
2θmax (deg)
2 (0.65 0.35 tan θ)
2.06-8.24
50.0
(-20, +19) (0-7) (0-17)
78.162
2 (0.80 + 0.35 tan θ)
3.30-8.24
45.0
(-8, +8) (0-12) (0-22)
92.568
0.20 × 0.30 × 0.40
0.570; 1.000
298.00
2 (0.65 + 0.35 tan θ)
2.06-8.24
50.0
(0-21) (0-7) (0-25)
67.199
hkl ranges
µ (cm-1
)
cryst size (mm)
transmissn
0.10 × 0.30 × 0.45
0.20 × 0.25 × 0.45
0.335; 1.000
0.757; 1.000
temp (K)
298.00
298.00
no. of measd rflns
no. of obsd rflns (I > 2.0σ(I))
no. of unique rflns
RF; Rw
2649
2346
2649
0.022; 0.020
2518
2237
2518
0.028; 0.028
2.21
2769
2057
2769
0.048; 0.050
GOF
2.39
2.04
refinement program
no. of atoms
NRCVAX
35
NRCVAX
39
NRCVAX
88
no. of refined params
minimize function
weighting scheme
q (2nd ext. coeff) × 104
(∆/σ)max
191 (2346 out of 2649 rflns)
209 (2237 out of 2518 rflns)
416 (2057 out of 2769 rflns)
2
2
2
∑(w|Fo - Fc| )
∑(w|Fo - Fc| )
∑(w|Fo - Fc| )
(1/σ2) (Fo)
0.61(3)
(1/σ2) (Fo)
0.71(3)
(1/σ2) (Fo)
1.42(13)
0.0188
-1.020, 0.780
0.0110
-1.030, 0.900
0.0550
-1.230; 3.850
(D map) min, max (e/Å3)
RF ) ∑(Fσ - Fc)/∑Fσ; Rw ) [∑(w(Fσ - Fc)2)/∑(wFσ2)]1/2; GOF ) [∑(w(Fσ - Fc)2)/(NO - NP)]1/2
.
a
(14) Syn th esis of Cp W(CO)I[η4-2-ben zyl-3-((iod om eth -
yl)vin yl)k eten e) (6c). This compound was similarly pre-
pared from the reaction between 2, CF3SO3H, and Bu4NI
according to the procedure for the synthesis of 6a . IR (cm-1):
υ(CO) 2003 (s), 1648 (s). 1H NMR (400 MHz, CDCl3): δ 7.36-
7.20 (5H, m, Ph), 5.31 (5H, s, Cp), 4.48 (1H, d, J ) 9.4 Hz,
CHH′Ph), 3.85 (1H, d, J ) 9.4 Hz, CHH′Ph), 3.69 (1H, d, J )
14.9 Hz, CHH′I), 3.62 (1H, d, J ) 14.9 Hz, CHH′I), 3.59 (1H,
d, J ) 3.2 Hz, H4s), 2.66 (1H, d, J ) 3.2 Hz, H4a). 13C NMR
(100 MHz, CDCl3): δ 253.7 (C1dO), 211.4 (CO), 137.1 (C2),
136.9, 129.8, 128.9 (Ph), 90.1 (Cp), 75.6 (C3), 39.7 (C4), 33.9
(CHH′Ph), 4.0 (CHH′I). Anal. Calcd for C18H16WO2I2: C,
30.80; H, 2.30. Found: C, 30.92; H, 2.42.
C3H), 2.51 (1H, s, H1s), 2.35 (3H, s, Me), 1.56 (3H, d, J ) 13.1
Hz, Me), 1.51 (1H, s, H1a). 13C NMR (100 MHz, CDCl3): δ
230.8, 229.8 (2 WsCO), 143.3 (C4), 141.5, 129.0, 128.1, 126.4
(Ph), 122.3 (C5), 97.8 (C2), 89.7 (Cp), 54.8 (C3), 27.7 (C1), 21.5
(Me), 15.0 (Me). Mass (75 eV, m/e): 476 (M+), 416 (M+ - 2CO).
Anal. Calcd for C20H20WO2: C, 50.44; H, 4.23. Found: C,
49.98; H, 4.20.
X-r a y Diffr a ction Stu d ies of 2, 6c, a n d 7. Single crystals
of 2, 6c, and 7 were sealed in glass capillaries under an inert
atmosphere. Data for 2, 6c, and 7 were collected on a Nonius
CAD 4 using graphite-monochromated Mo KR radiation, and
the structures were solved by the heavy-atom method; all data
reduction and structural refinements were performed with the
NRCCSDP package. Crystal data, details of data collection,
and structural analysis are summarized in Table 4. For all
structures, all non-hydrogen atoms were refined with aniso-
tropic parameters, and all hydrogen atoms included in the
structure factors were placed in idealized positions.
(15) Syn th esis of Cp W(CO)2(η3-2,5-d im eth yl-4-p h en yl-
2,4-p en ta d ien -1-yl) (7). To a diethyl ether solution of
compound 2 (0.20 g, 0.45 mmol) was added acetaldehyde (0.37
mmol, 4.50 mmol) and BF3‚Et2O (0.13 mL, 0.68 mmol) at -40
°C, and the solution was stirred for 3 h to produce an insoluble
precipitate. The diethyl ether layer was decanted away, and
the precipitate was washed with diethyl ether at -40 °C. This
precipitate in diethyl ether (5 mL) was treated with an
acetonitrile solution of NaBH3CN (0.12 g, 1.35 mmol) at -40
°C to cause disappearance of the precipitate. The solution was
stirred for 1 h at -40 °C before addition of an aqueous NH4Cl
solution. The product was extracted with diethyl ether,
concentrated, and eluted through a silica column (diethyl
ether/hexane ) 1/1) to yield a yellow band of 7 (Rf 0.81, 0.13
g, 0.27 mmol, 60%). IR (Nujol, cm-1): υ(CO) 1935 (s), 1856
(s). 1H NMR (400 MHz, CDCl3): δ 7.55-7.07 (5H, m, Ph), 5.93
(1H, q, J ) 6.3 Hz, dCHMe), 4.91 (5H, s, Cp), 3.22 (1H, s,
Ack n ow led gm en t. We wish to thank the National
Science Council and National Institute of Health of
Taiwan for financial support of this work.
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates, bond distances, bond angles, and thermal param-
eters for 2, 6c, and 7 (13 pages). Ordering information is given
on any current masthead page.
OM9507989