Syntheses and crystal structures of tungsten complexes containing various (thiazoliumyl)diphenylphosphine ligands

Article abstract of DOI:10.1021/om970418e

Alkylation reactions at the S atom of the anionic PPh₂C(=NPh)S^- ligand coordinated to a tungsten pentacarbonyl group afford the neutral complexes W(CO)₅PPh₂C(=NPh)SR (4, R = CH₂C≡CH; 5, R = CH₂C≡N; 6, R = CH₂CONH₂; 7, R = CH₂CH=CH₂; 8, R = CH₂CO₂-Me). Protonation of 4 with HBF₄ at room temperature causes cyclization to the cationic complex W(CO)₅PPh₂[CSCH₂C(CH₂)NPh]BF ₄ (10), which contains a (thiazoliumyl)diphenylphosphine ligand. Similarly, protonation reactions of 5 and 6 with HBF4 give the cationic complex [W(CO)₅PPh₂CSCHC(NH₂)NPh]BF₄ (11) and the neutral complex W(CO)₅PPh₂CSCHC-(OBF₃)NPh (12), respectively, both of which contain (thiazoliumyl)diphenylphosphine ligands. The structures of 10 and 12 are determined by X-ray diffraction analyses.

Full text of DOI:10.1021/om970418e

Organometallics 1998, 17, 513-518
513
Syn th eses a n d Cr ysta l Str u ctu r es of Tu n gsten
Com p lexes Con ta in in g Va r iou s
(Th ia zoliu m yl)d ip h en ylp h osp h in e Liga n d s
Kuang-Hway Yih, Sung-Chih Yeh, Ying-Chih Lin,* Gene-Hsiang Lee, and
Yu Wang
Department of Chemistry, National Taiwan University, Taipei, Taiwan 106, Republic of China
Received May 20, 1997
Alkylation reactions at the S atom of the anionic PPh2C(dNPh)S- ligand coordinated to
a tungsten pentacarbonyl group afford the neutral complexes W(CO)5PPh2C(dNPh)SR (4,
R ) CH2CtCH; 5, R ) CH2CtN; 6, R ) CH2CONH2; 7, R ) CH2CHdCH2; 8, R ) CH2CO2-
Me). Protonation of 4 with HBF4 at room temperature causes cyclization to the cationic
complex W(CO)5PPh2[CSCH2C(CH2)NPh]BF4 (10), which contains a (thiazoliumyl)diphen-
ylphosphine ligand. Similarly, protonation reactions of 5 and 6 with HBF4 give the cationic
complex [W(CO)5PPh2CSCHC(NH2)NPh]BF4 (11) and the neutral complex W(CO)5PPh2CSCHC-
(OBF3)NPh (12), respectively, both of which contain (thiazoliumyl)diphenylphosphine ligands.
The structures of 10 and 12 are determined by X-ray diffraction analyses.
In tr od u ction
Resu lts a n d Discu ssion
Coor d in a ted P P h 2C(dNP h )S- Liga n d a n d Its
Alk yla tion Rea ction s. Facile deprotonation of W-
(CO)5PPh2H by n-BuLi followed by exchange of the
cation with Et4NBr gives Et4N[W(CO)5PPh2] (1). The
IR spectrum of 1 has two relatively high frequency CO
stretching bands at 2070 and 1910 cm-1, indicating that
the anionic charge is localized at the phosphide ligand.
Thus, treatment of 1 with PhNdCdS leads to the
formation of a P-C bond to give [Et4N][W(CO)5PPh2C-
(dNPh)S] (2a ).8 Complex 2a can also be obtained
directly from W(CO)5PPh2H, without going through the
isolation of 1, in ca. 85% yield. Complex 2a is an air-
stable yellow solid. The IR spectrum in the νCO region
shows a pattern characteristic for an octahedral M(CO)5L
group, and the 31P NMR spectrum shows a resonance
at δ 34.3 with J W-P ) 238.9 Hz. These data indicate a
monodentate P-coordination mode of the phosphine
ligand in 2a . This bonding mode contrasts with the
chelation through P and S atoms by a similar ligand in
complexes reported by Kunze and co-workers.9 Inter-
estingly, there is no reaction between 1 and the aliphatic
isothiocyanate PhCH2NdCdS. A reaction between
PhNdCdO and 1 was found to occur, but no product
could be isolated and identified.
Thiazoles, mesoionic thiazoles, and thiazolium deriva-
tives have attracted considerable attention because of
their unusual charge distribution and possible aromatic
properties of the five-membered rings. Some methods
for the synthesis of thiazolium derivatives1 as well as
bivalent metal thiazolium salts2 have been reported.
Furthermore, much work has been carried out on the
nucleophilic reactivity,3 cycloaddition reactions,4 and
infrared, visible absorption, and resonance Raman5
studies of organic thiazolium compounds. However,
only a few metal thiazolium derivatives have been
reported.6 Our previous report dealt with alkylation
reactions of the complex [Et4N][W(CO)5PPh2(CS2)] by
unsaturated organic halides and their subsequent reac-
tions.7 In this paper, we wish to report a new method
for the synthesis of tungsten complexes containing
(thiazoliumyl)diphenylphosphine ligands.
(1) (a) Avalos, M.; Babiano, R.; Dianez, M. J .; Espinosa, J .; Estrada,
M. D.; J ime´nez, J . L.; Lo´pe-Castro, A.; Me´ndez, M. M.; Palacios, J . C.
Tetrahedron 1992, 48, 4193. (b) Potts, K. T.; Baum, J .; Datta, S. K.;
Houghton, E. J . Org. Chem. 1976, 41, 813.
(2) (a) Richardson, M. F.; Franklin, K.; Tompson, D. M. J . Am. Chem.
Soc. 1975, 97, 3204. (b) Hadjiliadis, N.; Yannopoulos, A.; Bau, R. Inorg.
Chim. Acta 1983, 69, 109. (c) Louloudi, M.; Hadjiliadis, N. J . Chem.
Soc., Dalton Trans. 1991, 1635.
(3) (a) Pirotte, B.; Delarge, J . J . Chem. Res., Synop. 1990, 208. (b)
Itoh, T.; Nagata, K.; Okada, M.; Ohsawa, A. Tetrahedron Lett. 1992,
33, 361.
(4) Cavalleri, P.; Clerici, F.; Erba, E.; Trimarco, P. Chem. Ber. 1992,
125, 883.
Photolysis of 2a by UV radiation leads to loss of CO
and formation of [Et4N]W(CO)4[η2-PPh2C(dNPh)S] (3a ),
in which the phosphine ligand binds to the metal in a
(5) Katayama, N.; Enomoto, S.; Sato, T.; Ozaki, Y. J . Phys. Chem.
1993, 97, 6880.
(6) (a) Cramer, R. E.; Maynard, R. B.; Evangelista, R. S. J . Am.
Chem. Soc. 1984, 106, 111. (b) Aoki, K.; Yamazaki, H. J . Am. Chem.
Soc. 1985, 107, 6242.
(7) (a) Yih, K. H.; Lin, Y. C.; Cheng, M. C.; Wang, Y. Organometallics
1994, 13, 1561. (b) Yih, K. H.; Lin, Y. C.; Cheng, M. C.; Wang, Y. J .
Chem. Soc., Chem. Commun. 1995, 233.
(8) (a) Yih, K. H.; Lin, Y. C.; Cheng, M. C.; Wang, Y. J . Chem. Soc.,
Chem. Commun. 1993, 1380. (b) Yih, K. H.; Lin, Y. C.; Cheng, M. C.;
Wang, Y. J . Chem. Soc., Dalton Trans. 1995, 1305.
(9) (a) Kunze, U.; J awad, H.; Burghardt, R.; Tittmann, R.; Kruppa,
V. J . Organomet. Chem. 1986, 302, C30. (b) Antoniadis, A.; Kunze,
U.; Moll, M. J . Organomet. Chem. 1982, 235, 177. (c) Ambrosius, H.
P. M. M.; Bosman, W. P.; Cras, J . A. J . Organomet. Chem. 1981, 215,
201.
S0276-7333(97)00418-4 CCC: $15.00 © 1998 American Chemical Society
Publication on Web 01/13/1998

514 Organometallics, Vol. 17, No. 4, 1998
Yih et al.
Sch em e 1
bidentate fashion through the P and S atoms. The IR
spectrum of 3a in the νCO region displays four bands
characteristic of a cis-M(CO)4L2 group. The 31P NMR
88% yield. The 31P NMR spectrum of 5 (δ 38.72 with
1J W-P ) 247.4 Hz) is similar to that of 4. The reaction
of 2a with ICH2CONH2 affords the analogous complex
W(CO)5PPh2C(dNPh)SCH2CONH2 (6) in high yield.
The same procedure was used to prepare W(CO)5PPh2-
C(dNPh)SCH2CHdCH2 (7) and W(CO)5PPh2C(dNPh)-
SCH2CO2Me (8), both in high yield. In the reactions of
2a with various acyl halides, both S-acylation and
N-acylation are observed.10
P r oton -In d u ced Cycliza tion . We previously re-
ported spontaneous intermolecular cycloaddition7 of
W(CO)5PPh2C(dS)SCH2CtCH (9) leading to dimeriza-
tion. In the presence of Et3N or PhCH2NH2, a different
type of dimerization of 9 yields a dinuclear complex of
6a-thiathiophthene.8 However, unlike 9, complex 4, by
itself or in the presence of an amine, is stable. Proton-
ation of 4 by HBF4 in n-hexane at room temperature
1
resonance of 3a appears at δ 14.89 with J W-P ) 189.6
Hz, shifted from δ 34.3 for 2a . The different chemical
shifts reflect the dissimilar bonding modes of the
phosphine ligand. The bonding of the chelating phos-
phine ligand in 3a is analogous to that reported by
Kunze and co-workers9 and is responsible for the
inactive nature of 3a . In comparison, the monodentate
P-coordinated bonding mode of the PPh2C(dNPh)S-
ligand in 2a results in this complex being much more
reactive.
Surprisingly, the reaction of 1 with EtOC(O)NdCdS
yields directly the decarbonylation product [Et4N]W-
(CO)4[η2-PPh2C(dNCO2Et)S] (3b), possibly due to higher
photosensitivity or thermal reactivity of its precursor
2b. The 31P NMR spectrum of the phosphine ligand in
3b has a resonance at δ 16.36 (1J W-P ) 193.8 Hz).
The alkylation reaction of 2a with alkyl halides leads
to formation of a S-C bond. Thus, the reaction of 2a
with BrCH2CtCH affords the neutral complex W(CO)5-
PPh2C(dNPh)SCH2CtCH (4) in 84% yield. In the FAB
mass spectrum of 4, the parent peaks as well as the
peaks due to fragmentation are in agreement with the
molecular formula. The IR spectrum of 4 shows two
results in formation of W(CO)5PPh2[CSCH2C(CH2)NPh]-
1
BF4 (10) (see Scheme 1). The H NMR spectrum of 10
has a resonance at δ 5.11 assignable to the S-bonded
methylene and a pair of resonances at δ 4.68 and 5.65
assignable to the terminal methylene protons. The 13C
NMR signal of the S-bonded methylene is at δ 74.06,
while that of the terminal methylene carbon is masked
by the aromatic carbon atoms.
Similarly, protonation of 5 by HBF4 results in the
formation of the cationic cyclic complex [W(CO)5PPh2-
terminal carbonyl stretchings at 2073 and 1934 cm-1
.
The higher frequencies compared to those of 2a indicate
that 4 is a neutral complex. The 31P NMR spectrum of
4 has a resonance at δ 38.03 with a pair of tungsten
satellites (1J W-P ) 246.8 Hz), similar to that of 2a ,
indicating monodentate phosphorus coordination. In
the 1H NMR spectrum of 4, a doublet resonance at δ
CSCHC(NH2)NPh]BF4 (11), which contains a (thia-
zoliumyl)diphenylphosphine ligand. In this reaction the
proton-induced cyclization is also accompanied by a 1,3-
hydrogen shift. In the 1H NMR spectrum of 11 the
methyne proton appears at δ 6.22. Protonation of 6
induces a similar cyclization with loss of a NH2 group
4
2.88 and a triplet resonance at δ 2.04 with J H-H ) 1.80
Hz are assigned to the S-methylene and terminal
methyne protons of the propargyl group, respectively.
In the 13C NMR spectrum the corresponding 13C reso-
nances appear at δ 21.6 and 72.8, respectively.
The synthetic methodology described above is ap-
plicable to primary organic halides with various sub-
stituents. Thus, the reaction of 2a with ICH2CtN in
CH2Cl2 affords W(CO)5PPh2C(dNPh)SCH2CtN (5) in
to yield W(CO)5PPh2CSCHC(OBF3)NPh (12). In 12, the
BF3 group acts as a Lewis acid and bonds to the oxygen
atom of the enol group. Under similar reaction condi-
tions complexes 7 and 8 are inert and no cyclization was
observed.
(10) Yeh, S. C.; Yih, K. H.; Lin, Y. C.; Cheng, M. X.; Wang, Y.
Manuscript in preparation.

Tungsten Complexes with Thiazolium Ligands
Organometallics, Vol. 17, No. 4, 1998 515
less than 0.006(5) Å. The C(7)-C(8) (1.353(5) Å)
distance is in the range of a regular aromatic C-C bond,
confirming the presence of an enol unit (which is
stabilized by a BF3 group attached to the oxygen atom).
The BF3 unit attached to an enol group has been
observed in several diiron complexes.11 The bond
distances C(6)-S (1.669(3) Å) and C(6)-N (1.353(4) Å)
in 12 are comparable to the corresponding bond dis-
tances of 10, but the other C(8)-S (1.691(4) Å) distance
is much shorter than the corresponding C(7)-S (1.808-
(11) Å) in 10. The thioazolium ring in 12 differs from
the thiazole in 10 by protonation at C(7) in the latter.
A few thiazolium complexes are known,12 but their
preparations do not involve protonation of a precursor.
Formation of the intramolecular cyclization product 10
is believed to proceed via protonation at the terminal
carbon of 4 to afford a cationic complex, followed by
nucleophilic attack of the nitrogen atom of the PhNCS
group at the center carbon of the propargyl unit to form
the cationic thiazolium ring. In the reaction of 5 with
acid, protonation very likely takes place at the nitrogen
atom of the nitrile group, and the cyclization is followed
by a 1,3-hydrogen shift, giving complex 11. In the
process of forming 12, the cyclization is accompanied
by loss of the amine group and is further assisted by
addition of a BF3 group to the oxygen atom.
F igu r e 1. ORTEP drawing for the cation of W(CO)5-
[PPh2CSCH2C(CH2)NPh][BF4] (10).
Treatment of 11 with n-Bu4NF at room temperature
affords W(CO)5PPh2F. The 31P NMR spectrum of this
product shows a doublet resonance at δ 171.37 with
J W-P ) 148.4 and J F-P ) 862.2 Hz, indicating P-
coordination of the PPh2F ligand. Interestingly, treat-
ment of analogous species 10 and 12 with n-Bu4NF gave
no reaction under the same reaction conditions.
In conclusion, the facile synthesis of the PPh2C-
(dNPh)SR ligand coordinated to a tungsten pentacar-
bonyl group is reported. For R ) propargyl, CH2CN,
and CH2CONH2, the organic part attached to the
diphenylphosphine unit is converted to the thiazolium
group by strong acid.
F igu r e 2. ORTEP drawing for W(CO)5[PPh2CSCHC-
(OBF3)NPh] (12).
Exp er im en ta l Section
Since the spectroscopic data of the thiazoliumylphos-
phine complexes are not sufficient for establishment of
their structure, single crystals of 10 and 12 were grown
and the structures determined by X-ray diffraction
analysis. ORTEP drawings are shown in Figures 1 and
2 for 10 and 12, respectively. The coordination geom-
etry around the tungsten metal center in 10 is pseu-
dooctahedral. The phosphine ligand with a thioazolium
group is coordinated to the tungsten metal center
through the phosphorus atom. In the five-membered
ring of 10, delocalization occurs only between the
S-C-N atoms, as indicated by the bond distances
C(6)-S (1.700(9) Å) and C(6)-N (1.312(11) Å), which
show partial double-bond character, and the C(7)-C(8)
bond distance (1.50(1) Å), which is close to a normal
C-C single bond. It is thus not unexpected that the
five atoms of the thiazolium ring are not planar.
Deviations from the average plane are in the range of
0.12(1) to -0.11(1) Å. The dihedral angle between the
planes S-C(6)-N and S-C(7)-C(8) is 12.6(9)°. The
bond length C(8)-C(9) (1.307(15) Å) is normal for a C-C
double bond.
Gen er a l P r oced u r es. All manipulations were performed
under nitrogen using vacuum-line, drybox, and standard
Schlenk techniques. CH3CN and CH2Cl2 were distilled from
CaH2 and diethyl ether and THF from Na/ketyl. All other
solvents and reagents were of reagent grade and were used
without further purification. NMR spectra were recorded on
the Bruker AC-200 and AM-300WB FT-NMR spectrometers
at room temperature (unless stated otherwise) and are re-
ported in units of δ with residual protons in the solvent as an
internal standard (CDCl3, δ 7.24; CD3CN, δ 1.93; C2D6CO, δ
2.04). FAB mass spectra were recorded on a J EOL SX-102A
spectrometer. Elemental analyses and X-ray diffraction stud-
ies were carried out at the Regional Center of Analytical
Instrumentation located at the National Taiwan University.
W(CO)6 and PPh2H were purchased from Strem Chemical,
PhNCS, ICH2CN, BrCH2CHdCH2, ICH2CONH2, and BrCH2-
CO2Me were purchased from Merck, and propargyl bromide,
purchased also from Merck, was distilled before use. W(CO)5-
(PPh2H) (1a ) was prepared according to a literature method.8a
(11) Snead, T. E.; Mirkin, C. A.; Lu, K. L.; Nguyen, S. T.; Feng, W.
C.; Beckman, H. L.; Geoffroy, G. L.; Rheingold, A. L.; Haggerty, B. S.
Organometallics 1992, 11, 2613.
(12) (a) Moore, S. S.; Whitesides, G. M. J . Org. Chem. 1982, 47, 1489.
(b) Al-Dulaymmi, M. F.; Hills, A.; Hitchcock, P. B.; Hughes, D. L.;
Richards, R. J . Chem. Soc., Dalton Trans. 1992, 241.
In 12 the five-membered thiazolium ring is planar.
The deviations from the average plane for all atoms are

516 Organometallics, Vol. 17, No. 4, 1998
Yih et al.
P r ep a r a tion of 2a . A solution of 1a (0.61 g, 1.20 mmol)
in diethyl ether (20 mL) was treated with n-BuLi (1.6 M, 0.80
mL, 1.28 mmol) at 0 °C, and the mixture was stirred for 5
min and slowly warmed to room temperature. To the mixture
was added 0.15 mL of PhNCS (1.30 mmol), and the solution
was stirred for 10 min. Addition of a solution of tetraethyl-
ammonium bromide (0.32 g, 1.52 mmol in 10 mL of methanol)
to the mixture caused formation of a yellow precipitate, which
was filtered, with 2 × 10 mL of hexane, and then dried under
vacuum to give [Et4N][W(CO)5PPh2C(dNPh)S] (2a ; 0.79 g, 85%
yield). Spectroscopic data for 2a are as follows. IR (THF):
at room temperature, the solution was stirred for 10 min, and
then the solvent was removed under vacuum. The residue was
extracted with 2 × 20 mL of diethyl ether. After filtration,
the volume of the solution was reduced to about 8 mL and the
solution was stored at -20 °C to yield a crystalline solid, which
was filtered and dried under vacuum to give W(CO)5PPh2C-
(dNPh)SCH2CONH2 (6; 0.57 g, 80% yield). Spectroscopic data
for 6 are as follows. IR (KBr): 2070 (s), 1934 (vs) cm-1 31P
.
NMR (CDCl3): δ 38.0 (J W-P ) 244.6 Hz). 1H NMR (CDCl3):
δ 2.98 (s, 2H, SCH2), 5.33 (br, 1H, NH2), 5.52 (br, 1H, NH2),
6.97-7.74 (m, 15H, Ph). 13C NMR (CDCl3): δ 36.0 (d, SCH2,
3
2062 (m), 1963 (w), 1919 (vs). 31P NMR (CDCl3): δ 34.3 (J W-P
3J P-C ) 1.9 Hz), 119.0 (s), 125.4 (s), 128.7 (d, J P-C ) 9.8 Hz),
3
2
) 238.9 Hz). 1H NMR (CDCl3): δ 1.15 (tt, 12H, CH3, J N-H
)
129.5 (s), 131.0 (s), 132.9 (d, J P-C ) 40.6 Hz), 133.6 (d, J P-C
3
1.7, J H-H ) 7.4 Hz), 3.08 (q, 8H, CH2, J H-H ) 7.4 Hz), 6.85-
) 11.7 Hz), 147.3 (d, J P-C ) 15.5 Hz), 163.1 (d, CS, J P-C
)
7.77 (m, 15H, Ph). 13C NMR (CDCl3): δ 7.3 (CH3), 52.2 (CH2),
45.0 Hz), 168.5 (s, CO), 196.6 (d, cis-CO, 2J P-C ) 6.6 Hz), 198.7
3
2
121.3 (s), 122.3 (s), 127.4 (d, J P-C ) 8.7 Hz), 128.8 (s), 129.8
(d, trans-CO, J P-C ) 24.0 Hz). MS: m/ z 702 (M+), 674 (M+
2
(s), 134.0 (d, J P-C ) 9.8 Hz), 134.9 (s), 139.0 (d, J P-C ) 35.7
- CO), 646 (M+ - 2CO), 618 (M+ - 3CO), 590 (M+ - 4CO),
562 (M+ - 5CO), 504 (M+ - 5CO - CH2CONH2). Anal. Calcd
for C26H19N2O6PSW: C, 44.46; N, 3.99; H, 2.73. Found: C,
45.21; N, 4.16; H, 3.02. W(CO)5PPh2C(dNPh)SCH2CtCH (4),
W(CO)5PPh2C(dNPh)SCH2CtN (5), W(CO)5PPh2C(dNPh)-
SCH2CHdCH2 (7), and W(CO)5PPh2C(dNPh)SCH2CO2Me (8)
were synthesized using the same procedure as that used in
the synthesis of 6 by employing 2a and the corresponding
halides BrCH2CtCH, ICH2CtN, BrCH2CHdCH2, and BrCH2-
CO2Me, respectively. The yields are 84%, 88%, 86%, and 75%
for 4, 5, 7, and 8, respectively.
2
Hz), 190.3 (d, CS, J P-C ) 29.3 Hz), 198.8 (dd, cis-CO, J P-C
)
2
6.8, J W-C ) 123.8 Hz), 201.9 (d, trans-CO, J P-C ) 22.5 Hz).
MS: m/ z 774 (M+ + Et4N), 611 (M+ + Et4N - CO - PhNCS).
Anal. Calcd for C32H35O5N2PSW: C, 49.62; N, 3.62; H, 4.56.
Found: C, 49.54; N, 3.54; H, 4.23.
P h otod eca r bon yla tion of 2a . Complex 2a (0.14 g, 0.18
mmol) was dissolved in 10 mL of benzene, and the solution
was photolyzed by UV radiation for 5 min at room tempera-
ture. The solvent was removed under vacuum, and the
product was redissolved in 10 mL of CH2Cl2/hexane (1/2). The
mixture was stored at -20 °C for 12 h to give the yellow
crystalline product [Et4N]W(CO)4[η2-PPh2C(dNPh)S] (3a ; 0.09
g, 68% yield). Spectroscopic data for 3a are as follows. IR
Spectroscopic data for 4 are as follows. IR (CH2Cl2): 2073
(m), 1934 (vs) cm-1
.
31P NMR (CDCl3): δ 38.03 (J W-P ) 246.8
Hz). 1H NMR (CDCl3): δ 2.04 (t, 1H, CH, J H-H ) 1.80 Hz),
2.88 (d, 2H, S-CH2, 4J H-H ) 1.80 Hz), 7.04-7.74 (m, 15H, Ph).
13C NMR (CDCl3): δ 1.64 (S-CH2), 72.82 (tCH), 77.82
(CtCH), 118.92 (s), 125.1 (s), 128.52 (d, 3J P-C ) 7.5 Hz), 129.21
4
(THF): 1987 (m), 1919 (m), 1871 (vs), 1819 (s) cm-1 31P NMR
.
(CD3CN): δ 14.89 (J W-P ) 189.61 Hz). 1H NMR (CD3CN): δ
1.18 (tt, 12H, CH3, 3J N-H ) 1.93 Hz, 3J H-H ) 7.23 Hz), 3.12 (q,
2
3
8H, CH2, J H-H ) 7.25), 7.01-7.88 (m, 15H, Ph). 13C NMR
(s), 132.8 (s), 133.66 (d, J P-C ) 11.3 Hz), 132.84 (s), 147.73
(d, J P-C ) 18.0 Hz), 162.92 (d, CS, J P-C ) 51.2 Hz), 196.70
(CD3CN): δ 7.7 (s, CH3), 53.0 (s, CH2), 122.5 (s), 124.4 (s), 129.2
2
3
(dd, cis-CO, J P-C ) 7.5, J W-C ) 127.5 Hz), 199.12 (d, trans-
(d, J P-C ) 9.1 Hz), 129.5 (s), 131.0 (s), 135.8 (d, J P-C ) 26.0
2
CO, J P-C ) 24.0 Hz). MS: m/ z 683 (M+), 655 (M+ - CO).
2
3
Hz), 133.9 (d, J P-C ) 12.3 Hz), 150.4 (d, J P-C ) 16.9 Hz),
2
Anal. Calcd for C27H18NO5PSW: C, 47.46; N, 2.05; H, 2.66.
Found: C, 48.22; N, 2.31; H, 2.94.
189.2 (d, CS, J P-C ) 42.8 Hz), 205.7 (d, 2C, cis-CO, J P-C
)
2
7.3 Hz), 213.5 (d, 1C, cis-CO, J P-C ) 7.3 Hz), 215.8 (d, trans-
CO, J P-C ) 29.1 Hz). MS: m/ z 876 (M+ + Et4N), 848 (M+
+
2
Spectroscopic data for 5 are as follows. IR (CH2Cl2): 2073
(m), 1936 (vs) cm-1 31P NMR (CDCl3): δ 38.72 (J W-P ) 247.4
.
Et4N - CO). Anal. Calcd for C31H35O4N2PSW: C, 49.88; N,
3.75; H, 4.73. Found: C, 49.77; N, 3.71; H, 5.01.
Hz). 1H NMR (CDCl3): δ 2.97 (s, 2H, CH2), 7.04-7.74 (m, 15H,
Ph). 13C NMR (CDCl3): δ 17.81 (CH2), 114.6 (CN), 118.86 (s),
P r ep a r a tion of 3b. A solution of W(CO)5(PPh2H) (1a ; 0.61
g, 1.20 mmol) in diethyl ether (20 mL) was treated with n-BuLi
(1.6 M, 0.80 mL, 1.28 mmol) at 0 °C, and the mixture was
stirred for 5 min and slowly warmed to room temperature. To
the mixture was added 0.17 mL of EtOC(O)NCS (1.45 mmol),
and the solution was stirred for 10 min. Addition of a solution
of tetraethylammonium bromide (0.32 g, 1.52 mmol in 10 mL
of methanol) to the mixture caused formation of a yellow
precipitate, which was filtered and washed with 2 × 10 mL of
hexane to give [Et4N]W(CO)4[η2-PPh2C(dNCO2Et)S] (3b) (0.42
g, 47% yield). Single crystals of 3b can be obtained by
recrystallization from a mixture of 1/1 CH2Cl2/hexane. Spec-
troscopic data for 3b are as follows. IR (CH2Cl2): 2003 (m),
3
125.76 (s), 128.77 (d, J P-C ) 9.8 Hz), 129.59 (s), 131.19 (s),
2
133.59 (d, J P-C ) 8.3 Hz), 134.92 (s), 146.72 (d, J P-C ) 15.0
Hz), 160.92 (d, CS, J P-C ) 48.5 Hz), 196.43 (d, cis-CO, 2J P-C
)
2
6.8 Hz), 198.50 (d, trans-CO, J P-C ) 24.8 Hz). MS: m/ z 684
(M+), 656 (M+ - CO), 544 (M+ - 5CO). Anal. Calcd for C26
17N2O5PSW: C, 45.63; N, 4.09; H, 2.50. Found: C, 45.92;
N, 4.11; H, 2.97.
Spectroscopic data for 7 are as follows. IR (CH3CN): 2072
(m), 1931 (vs) cm-1 31P NMR (CDCl3): δ 39.13 (J W-P ) 244.4
-
H
.
Hz). 1H NMR (CDCl3): δ 2.87 (d, 2H, SCH2, J H-H ) 6.8 Hz),
4.76 (dd, 1H, dCH, J H-H ) 16.9, 1.2 Hz), 4.83 (d, 1H, dCH,
J H-H ) 9.5 Hz), 5.22 (m, 1H, dCH), 7.07-7.76 (m, 15H, Ph).
MS: m/ z 685 (M+), 657 (M+ - CO), 601 (M+ - 3CO), 573 (M+
- 4CO), 545 (M+ - 5CO), 504 (M+ - 5CO - C3H5). Anal. Calcd
for C27H20O5NPSW: C, 47.32; N, 2.04; H, 2.94. Found: C,
48.01; N, 2.25; H, 3.11.
1993 (m), 1877 (vs), 1817 (s) cm-1 31P NMR (CDCl3): δ 16.4
.
(J W-P ) 193.8 Hz). 1H NMR (CDCl3): δ 1.22 (tt, 12H, CH3,
3
3
3J N-H ) 1.8, J H-H ) 7.3 Hz), 1.29 (t, 3H, CH3, J H-H ) 7.3
Hz), 3.18 (q, 8H, CH2, 3J H-H ) 7.3 Hz), 4.16 (q, 2H, CH2, 3J H-H
) 7.3 Hz), 7.35-7.78 (m, 10H, Ph). 13C NMR (CDCl3): δ 7.6
(s, NCH2CH3), 14.6 (s, OCH2CH3), 52.6 (t, NCH2, J N-C ) 2.8
Spectroscopic data for 8 are as follows. IR (CH3CN): 2073
(m), 1935 (vs) cm-1 31P NMR (CDCl3): δ 38.17 (J W-P ) 248.8
.
3
Hz). 1H NMR (CDCl3): δ 3.07 (s, 2H, SCH2), 3.48 (s, 3H, CH3),
6.97-7.75 (m, 15H, Ph). MS: m/ z 717 (M+), 689 (M+ - CO),
633 (M+ - 3CO), 605 (M+ - 4CO), 532 (M+ - 4CO - CH2-
CO2CH3). Anal. Calcd for C27H20O7NPSW: C, 45.21; N, 1.95;
H, 2.81. Found: C, 45.79; N, 2.15; H, 2.99.
Hz), 62.1 (s, OCH2), 128.3 (d, J P-C ) 9.1 Hz), 130.1 (s), 133.5
2
(d, J P-C ) 26.8 Hz), 133.2 (d, J P-C ) 13.2 Hz), 197.6 (d, CS,
2
J P-C ) 32.9 Hz), 204.5 (d, 2C, cis-CO, J P-C ) 7.3 Hz), 212.3
2
2
(d, 1C, cis-CO, J P-C ) 7.8 Hz), 214.9 (d, trans-CO, J P-C
)
29.6 Hz). MS: m/ z 872 (M+ + 2Et4N), 844 (M+ + 2Et4N -
CO), 816 (M+ + 2Et4N - 2CO). Anal. Calcd for C28H35O6N2-
PSW: C, 45.29; N, 3.77; H, 4.75. Found: C, 46.79; N, 4.01;
H, 4.51.
P r oton a tion of 4. To a solution of complex 4 (0.79 g, 1.16
mmol) in 10 mL of hexane was slowly added HBF4 (0.25 mL
of a 54% solution in ether, 1.23 mmol) at 0 °C. The mixture
was stirred for 5 min at 0 °C and slowly warmed to room
temperature. A precipitate formed, which was filtered and
P r ep a r a tion of 6. To a solution of 2a (0.79 g, 1.02 mmol)
in CH3CN (40 mL) was added ICH2CONH2 (0.20 g, 1.10 mmol)

Tungsten Complexes with Thiazolium Ligands
Organometallics, Vol. 17, No. 4, 1998 517
Ta ble 1. Cr ysta l a n d In ten sity Collection Da ta for
W(CO)5[P P h 2CSCH2C(CH2)NP h ]BF 4 (10) a n d
W(CO)5[P P h 2CSCHC(OBF 3)NP h ] (12)
Ta ble 2. Selected In ter a tom ic Dista n ces (Å) a n d
Bon d An gles (d eg) of th e
W(CO)5[P P h 2CSCH2C(CH2)NP h ] Ca tion a n d
W(CO)5[P P h 2CSCHC(OBF 3)NP h ] (12)a
mol formula
C27H19O5NSPWBF4 C27H18O6NSCl2PWBF3
(10)
(12)a
cation of 10
12
space group
a, Å
b, Å
P1h
P1h
8.905(5)
10.437(4)
17.044(4)
85.84(3)
83.32(4)
83.78(4)
1419.2(11)
2
9.3967(10)
10.6208(13)
16.7676(12)
76.979(8)
86.792(7)
72.73(9)
1556.8(3)
2
W-P
2.532(3)
W-P
2.5185(10)
2.047(4)
2.077(5)
1.982(4)
2.040(4)
2.024(4)
1.842(3)
1.825(3)
1.827(4)
1.669(3)
1.691(4)
1.353(4)
1.399(4)
1.456(4)
1.131(5)
1.120(6)
1.154(5)
1.137(5)
1.144(5)
1.353(5)
1.304(4)
1.500(5)
1.377(5)
1.369(5)
1.367(5)
W-C(1)
W-C(2)
W-C(3)
W-C(4)
W-C(5)
P-C(6)
P-C(16)
P-C(22)
S-C(6)
S-C(7)
1.999(11)
1.998(10)
1.995(11)
2.034(12)
2.000(10)
1.860(10)
1.830(9)
W-C(1)
W-C(2)
W-C(3)
W-C(4)
W-C(5)
P-C(6)
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
P-C(15)
P-C(21)
S-C(6)
1.829(9)
1.700(9)
cryst dimens, mm 0.10 × 0.40 × 0.45 0.30 × 0.30 × 0.40
radiation
Mo KR, λ ) 0.7107 Å
1.808(11)
1.163(14)
1.165(13)
1.129(13)
1.131(15)
1.155(12)
1.312(11)
1.497(14)
1.307(15)
1.448(12)
1.455(11)
S-C(8)
2θ range, deg
scan type
total no. of rflns
no. of unique rflns, 4162
I > 2σ(I)
R, Rw (I > 2σ(I))
R, Rw (all data)
2-50
θ/2θ
5458
4839
C(1)-O(1)
C(2)-O(2)
C(3)-O(3)
C(4)-O(4)
C(5)-O(5)
C(6)-N
N-C(6)
N-C(7)
N-C(9)
C(1)-O(1)
C(2)-O(2)
C(3)-O(3)
C(4)-O(4)
C(5)-O(5)
C(7)-C(8)
C(7)-O
B-O
4999
0.053, 0.055
0.068, 0.056
0.023, 0.018
0.029, 0.018
C(7)-C(8)
C(8)-C(9)
C(8)-N
a
The lattice of single crystals of 12 contains solvated CH2Cl2
molecules.
C(10)-N
washed with 2 × 20 mL of hexane to give the crude product,
which was further purified by recrystallization from CH2Cl2/
B-F(2)
B-F(3)
hexane (2/1) to give W(CO)5PPh2[CSCH2C(CH2)NPh]BF4 (10;
0.58 g, 65%). Spectroscopic data for 10 are as follows. IR (CH2-
B-F(4)
P-W-C(1)
89.6(3)
93.1(3)
175.8(4)
94.0(3)
89.1(3)
P-W-C(1)
P-W-C(2)
P-W-C(3)
P-W-C(4)
P-W-C(5)
W-P-C(6)
W-P-C(15)
W-P-C(21)
C(6)-P-C(15)
C(6)-P-C(21)
C(15)-P-C(21)
C(6)-S-C(8)
C(6)-N-C(7)
C(6)-N-C(9)
C(7)-N-C(9)
P-C(6)-S
P-C(6)-N
S-C(6)-N
N-C(7)-C(8)
N-C(7)-O
C(8)-C(7)-O
S-C(8)-C(7)
O-B-F(2)
O-B-F(3)
O-B-F(4)
88.02(11)
90.44(12)
175.89(13)
96.00(11)
92.93(12)
114.43(11)
112.31(11)
115.10(12)
104.36(15)
101.64(15)
107.94(16)
93.67(17)
113.6(3)
125.9(3)
120.4(3)
118.40(20)
131.27(24)
110.20(23)
112.1(3)
115.9(3)
131.9(3)
110.4(3)
110.8(3)
104.9(3)
108.6(3)
111.6(3)
109.2(4)
Cl2): 2077 (m), 1941 (s) cm-1
.
31P NMR (C2D6CO): δ 41.42
P-W-C(2)
(J W-P ) 254.2 Hz). 1H NMR (C2D6CO): δ 4.68 (m, 1H, dCH2),
5.11 (m, 2H, CH2), 5.65 (m, 1H, dCH2), 6.93-7.53 (m, 15H,
Ph). 13C NMR (C2D6CO): δ 74.06 (CH2), 118-135 (m, Ph),
163.45 (d, CS, J P-C ) 25.2 Hz), 196.02 (br, cis-CO), 196.81 (d,
P-W-C(3)
P-W-C(4)
P-W-C(5)
W-P-C(6)
105.3(3)
120.3(3)
118.0(3)
108.5(4)
100.6(4)
102.2(4)
92.4(5)
115.7(5)
128.9(7)
114.7(7)
105.9(7)
126.7(10)
109.8(8)
123.4(9)
114.9(7)
127.0(8)
118.0(7)
2
trans-CO, J P-C ) 7.5 Hz). MS: m/ z 684 (M+ - BF4), 628
W-P-C(16)
W-P-C(22)
C(6)-P-C(16)
C(6)-P-C(22)
C(16)-P-C(22)
C(6)-S-C(7)
P-C(6)-S
(M+ - BF4 - 2CO). Anal. Calcd for C27H19BF4NO5PSW: C,
42.05; N, 3.63; H, 2.48. Found: C, 41.77; N, 3.53; H, 3.10.
Protonation of 5 (0.92 g, 1.34 mmol) was similarly carried
out in hexane to give [W(CO)5PPh2CSCHC(NH2)NPh]BF4 (11;
0.67 g) in 65% yield. Spectroscopic data for 11 are as follows.
P-C(6)-N
S-C(6)-N
IR (CH2Cl2): 2079 (m), 1941 (vs) cm-1
.
31P NMR (C2D6CO):
δ 18.89 (J W-P ) 256.5 Hz). 1H NMR (C2D6CO): δ 6.02 (br,
NH2), 6.22 (br, 1H, CH), 6.85-7.60 (m, 15H, Ph). 13C NMR
(C2D6CO): δ 102.67 (d, dC, 3J P-C ) 5.5 Hz), 127-133 (m, Ph),
158.76 (s, CNH2), 160.88 (br, CS), 196.91 (br, cis-CO), 198.56
S-C(7)-C(8)
C(7)-C(8)-C(9)
C(7)-C(8)-N
C(9)-C(8)-N
C(6)-N-C(8)
C(6)-N-C(10)
C(8)-N-C(10)
(d, trans-CO, J P-C ) 32.0 Hz). MS: m/ z 685 (M+ - BF4),
2
601 (M+ - BF4 - 3CO), 573 (M+ - BF4 - 4CO), 545 (M+
-
BF4 - 5CO). Anal. Calcd for C26H18BF4N2O5PSW: C, 40.44;
H, 2.35. Found: C, 40.71; H, 2.83.
P r oton a tion of 6. An aliquot of HBF4 (0.22 mL, 1.10
mmol) was added at room temperature to complex 6 (0.70 g,
1.0 mmol) dissolved in 40 mL of diethyl ether. The solution
was stirred for 10 min, and then the solvent was removed
under vacuum. The residue was washed with 2 × 10 mL of
hexane, and the product was purified by recrystallization from
F(2)-B-F(3)
F(2)-B-F(4)
F(3)-B-F(4)
C(7)-O-B
111.6(4)
122.4(3)
a
Bond distances and angles of the three phenyl groups for both
complexes are listed in the Supporting Information.
CH2Cl2/hexane (2/1) to give W(CO)5PPh2CSCHC(OBF3)NPh
(12; 0.54 g, 72% yield). Spectroscopic data for 12 are as follows.
X-r a y An a lysis of 10 a n d 12. Single crystals of 10 suitable
for an X-ray diffraction study were grown as mentioned above.
A single crystal of dimensions 0.10 × 0.40 × 0.45 mm3 was
glued to a glass fiber and mounted on an Enraf-Nonius CAD4
diffactometer. Initial lattice parameters were determined from
a least-squares fit to 25 accurately centered reflections with
10.0° < 2θ < 25°. Cell constants and other pertinent data are
collected in the Supporting Information. Data were collected
using the θ/2θ scan method. The final scan speed for each
reflection was determined from the net intensity gathered
during an initial prescan and ranged from 2 to 7° min-1. The
scan angle was determined for each reflection according to the
equation 0.8 + 0.35 tan θ.
IR (KBr): 2076 (s), 1920 (vs), (CN) 1579 cm-1
.
31P NMR
(CDCl3): δ 23.47 (J W-P ) 261.7 Hz). 1H NMR (CDCl3): δ 7.26
(1H), 6.4-7.6 (m, 15H, Ph). 13C NMR (CDCl3): δ 101.1 (s, CH),
127.1 (s, m-C of Ph), 129.47 (s, p-C of Ph), 129.5 (d, m-C of Ph,
3J P-C ) 10.6 Hz), 130.9 (s, p-C of Ph), 132.0 (s, o-C of Ph), 130.4
2
(d, ipso C of Ph, J P-C ) 44.4 Hz), 131.7 (d, o-C of Ph, J P-C
)
12.9 Hz), 133.7 (s, ipso C of Ph), 159.1 (s, COB), 162.7 (s, PCN),
2
2
195.5 (d, cis-CO, J P-C ) 6.3 Hz), 196.7 (d, trans-CO, J P-C
)
25.9 Hz). 19F NMR (CDCl3): -154.70 (s), -154.76 (s). MS:
m/ z 773 (M+ + HF), 689 (M+ + HF - 3CO), 661 (M+ + HF -
4CO). Anal. Calcd for C26H16BNF3O6PSW: C, 41.46; N, 1.86;
H, 2.14. Found: C, 40.96; N, 1.88; H, 2.40.

518 Organometallics, Vol. 17, No. 4, 1998
Yih et al.
squares converged smoothly to values of R ) 0.053 and Rw
0.055. Crystal and intensity collection data are given in Table
1, while bond distances and angles are given in Table 2. Final
values of all refined atomic positional parameters (with esd’s)
and tables of thermal parameters are given in the Supporting
Information.
The procedures for 12 were similar. The final residuals of
the refinement were R ) 0.023 and Rw ) 0.018. Final values
of all refined atomic positional parameters (with esd’s) and
tables of thermal parameters are given in the Supporting
Information.
The raw intensity data were converted to structure factor
amplitudes and their esd’s by correction for scan speed,
background, Lorentz, and polarization effects. An empirical
correction for absorption, based on the azimuthal scan, was
appplied to the data set. Crystallgraphic computations were
carried out on a Microvax III computer using the NRCC
structure determination package.13 Merging of equivalent and
duplicate reflections gave a total of 4999 unique measured
data, from which 4162 were considered observed (I > 2.0σ(I)).
The structure was first solved by using the heavy-atom method
(Patterson synthesis), which revealed the position of the metal,
and then refined via standard least-squares and difference
Fourier techniques. The quantity minimized by the least-
squares program was w(|Fo| - |Fc|)2. The analytical forms of
the scattering factor tables for the neutral atoms were used.14
All other non-hydrogen atoms were refined by using anisotro-
pic thermal parameters. Hydrogen atoms were included in
the structure factor calculations in their expected positions on
the basis of idealized bonding geometry but were not refined
in least squares. Final refinement using full-matrix least
)
Ack n ow led gm en t. We wish to thank the National
Science Council of Taiwan, Republic of China, for
financial support.
Su p p or tin g In for m a tion Ava ila ble: Details of the struc-
tural determination for complexes 10 and 12, including tables
of crystal data and structure refinement, fractional coordi-
nates, anisotropic thermal parameters, and all bond distances
and angles (11 pages). Ordering information is given on any
current masthead page.
(13) Gabe, E. J .; Lee, F. L.; Lepage, Y. In Crystallographic Comput-
ing 3; Sheldrick, G. M., Kruger, C., Goddard, R., Eds.; Clarendon
Press: Oxford, England, 1985; p 167.
(14) International Tables for X-ray Crystallography; Reidel: Dor-
drecht, The Netherlands, 1974; Vol. IV.
OM970418E