Novel phosphine- and phosphite-induced imido migration to a cyclopentadienyl ring in an imido-bridged cobaltadithiolene complex

Article abstract of DOI:10.1021/om0207212

The mechanism of phosphine- and phosphite-induced migration of the imido group from sulfur to a Cp ring in a tosylimido-bridged cobaltadithiolene complex was investigated, and a probable intermediate was isolated and characterized. The presence of a large excess of PPh₃ causes the formation of the imido- and phosphine-substituted Cp complex.

Full text of DOI:10.1021/om0207212

Organometallics 2003, 22, 195-198
195
Notes
Novel P h osp h in e- a n d P h osp h ite-In d u ced Im id o
Migr a tion to a Cyclop en ta d ien yl Rin g in a n
Im id o-Br id ged Coba lta d ith iolen e Com p lex
Mitsushiro Nomura,† Chikako Takayama,† Gerardo C. J anairo,‡ Toru Sugiyama,†
Yasuo Yokoyama,† and Masatsugu Kajitani*,†
Department of Chemistry, Faculty of Science and Technology, Sophia University, 7-1, Kioi-cho,
Chiyoda-ku, Tokyo 102-8554, J apan, and Department of Chemistry, De La Salle University,
2401 Taft Avenue, 1104 Manila, Philippines
Received September 3, 2002
Sch em e 1
Summary: The mechanism of phosphine- and phosphite-
induced migration of the imido group from sulfur to a
Cp ring in a tosylimido-bridged cobaltadithiolene com-
plex was investigated, and a probable intermediate was
isolated and characterized. The presence of a large excess
of PPh3 causes the formation of the imido- and phos-
phine-substituted Cp complex.
Sch em e 2
In tr od u ction
The migrations of monodentate ligands from the
central transition metal to the Cp ring of η5-cyclopen-
tadienyl (Cp) complexes are well-known (Scheme 1).
This unique reaction is induced by a strong base. The
migrating ligands include acyl,1 alkoxycarbonyl,1d
formyl,1e,g acetylide,2 silyl,3 germyl,3k,4 stannyl,4b plum-
byl,4b hydride,5 and phosphorus ligands.6 In addition,
polysilane migration to the Cp ring with alkyl rearrange-
ment3f has been reported. The proposed mechanism of
these base-induced migrations involves the deprotona-
tion of the Cp ring by a strong base followed by the
migration of the ligand from the metal center to the Cp
ring. In addition, base-induced migration of silyl ligands
from iron to the η5-indenyl ligand has been also re-
ported.7 Quite recently, Esteruelas et al. reported other
migration reactions to the Cp ring (Scheme 2).8 The
reactions of [CpOs(H)(Cl)(EPh3)(PiPr3)] (E ) Si, Ge)
with LiCH2CN lead to EPh3 migration to the Cp ring
by EPh3(Os)/H(Cp) exchange. Furthermore, in this
cyclopentadienyl osmium(IV) chemistry, various ligand
migration reactions to the Cp ring have been observed
by ligand(Os)/H(Cp) exchange reaction (ligand ) Me,
n-Bu, s-Bu, NEt2, N(allyl)2, PPh2). An interesting mi-
gration reaction of the cyclopentadienyl rhodium car-
bene complex [CpRh(dCPh2)(PiPr3)] with PF3 has been
reported (Scheme 3). The carbene ligand underwent a
migratory insertion from the metal center into the C-H
bond of the Cp ring.9a A similar migratory insertion has
† Sophia University.
‡ De La Salle University.
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194. (b) Heah, P. H.; Gladysz, J . A. J . Am. Chem. Soc. 1984, 106, 7636.
(c) Abbott, S.; Baird, G. J .; Davies, S. G.; Dordor-Hedgecock, I. M.;
Maberly, T. R.; Walker, J . C.; Warner, P. J . Organomet. Chem. 1985,
289, C13. (d) Heah, P. C.; Patton, A. T.; Gladysz, J . A. J . Am. Chem.
Soc. 1986, 108, 1185. (e) Akita, M.; Kondoh, A. J . Organomet. Chem.
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Pannell, K. H.; Cervantes, J .; Parkanyi, L.; Cervantes-Lee, F. Orga-
nometallics 1990, 9, 859. (j) Sharma, S.; Cervantes, J .; Mata-Mata, J .
L.; Brun, M.-C.; Cervantes-Lee, F.; Pannell, K. H. Organometallics
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tallics 1992, 11, 3139.
(4) (a) Dean, W. K.; Graham, W. A. G. Inorg. Chem. 1977, 16, 1061.
(b) Cervantes, J .; Vicenti, S. P.; Kappor, R. N.; Pannell, K. H.
Organometallics 1989, 8, 744.
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tallics 2001, 20, 240.
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10.1021/om0207212 CCC: $25.00 © 2003 American Chemical Society
Publication on Web 12/05/2002

196 Organometallics, Vol. 22, No. 1, 2003
Notes
Sch em e 3
Sch em e 4
also been described in the reaction of the η5-indenyl
rhodium carbene complex [(C9H7)Rh(dCPh2)(PiPr3)]
with CO.9b
We have also reported the migration of an imido
group in the tosylimido-bridged cobaltadithiolene com-
plex [CpCo{S2C2(COOMe)2}(NTs)] (1). Complex 1 re-
acted with 2 equiv of PPh3 to give the amide-substituted
Cp complex [(C5H4NHTs)Co{S2C2(COOMe)2}] (3), in
which the tosylimido group was inserted into the C-H
of the Cp ring.10 This has been reported as the first
example of nitrogen migration to the Cp ring in orga-
nometallic complexes. An amide is a useful group,
because this group can be easily converted to other
nitrogen groups. Therefore, amide-substituted Cp com-
plexes are very important precursors of novel nitrogen-
substituted Cp complexes. Here we report on the
migration intermediate and plausible mechanism of the
reaction. Furthermore, we also describe an unexpected
formation of a disubstituted Cp complex in complex 1
when treated with a large excess of PPh3.
F igu r e 1. ORTEP drawing of 2b‚3H2O. Selected bond
lengths (Å): Co1-S1 2.230(4), Co1-S2 2.206(4), S1-C1
1.77(1), S2-C2 1.71(1), C1-C2 1.37(2), Co1-P1 2.144(4),
S1-N1 1.65(1). Selected bond angles (deg): S1-Co1-S2
90.8(2), Co1-S1-C1 102.6(5), Co1-S2-C2 102.9(5), S1-
C1-C2 117(1), S2-C2-C1 123(1), S1-Co1-P1 95.4(1),
Co1-S1-N1 112.2(4).
supported by an IR absorption band at 932 cm-1, which
corresponds to a S+-N- stretching vibration. The imido
group bonded to the sulfur atom and the phosphite
ligand is located at the same side of the cobaltadithio-
lene ring (Figure 1). This syn arrangement is contrary
to the corresponding alkylidene complex [CpCo{S2C2-
(COOMe)2}{C(COOMe)2}{P(OMe)3}], which was re-
ported to have the sulfonium ylide (S+-C-) in anti
form.12
This novel migration reaction may proceed by two
possible mechanisms: through either intramolecular
migration or intermolecular migration via a nitrene. To
exclude one of those possibilities, we performed the
reaction shown in Scheme 4 in the presence of cyclo-
hexene. If the migration of the imido group is intermo-
lecular, then the formation of the corresponding aziri-
dine and allylamine compounds due to addition and
C-H insertion, respectively, should be observed. How-
ever, no aziridine or allylamine could be detected. In
addition, a crossover experiment was performed as
illustrated in Scheme 5. In this experiment, a mixture
of the tosylimido-bridged complex having a methylated
Cp ligand [(C5H4-Me)Co{S2C2(COOMe)2}(NTs)] and the
mesylimido-bridged complex having the unsubstituted
Cp ligand [CpCo{S2C2(COOMe)2}(NMs)]10 was made to
react with PPh3. The only products were the intramo-
lecular migrated ones, and no crossover products were
found. These results suggest that the imido group
migration to the Cp ring is an intramolecular process.
The effect of a large excess of PPh3 in this migration
reaction was also investigated. Complex 1 was treated
Resu lts a n d Discu ssion
Complex 1 was prepared from [CpCo{S2C2(COOMe)2}]
using a procedure developed in our laboratory. The
reaction of complex 1 with 2 equiv of PPh3 in refluxing
benzene yielded complex 3. However, when the same
reaction is done at room temperature, it gives complex
2a .10 A similar migration reaction occurred in the
reaction of complex 1 with 5 equiv of P(OPh)3, forming
complex 2b at room temperature and complex 3 under
heating (refluxing benzene), respectively. When com-
plexes 2a and 2b were reacted under heating (refluxing
benzene), complex 3 was formed. Therefore, complexes
2a and 2b seem to be the intermediate of the imido
migration reaction (Scheme 4). It is supported that the
first attack is to the cobalt atom of phosphine or
phosphite as a nucleophile, and then the Co-N bond is
cleaved. Although spectroscopic and elemental analysis
data of complex 2a have already been reported,10 the
X-ray structure of complex 2a was not clear because
crystallization of complex 2a was difficult. However,
crystallization of analogous complex 2b was successful
in the presence of excess P(OPh)3. The ORTEP drawing
of complex 2b shows a sulfilimine structure (S+-N-).
The bond length of 1.65 Å between S1 and N1 is in close
agreement with a literature value of 1.636 Å for the S+-
N- bond length of Me2S+-N-Ts.11 This is further
(11) Cameron, A. F.; Hair, N. J .; Morris, D. C. J . Chem. Soc., Perkin
Trans. 2 1973, 1951.
(10) Nomura, M.; Yagisawa, T.; Takayama, C.; Sugiyama, T.;
Yokoyama, Y.; Shimizu, K.; Sugimori, A.; Kajitani, M. J . Organomet.
Chem. 2000, 611, 376.
(12) Takayama, C.; Takeuchi, K.; Ohkoshi, S.; J anairo, G. C.;
Sugiyama, T.; Kajitani, M.; Sugimori, A. Organometallics 1999, 18,
2843.

Notes
Organometallics, Vol. 22, No. 1, 2003 197
planar structure of the Cp ring of complex 4 (Figure 2),
it is concluded that the N1-C7(Cp) is a single bond. The
31P NMR spectrum of complex 4 (δ 23.4 ppm, singlet)
is similar to that of a typical phosphonium salt such as
PPh4+I- (δ 22.0). This suggests that a triphenylphos-
phonium-substituted Cp ligand is present in complex
4. This type of ligand is also observed from [(C5H4-P+-
Ph3)Rh(CO)2]15 and [(η5-Cp)Ru(µ2-η:5η5-C10H8)Ru(η5-
C5H4-P+Ph3)].16 In another reaction, complex 3 was
treated with PPh3. However, complex 4 was not ob-
tained. This result suggests that complex 4 is not formed
via intermediate 3. The formation mechanism of com-
plex 4 is currently under investigation.
Exp er im en ta l Section
All reactions were carried out under argon atmosphere by
means of standard Schlenk techniques. Solvents were dried
by known procedures and distilled before use. PPh3 and
P(OPh)3 were used without further treatment. Silica gel,
Wakogel C-300, was obtained from Wako Pure Chemical
Industries, Ltd. A thin-layer chromatography plate filled with
silica gel 60 (20 × 20 cm, 0.25 mm thick) was obtained from
Merck J apan Ltd. HPLC was model LC-908 produced by J apan
Analytical Industry Co. Mass and IR spectra were recorded
on a J EOL J MS-D300 and Shimadzu model FTIR 8600PC,
respectively. NMR spectra were measured with a J EOL LA500
spectrometer. UV-vis were recorded on Hitachi model UV-
2500PC. Elemental analyses were determined by using a
Shimadzu PE2400-II instrument. Melting points were mea-
sured by a Yanaco model micromelting point apparatus.
Rea ction of Com p lex 1 w ith P (OP h )3 a t Room Tem -
p er a tu r e. A solution of complex 1 (50 mg, 0.1 mmol) and
P(OPh)3 (131 µL, 0.5 mmol) in dichloromethane (10 mL) was
stirred at room temperature for 5 min. After the reaction,
hexane was added and the mixture was recrystallized at -30
°C. Product 2b was obtained as a brown crystalline solid in
80% yield.
F igu r e 2. ORTEP drawing of 4. Selected bond lengths
(Å): Co1-S1 2.124(8), Co1-S2 2.107(8), S1-C1 1.72(3),
S2-C2 1.74(2), C1-C2 1.37(3), P1-C11, 1.76(2), P1-C19,
1.78(3), N1-C7 1.32(3). Selected bond angles (deg): S1-
Co1-S2 90.7(3), Co1-S1-C1 105(1), Co1-S2-C2 107(1),
S1-C1-C2 120(2), S2-C2-C1 116(2), S3-N1-C7 121(1).
Sch em e 5
Rea ction of Com p lex 1 w ith P (OP h )3 u n d er Hea tin g.
A solution of complex 1 (50 mg, 0.1 mmol) and P(OPh)3 (131
µL, 0.5 mmol) in benzene (10 mL) was refluxed for 5 h. After
the solvent was removed under reduced pressure, the residue
was separated by thin-layer chromatography (silica gel 60,
eluent dichloromethane/ethyl acetate, 10:1). Product 3 was
obtained as a purple solid in 40% yield.
Sch em e 6
P r ep a r a tion of [(Me-C5H4)Co{S2C2(COOMe)2}(NTs)].
A solution of [(C5H4-Me)Co{S2C2(COOMe)2}] (344 mg, 1.0
mmol) and TsN3 (153 µL, 1.0 mmol) in benzene (10 mL) was
refluxed for 2 h. After the solvent was removed under reduced
pressure, the residue was separated by column chromatogra-
phy (silica gel 60, eluent n-hexane/ethyl acetate, 1:1). The
product was obtained as a dark green solid in 84% yield.
Cr ossover Exp er im en t. A solution of [(C5H4-Me)Co{S2C2-
(COOMe)2}(NTs)] (26 mg, 0.05 mmol), [CpCo{S2C2(COOMe)2}-
(NMs)] (21 mg, 0.05 mmol), and PPh3 (52 mg, 0.2 mmol) in
benzene (10 mL) was refluxed for 5 h. After the solvent was
removed under reduced pressure, the residue was separated
by thin-layer chromatography (silica gel 60, eluent dichlo-
romethane/ethyl acetate, 1:1). The products [(C5H3-Me-NHTs)-
Co{S2C2(COOMe)2}] (mixture of 1,2- and 1,3-substituted Cp
isomers) and [(C5H4-NHMs)Co{S2C2(COOMe)2}] were ob-
tained as a purple solid in 50% and 48% yield, respectively.
The mixture of 1,2- and 1,3-isomers of [(C5H3-Me-NHTs)Co-
{S2C2(COOMe)2}] was further separated by HPLC.
with 10 equiv of PPh3 in refluxing benzene. The reaction
yielded the disubstituted cyclopentadienyl complex
[(C5H3-NTs-PPh3)Co{S2C2(COOMe)2}] (4) in 17% yield
(Scheme 6). Complex 3 and the corresponding precursor
of complex 1, [CpCo{S2C2(COOMe)2}], were also formed
in 25% and 34% yields, respectively. X-ray diffraction
data reveal that complex 4 has the imido and the
phosphine group in the 1,2-position of the Cp ligand
(Figure 2). None of the 1,3-isomer was found.13 The bond
length of the P1-C11(Cp) was 1.76 Å, which was almost
the same as that of the P1-C19(Ph) (1.78 Å). Thus, the
P1-C11(Cp) is a single bond. The bond length of the
N1-C7(Cp) was 1.32 Å, which was shorter than the
N-C bond of the corresponding complex 3 (1.38 Å).10
However, its bond length was quite longer than that of
a typical N-C double bond (1.24 Å).14 According to the
Rea ction of Com p lex 1 w ith Excess P P h 3. A benzene
solution (30 mL) of complex 1 (50 mg, 0.1 mmol) was poured
(15) Tresoldi, G.; Recca, A. Finocchiaro, P.; Faraone, F. Inorg. Chem.
1981, 20, 3103.
(16) Watanabe, M.; Sato, M.; Takayama, T. Organometallics 1999,
18, 5201.
(13) NMR analysis of the reaction solution indicated only the
presence of the 1,2-isomer.
(14) Layer, R. W. Chem. Rev. 1963, 63, 489.

198 Organometallics, Vol. 22, No. 1, 2003
Notes
into a refluxed benzene (10 mL) solution of PPh3 (262 mg, 1.0
mmol), and then the reaction mixture was heated for 5 h under
refluxed benzene. After the solvent was removed under
reduced pressure, the residue was separated by thin-layer
chromatography (silica gel 60, eluent ethyl acetate), and then
the product was further separated by HPLC. Product 4 was
obtained as a blue crystalline solid in 17% yield.
13C NMR (125 MHz, CDCl3, vs TMS): δ 165.3, 158.3, 145.2,
130.5, 129.6, 127.4, 107.8, 86.9, 76.2, 73.5, 66.3, 52.8, 21.3, 10.5.
UV-vis (CH2Cl2): λmax (ꢀ) 574 (6600), 364 (3700), 297 (21000).
[(C5H3-Me-NHTs)Co{S2C2(COOMe)2}] (1,3-su bstitu t-
ed Cp isom er ). Mp: 224-225 °C (dec). Mass (EI+, 70 eV) m/z
(rel intensity): 513 (M+, 14.2), 371 ((NHTs-Me-C5H3)CoS2
,
+
3.3), 155 (Ts+, 19.9), 91 (C6H4Me+, 100). H NMR (500 MHz,
CDCl3, vs TMS): δ 7.37 (d, J ) 8.19, 2H, Ar), 6.98 (d, J )
8.19, 2H, Ar), 5.63 (s, 1H, Cp), 5.52 (t, J ) 2.17, 1H, Cp), 4.88
(t, J ) 2.17, 1H, Cp), 3.88 (s, 6H, OMe), 2.25 (s, 3H, Me), 1.88
(s, 3H, Me). 13C NMR (125 MHz, CDCl3, vs TMS): δ 165.3,
157.5, 145.0, 130.7, 129.5, 127.3, 108.5, 94.8, 73.8, 70.7, 67.7,
52.8, 21.3, 14.2. UV-vis (CH2Cl2): λmax (ꢀ) 577 (6300), 365
(3900), 296 (20000).
1
X-r a y Diffr a ction Stu d y. Measurements of complex 2b
and 4 were made on a Rigaku AFC 5S diffractometer with
graphite-monochromated Mo KR radiation. Each structure was
solved by direct methods and expanded Fourier techniques.
The non-hydrogen atoms were refined anisotropically. Com-
plexes 2b and 4 of idealized positions were used for the teXsan
crystallographic software package of Molecular Structure Corp.
[Cp Co{S2C2(COOMe)2}(NTs)(P (OP h )3)], 2b. Mp: 102-
104 °C (dec). Mass (FAB+, 70 eV): m/z 810 (M+ + 1), 500
[(C5H3-NTs-P P h 3)Co{S2C2(COOMe)2}], 4. Mp: 173-174
°C. Mass (FAB+, 70 eV): m/z 760 (M+ + 1). 1H NMR (500 MHz,
CDCl3, vs TMS): δ 7.58-7.90 (m, 15H, Ph), 7.41 (d, J ) 8.24
Hz, 2H, Ar), 6.94 (d, J ) 8.24 Hz, 2H, Ar), 6.24 (1H, Cp), 5.31
(1H, Cp), 4.83 (1H, Cp), 3.80 (s, 6H, OMe), 2.23 (s, 3H, Me).
13C NMR (125 MHz, CDCl3, vs TMS): δ 165.5, 154.0, 141.3,
138.6, 136.5, 134.82, 134.79, 134.73, 129.9, 129.8, 128.6, 126.5,
119.1, 118.3, 78.7, 78.6, 78.4, 78.3, 77.2, 67.0, 66.9, 58.6, 57.8,
52.6, 30.9. 31P NMR (200 MHz, CDCl3, vs 85% H3PO4): δ 23.4
(PPh3). UV-vis (CH2Cl2): λmax (ꢀ) 758 (1500), 586 (5900), 294
(23000). IR (KBr disk): 1705, 1489, 1236 cm-1. Anal. Calcd
for C37H33NO6PS3Cl2Co: C, 52.61; H, 3.94; N, 1.66. Found: C,
52.47; H, 3.84; N, 1.59.
Cr ysta l Da ta of 4 (C36H31NO6S3PCo): M ) 759.73, triclinic,
a ) 11.477(3) Å, b ) 16.066(3) Å, c ) 9.803(3) Å, R ) 95.70-
(2)°, â ) 96.72(2)°, γ ) 76.91(2)°, V ) 1743.6(8) Å3, T ) 296 K,
space group P1h(#2), Z ) 2, µ(Mo KR) ) 7.64 cm-1, 5639
reflections measured, 5317 unique (Rint ) 0.027), R(I >
3σ(I)) ) 0.070 and Rw ) 0.081.
1
(M+ - P(OPh)3 + 1). H NMR (500 MHz, CDCl3, vs TMS): δ
7.86 (d, J ) 8.24 Hz, 2H, Ar), 7.44 (d, J ) 8.24 Hz, 2H, Ar),
7.29-7.39 (m, 15H, OPh), 5.07 (s, 5H, Cp), 3.86 (s, 3H, OMe),
3.00 (s, 3H, OMe), 2.37 (s, 3H, Me). 31P NMR (200 MHz,
CDCl3): δ 126.6 (P(OPh)3). IR (KBr disk): 1732, 1691, 1252,
1182, 932 cm-1
.
Cr ysta l Da ta of 2b‚3H2O (C36H39NO12S3PCo): M ) 863.79,
triclinic, a ) 11.884(1) Å, b ) 16.359(2) Å, c ) 11.725(1) Å,
R ) 108.390(10)°, â ) 101.01(1)°, γ ) 69.427(9)°, V ) 2016.9-
(5) Å3, T ) 296 K, space group P1h(#2), Z ) 2, µ(Mo KR) ) 6.81
cm-1, 9716 reflections measured, 9272 unique (Rint ) 0.034),
R(I > 3σ(I)) ) 0.094 and Rw ) 0.127.
[(C5H4-Me)Co{S2C2(COOMe)2}(NTs)]. Mp: 180-181 °C.
Mass (EI+, 70 eV) m/z (rel intensity): 513 (M+, 2.0), 344
(M+ - NTs, 77.3), 202 ((C5H4-Me)CoS2+, 100), 138 ((C5H4-
Me)Co+, 18.4). 1H NMR (500 MHz, CDCl3, vs TMS): δ 7.73
(d, J ) 8.24 Hz, 2H, Ar), 7.22 (d, J ) 8.24 Hz, 2H, Ar), 5.83
(m, 1H, Cp), 5.70 (m, 2H, Cp), 5.19 (s, 1H, Cp), 3.80 (s, 3H,
OMe), 3.55 (s, 3H, OMe), 2.38 (s, 3H, Me), 2.13 (s, 3H, Me).
13C NMR (125 MHz, CDCl3, vs TMS): δ 184.5, 166.1, 161.5,
143.2, 137.8, 129.3, 127.2, 114.6, 104.6, 85.1, 83.1, 82.1, 81.4,
53.3, 52.0, 21.5, 13.5. UV-vis (CH2Cl2): λmax (ꢀ) 638 (1000),
390 (3300), 295 (28000). Anal. Calcd for C19H20NO6S3Co: C,
44.44; H, 3.93; N, 2.73. Found: C, 44.43; H, 3.87; N, 2.65.
[(C5H3-Me-NHTs)Co{S2C2(COOMe)2}] (1,2-su bstitu t-
Ack n ow led gm en t. The present work was supported
by a grant-in-aid for Scientific Research No. 14740369
and by grants-in-aid on Priority Area-Researches on
‘Interelements’ No. 09239246 and 11120251 from the
Ministry of Education, Science, Sports and Culture,
J apan.
ed Cp isom er ). Mp: 209-210 °C (dec). Mass (EI+, 70 eV) m/z
Su p p or tin g In for m a tion Ava ila ble: Table of atomic
coordinates, isotropic and anisotropic displacement param-
eters, and all bond length and angles. This material is
available free of charge via the Internet at http://pubs.acs.org.
(rel intensity): 513 (M+, 95.4), 371 ((NHTs-Me-C5H3)CoS2
,
+
11.4), 91 (C6H4Me+, 100). 1H NMR (500 MHz, CDCl3, vs
TMS): δ 7.35 (d, J ) 8.34, 2H, Ar), 6.98 (d, J ) 8.34, 2H, Ar),
6.53 (br, 1H, NH), 5.65 (m, 1H, Cp), 5.16 (m, 1H, Cp), 4.70 (m,
1H, Cp), 3.88 (s, 6H, OMe), 2.41 (s, 3H, Me), 2.25 (s, 3H, Me).
OM0207212