Imido-transfer reactions to carbonyl moiety induced by the reactions of imido-bridged cobaltadithiolene complexes with trivalent phosphorus halides

Article abstract of DOI:10.1016/S0022-328X(03)00213-4

The reactions of the imido-bridged cobaltadithiolene complexes [CpCo{S₂C₂(COOMe)₂}(NR)] (R=Ts, Ms) with PCl₃ led to the imido-transfer reactions to the carbonyl moiety, and these reactions gave the novel imine c

Full text of DOI:10.1016/S0022-328X(03)00213-4

Journal of Organometallic Chemistry 674 (2003) 63ꢁ72
/
www.elsevier.com/locate/jorganchem
Imido-transfer reactions to carbonyl moiety induced by the reactions
of imido-bridged cobaltadithiolene complexes with trivalent
phosphorus halides
Mitsushiro Nomura a,*, Chikako Takayama a,1, Gerardo C. Janairo b, Toru Sugiyama a,
Yasuo Yokoyama a, Masatsugu Kajitani a
a Department of Chemistry, Faculty of Science and Technology, Sophia University, 7-1, Kioi-cho, Chiyoda-ku, Tokyo 102-8554, Japan
b Department of Chemistry, De La Salle University, 2401 Taft Avenue, 1104 Manila, Philippines
Received 16 January 2003; received in revised form 25 March 2003; accepted 27 March 2003
Abstract
The reactions of the imido-bridged cobaltadithiolene complexes [CpCo{S2C2(COOMe)2}(NR)] (Rꢀ/Ts, Ms) with PCl3 led to the
imido-transfer reactions to the carbonyl moiety, and these reactions gave the novel imine complexes [CpCo{S2C2(COOMe)(CÄ
/
NROMe)}]. In the case of PI3, another imido-transfer reaction to carbonyl moiety occurred and the novel amide complexes
[CpCo{S2C2(COOMe)(CONHR)}] were formed. PBr3 showed an intermediate reactivity value in between that of PCl3 and that of
PI3. Both novel imido-transfer reactions were caused by intermolecular reactions, these reaction processes were determined by
crossover experiments.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Cobaltadithiolene; Imido-transfer; Imine; Amide; Phosphorus trihalide
1. Introduction
(R1, R2ꢀ
H, H; H, COOEt; COOMe, COOMe) [3].
/
The corresponding alkene [4]- or norbornene [5]-bridged
metalladithiolene complexes are also obtained by the
reactions with alkyne or quadricyclane, respectively.
Recently, it has been reported that cyclopentadienyl o-
carboranedithiolato cobalt complexes [CpCo{S2C2-
(B10H10)}] also undergo similar addition reactions [6].
Likewise, the reaction of cobaltadithiolene complex
[CpCo{S2C2(COOMe)2}] with (N-tosylimino)phenylio-
Metalladithiolene complexes are unique and interest-
ing compounds because of their ability to exhibit both
the unsaturated and the aromatic character [1]. The
substitution [2] and the addition reactions [3ꢁ7] of
/
cyclopentadienyl metalladithiolene complexes have
been reported. These reactions can be explained as due
to the dual characters of metalladithiolene complexes. A
typical addition reaction often occurs between the metal
dinane (PhIÄ
tosylimido-bridged
[CpCo{S2C2(COOMe)2}(NTs)] (1a) [7].
Imido metal complexes (MꢀNTs) often lead to
/
NTs) or tosyl azide give the corresponding
and the sulfur (MÃ
in the case of the reactions of cyclopentadienyl metalla-
dithiolene complexes [CpM(S2C2Z2)] (MꢀCo, Rh; Zꢀ
/S) bond of metalladithiolene ring. As
cobaltadithiolene complex
/
/
/
imido-transfer reactions, which are important as analo-
gous oxo-transfer reactions [8]. According to a recent
report, the reactions of bis(tosylimido)ruthenium por-
COOMe, Ph, and so on) with diazo compounds
(R1R2CN2), these reactions yield the alkylidene-bridged
metalladithiolene complexes [CpM(S2C2Z2)(CR1R2)]
phyrin complexes [RuVI(Por)(NTs)2] (Porꢀ
porphyri-
/
nato ligand) with alkenes or hydrocarbons give
aziridination and amidation products (Scheme 1) [9].
Mechanistic and kinetic studies are also discussed in this
report. The most useful imido-transfer reaction is the
* Corresponding author. Tel.:
2383361.
E-mail address: m-nomura@sophia.ac.jp (M. Nomura).
ꢂ
/
81-33-2383366; fax:
ꢂ81-33-
/
1
Present address: Department of Chemistry, University of British
Columbia Vancouver, British Columbia, Canada V6T 1Z1.
reaction of PhIÄ
/
NTs [10] with alkenes and hydrocar-
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00213-4

64
M. Nomura et al. / Journal of Organometallic Chemistry 674 (2003) 63ꢁ72
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Scheme 1.
bons in the presence of a catalyst. A large number of
examples of catalytic aziridinations [11] and amidations
2. Results and discussion
[12] have been reported using PhIÄ
intermediates of these catalytic reactions are also imido
metal complexes (MꢀNTs). Similarly, the trifluoroace-
/
NTs. Proposed
2.1. Reactions of imido-bridged cobaltadithiolene
complexes with trivalent phosphorus halide, PCl3
/
tylimido manganese complexes formed by the corre-
sponding nitrido manganese complexes are also imido-
transfer reagents, and these complexes react with
alkenes to give aziridines and amides [13]. In addition,
the reactions of tosylimido molybdenum complexes
Each imido-bridged cobaltadithiolene complex 1a or
1b was prepared from [CpCo{S2C2(COOMe)2}] (4) with
TsN3 or MsN3 using the procedure developed in our
laboratory [7]. Complex 1a reacted with two equivalents
of PCl3 in refluxing benzene to give complex 4 and the
[Mo(NTs)2(Et2dtc)2] (Et2dtcꢀN,N-diethydithiocarba-
/
novel tosylimine complex [CpCo{S2C2(COOMe)(CÄ
/
mate) with phosphines give iminophosphoranes by the
imido-transfer reactions from molybdenum to phos-
phines [14]. Therefore, imido metal complexes are very
important complexes as imido sources.
NTsOMe)}] (2a) in yields of 39 and 4% (Scheme 3 and
Table 1). The analogue complex 1b led to same reaction,
and this reaction gave the corresponding mesylimine
complex [CpCo{S2C2(COOMe)(CÄ
/
NMsOMe)}] (2b)
We have focused on the tosylimido-bridged cobalta-
dithiolene complex 1a as a source of a novel imido-
transfer reaction, because such a reaction in an organo-
metallic complex has never been reported. Complex 1a
has the three-membered ring consisting of cobalt, sulfur
and nitrogen (cobaltathiaziridine), and it is a distorted
and a reactive ring like a typical aziridine. A previous
report explained that complex 1a undergoes an azir-
idine-like reaction, namely, the ring opening of the
three-membered ring by a protic acid [7]. However, we
have also discovered that the reaction of complex 1a
with phosphine or phosphite leads to the intramolecular
imido-migration reaction to the Cp ring [15]. Complex
1a reacts with phosphine or phosphite at room tem-
(5% yield) and complex 4 (39% yield), respectively.
These reactions were complicated, and other products
were not determined. The structures of complexes 2a
and 2b were determined by X-ray structure analyses.
The ORTEP drawings of complexes 2a and 2b are shown
in Fig. 1a and b, respectively. In Fig. 1a, the bond
lengths of cobaltadithiolene are similar to those of a
typical cyclopentadienyl cobaltadithiolene complex 4
˚
C4 is 1.271 A, which is
[3e]. The bond length of N1Ã
/
˚
N bond (1.24 A)
slightly longer than that of a typical CÄ
/
[16]. The tosyl group is oriented at the syn form to the
plane of the cobaltadithiolene ring. The IR spectrum of
complex 2a showed two strong bands at 1699 and 1600
cmꢃ1 corresponding to CÄ
/
O and CÄ/N stretching
perature to give the sulfilimine (Sꢂ Ã
/
Nꢃ) intermediate
vibrations, respectively. These results support the tosy-
limine structure of complex 2a. Similarly, the X-ray data
and the spectroscopic data of complex 2b also support
its mesylimine structure. Therefore, the reaction of
complexes 1a and 1b with PCl3 lead to the imido-
transfer reaction to the carbonyl moiety of cobalta-
dithiolene substituent, and the novel imine complexes
are formed.
due to the ring opening of the cobaltathiaziridine. Upon
heating, this sulfilimine intermediate further undergoes
the migration reaction of the imido group to the Cp
ring; here the novel amide-substituted Cp complex
[(C5H4Ã/NHTs)Co{S2C2(COOMe)2}] is formed (Scheme
2). Since the migration reaction is induced by trivalent
phosphorus compounds, we focused our attention on
the reactions of trivalent phosphorus halides with
complex 1a and the corresponding mesylimido-bridged
complex [CpCo{S2C2(COOMe)2}(NMs)] (1b).
2.2. Reactions of imido-bridged cobaltadithiolene
complexes with trivalent phosphorus halides, PBr3 and
PI3
Here we report the novel imido-transfer reactions to
carbonyl moiety induced by the reactions of imido-
bridged cobaltadithiolene complexes having carbonyl
groups with trivalent phosphorus halides.
The reactions of complexes 1a and 1b with other
trivalent phosphorus halides, PBr3 and PI3, were also

M. Nomura et al. / Journal of Organometallic Chemistry 674 (2003) 63ꢁ
/72
65
Scheme 2.
investigated. The reaction of complex 1a with two
equivalents of PBr3 in refluxing benzene gave complex
4 (61% yield), tosylimine complex 2a (trace amount),
and the novel tosylamide complex [CpCo{S2C2(COO-
Me)(CONHTs)}] (3a) (10% yield). In the case of PI3,
complex 2a was not formed. The only products were
complex 4 (77% yield) and complex 3a (14% yield,
Scheme 3 and Table 1). The analogue complex 1b was
allowed to experience the same reaction by PI3, and this
reaction gave the corresponding mesylamide complex
imination and the amidation reactions to carbonyl
moiety. We assume that PBr3 has an intermediate
reactivity value in between that of PCl3 and that of
PI3 in the reaction with imido-bridged cobaltadithiolene
complex.
2.3. Reactions of imido-bridged cobaltadithiolene
complex with pentavalent phosphorus halides and Lewis
acids
[CpCo{S2C2(COOMe)(CÄ
/
NMsOMe)}] (3b) (9% yield)
The reactions of pentavalent phosphorus chloride
were also investigated. Complex 1a was made to react
and complex 4 (78% yield). The structure of complex 3a
was determined by X-ray structure analyses. The ORTEP
drawing of complex 3a is shown in Fig. 2. The bond
lengths of cobaltadithiolene are similar to those of
complex 2a and to those of a typical cyclopentadienyl
cobaltadithiolene complex [CpCo{S2C2(COOMe)2}]
[3e]. The IR spectrum of complex 3a showed two strong
bands at 1713 and 1680 cmꢃ1 corresponding to two
with PCl5 or OÄ/PCl3 as a pentavalent phosphorus
chloride instead of PCl3. In the case of PCl5, although
a trace amount of complex 4 was formed under same
reaction conditions shown in Table 1, most complexes
were decomposed and then various unknown products
were formed. Likewise, in the case of OÄ/PCl3, although
complex 4 was obtained in 26% yield and complex 1a
was recovered in 47% yield, respectively, target product
2a was not obtained. A pentavalent phosphorus halide
often behaves as a Lewis acid. The reactions of complex
1a with AlCl3 and TiCl4 as a Lewis acid were also
performed. Similarly, complex 1a decomposed and
target product 2a was not obtained. Therefore, the
reaction of complex 1a with Lewis acid was a compli-
cated decomposition reaction. We conclude that a
trivalent phosphorus halide is needed in the imination
and the amidation reactions.
different CÄ
/
O stretching vibrations. In addition, the
broad bands of 3113 cmꢃ1 in IR and 9.7 ppm in H-
NMR spectra were attributed to the NH group of
amide. These results support the tosylamide structure of
complex 3a. The structure of complex 3b was also
determined by spectroscopic data. Therefore, the reac-
tion of complexes 1a and 1b with PI3 lead to the imido-
transfer reaction to the carbonyl moiety of cobalta-
dithiolene substituent, and the novel amide complexes
are formed. On the other hand, PBr3 caused the
1
Scheme 3.

66
M. Nomura et al. / Journal of Organometallic Chemistry 674 (2003) 63ꢁ72
/
Table 1
Reactions of imido-bridged cobaltadithiolene complexes [CpCo{S2C2(COOMe)2}(NR)] with trivalent phorphorus halides PX3 (two equivalents)
X
R
Scavenger
Solvent
Yield of 2a (%)
Yield of 3a (%)
Yield of 4 (%)
Cl
Cl
Br
I
Ts
Ms
Ts
Ts
Ms
Ts
Ts
Ts
Ts
None
None
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
PhCOMe
4
0
0
39
39
61
77
78
43
96
43
36
5
Trace
None
None
None
10
14
9
0
I
0
Cl
Cl
Cl
Cl
Cyclohexene
Complex 4
PhCOMe
None
5
0
13
3
0
0
0
0
All reaction times are 1 h, and all yields are isolated pure ones.
˚
Fig. 1.
1.357(8), N1Ã
C1 120.1(4), N1Ã
2.109(2), S1ÃC1 1.719(7), S2Ã
Co1ÃS2ÃC2 104.5(3), S1ÃC1Ã
(
a
) ORTEP drawing of complex 2a. Selected bond lengths (A): Co1Ã
C4 1.271(7). Selected bond angles (8): S1ÃCo1ÃS2 92.29(7), Co1Ã
C4ÃC2 128.9(8), S3ÃN1ÃC4 121.0(4). (b) ORTEP drawing of complex 2b. Selected bond lengths (A): Co1Ã
C2 1.711(7), C1ÃC2 1.364(10), N1ÃC4 1.282(9). Selected bond angles (8): S1ÃCo1ÃS2 92.35(9), Co1Ã
C2 119.1(6), S2ÃC2ÃC1 119.5(5), N1ÃC4ÃC2 129.8(8), S3ÃN1ÃC4 123.4(6).
/
S1 2.103(2), Co1Ã
/
S2 2.105(2), S1Ã
/
C1 1.731(6), S2Ã
C1ÃC2 118.2(5), S2Ã
S1 2.106(2), Co1Ã
S1ÃC1 104.6(3),
/
C2 1.715(6), C1Ã
C2Ã
S2
/
C2
/
/
/
/
S1ÃC1 104.9(2), Co1Ã
/
/
S2ÃC2 104.5(2), S1Ã
/
/
/
/
/
˚
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/

M. Nomura et al. / Journal of Organometallic Chemistry 674 (2003) 63ꢁ
/72
67
˚
Fig. 2. ORTEP drawing of complex 3a. Selected bond lengths (A): Co1Ã
/
S1 2.1070(10), Co1Ã
/
S2 2.1050(10), S1Ã
/
C1 1.728(2), S2Ã
/
C2 1.718(2), C1Ã
/
C2
1.360(3). Selected bond angles (8): S1ÃCo1ÃS2 91.70(3), Co1ÃS1ÃC1 105.22(9), Co1Ã
/
/
/
/
/
S2ÃC2 105.42(9), S1Ã
/
/
C1Ã
/
C2 118.6(2), S2Ã
/
C2ÃC1 119.0(2).
/
2.4. Investigation of reaction mechanism
elimination and the formation of TsNH2 [7]. On the
other hand, the reaction of complex 1 with PCl3 in the
presence of deuterated water was attempted, and the
deuterated p-toluenesulfonylamide (TsND2) was de-
tected. Therefore, the hydrogen source of p-toluene
sulfonyl amide is the water slightly containing in the
solution or the HCl formed by the hydrolysis of PCl3.
Imine compounds can be also synthesized by the
reaction of carbonyl compounds with iminophosphor-
In the imination reaction, the 1H-NMR and GC-Mass
spectra of the reaction mixture also showed the presence
of p-toluenesulfonylamide (TsNH2) [17].
A trace
amount of TsNH2 was detected. The possible role of
TsNH2 in the formation of the tosylimine complex 2a
was also investigated. A typical imine compound is
prepared by the reactions of amines with aldehydes or
ketones involving dehydration [16], so the possibility of
TsNH2 as an imine source can be not ignored. An
attempt to synthesize complex 2a by the reaction of
complex 4 with TsNH2 in the presence of PCl3 did not
occur reaction, and complex 4 was quantitatively
recovered. Such a result suggests that TsNH2 does not
concern in the formation of complex 2a. In amidation
by the reaction of complex 1a with PI3, TsNH2 was also
detected. Occasionally, the reactions of carboxylic ester
with amines give amides [18]. Likewise, though we tried
to synthesize complex 3a using TsNH2 as an amide
source, complex 3a was not formed and the effect of
TsNH2 was also not confirmed.
The reaction of complex 1a with PCl3 in the presence
of water was performed under same condition shown in
Table 1. The yield of expected imination product 2a
decreased, and a trace amount of complex 2a was
obtained. Therefore, the water containing in the reaction
prevents this imido-transfer reaction. We assume that
complex 1a reacted with the HCl formed by the
hydrolysis of PCl3, and this reaction led to the imido
anes (R3Pꢂ Ã
/
NꢃTs) through the Wittig-type reaction.
Namely, it is conceivable that tosylimine complex 2a
was formed by the reaction of the iminophosphorane
(Cl3Pꢂ Ã
/
NꢃTs). This type of iminophosphorane occa-
sionally leads to conversion from an isocyanate (Ã
CÄO) to a carbodiimide (ÃNÄCÄNR) [19]. Probable
precursors of Cl3Pꢂ ÃNꢃTs in this reaction are tosyl
nitrene (:NTs) and tosylsulfilimine (R2Sꢂ ÃNꢃTs).
/
NÄ
/
/
/
/
/
/
/
Complex 1a was made to react with PCl3 under a large
excess of cyclohexene as a nitrene scavenger (Table 1). It
is known that nitrenes react with alkenes to give the
corresponding allylamines or aziridines. However, the
presence of amine or aziridine in the reaction mixture
was not detected even at GC-Mass sensitivity level.
Therefore, the detected TsNH2 [17] is not formed by the
hydrogen abstraction of tosyl nitrene. On the other
hand, we have reported the isolation and the character-
ization of a stable sulfilimine complex by the reactions
of complex 1a with PPh3 or P(OPh)3 as a nucleophile
[7,15]. Similarly, the mechanism for the reaction of
complex 1a with PCl3 seems to involve the formation of

68
M. Nomura et al. / Journal of Organometallic Chemistry 674 (2003) 63ꢁ72
/
an analogous but unstable sulfilimine intermediate. This
intermediate was probably formed through the nucleo-
philic attack of PCl3 on the cobalt atom of complex 1a.
However, the isolation and the characterization of
sulfilimine intermediate and iminophosphorane have
not succeeded.
These products were detected by GC-Mass spectra.
Therefore, this imination reaction can be applied to a
typical carbonyl compound. Especially, tosylimines are
very important imines because they are one of the few
types of electron-deficient imines that are stable enough
to be isolated but reactive enough to undergo addition
reactions [20]. However, the synthetic methods of
tosylimines have been limited to aldehydes and ketones
as a starting material. In this method, the tosylimination
is also applied to esters. However, a weak point in this
reaction condition is the low efficiency of the reaction.
In the future, the reaction condition should be improved
and re-investigated.
2.5. Crossover experiments
The crossover experiment as shown in Scheme 4 was
performed. A mixture of complex 1a and 10 equivalents
of [CpCo{S2C2(COOEt)2}] was heated in the presence of
PCl3. Results revealed that not only complex 2a but also
[CpCo{S2C2(COOEt)(CÄNTsOEt)}] (2a?) were formed.
/
If this imine formation is caused by an intramolecular
reaction, only complex 2a should be formed. The
formation of complex 2a? suggests that this reaction is
caused by an intermolecular imido-transfer reaction.
The formation ratio of complexes 2a to 2a? was about
2.6. Conclusion
Imido metal complexes (MꢀNTs) often lead to the
aziridination of alkenes and the amidation of hydro-
carbons. On the other hand, the imido-bridged cobalta-
/
1
2:3, according to H-NMR spectra. In addition, when
dithiolene complex [CpCo{S2C2(COOMe)2}(NR)] (Rꢀ
/
ten equivalents of complex 4 were used as scavenger, the
yield of complex 2a increased on the basis of the amount
of 1a (Table 1). A similar crossover experiment was also
performed using PI3. Two different amide complexes 3a
and [CpCo{S2C2(COOEt)(CONHTs)}] (3a?) were
formed. So we conclude that the amide formation in
this case is also caused by an intermolecular imido-
transfer reaction.
Furthermore, in another series of crossover experi-
ments, the reactions of complex 1a with PCl3 in the
presence of various carbonyl compounds were per-
formed. Benzaldehyde, acetophenone, benzophenone,
3-pentanone, methyl benzoate and acetylferrocene were
used as typical carbonyl compounds. When 10 equiva-
lents of the carbonyl compound were used, the reaction
yielded complex 2a and the corresponding imination
products of the carbonyl compounds. When these
carbonyl compounds were used as the solvents of the
reaction, complex 2a was not formed at all (Table 1).
Ts (1a), RꢀMs (1b)) led to the novel imination and
/
amidation reactions to carbonyl moiety through an
intermolecular imido-transfer reaction by the reactions
with trivalent phosphorus halides. Although the yields
of products were not good, the novel imine complexes
[CpCo{S2C2(COOMe)(CÄ
RꢀMs (2b)) and the novel amide complexes
[CpCo{S2C2(COOMe)(CONHR)}] (RꢀTs (3a), Rꢀ
/
NROMe)}] (Rꢀ
/
Ts (2a),
/
/
/
Ms (3b)) were isolated and characterized. An amide
group and an imine group are useful for conversions to
other nitrogen groups. Therefore, we will be able to
obtain the novel cobaltadithiolene complexes with
various nitrogen groups. The formations of complexes
2aꢁ
/
b and 3aꢁb reveal that cobaltathiaziridine as an
/
aziridine analogue showed not only the reactivity of
aziridines [7] but also the reactivity of imido metal
complexes. It is interesting that the imido-transfer
reactions of complexes 1a and 1b are different from
Scheme 4.

M. Nomura et al. / Journal of Organometallic Chemistry 674 (2003) 63ꢁ
/72
69
the intramolecular imido-migration by the reaction with
PPh3 or P(OPh)3.
chromatography (Wako-gel C300, eluent dichloro-
methane). Products 2a and 4 were obtained in trace
amount and 36% (59 mg, 0.179 mmol) yields, respec-
tively.
3. Experimental
A solution of complex 1b (42 mg, 0.1 mmol) and PCl3
(17.5 ml, 0.2 mmol) in benzene (10 ml) was refluxed for 1
h. After the solvent was removed under reduced
pressure, the residue was separated by column chroma-
tography (Wako-gel C300, eluent dichloromethane).
Products 2b and 4 were obtained in 5 (2.0 mg, 0.005
mmol) and 39% (13 mg, 0.039 mmol) yields, respec-
3.1. Gneneral remarks
All reactions were carried out under argon atmo-
sphere by means of standard Schlenk techniques.
Solvents were purified by ketyl distillation before use.
The cobaltadithiolene complexes [CpCo(S2C2Z2)] (Zꢀ
/
tively. Purple solid (2b); m.p. 194ꢁ
1.3 kV) m/z (rel. intensity) 407 (Mꢂ, 34.9), 328 (Mꢂꢃ
Ms, 32.5), 188 (
CpCoSꢂ2 ; 100), 124 (CpCoꢂ, 37.3), 79
/
195 8C, Mass (EIꢂ,
COOMe (4), COOEt) were prepared by the literature
methods [21]. The phosphorus trihalides, PCl3, PBr3 and
PI3, were used without further treatment. Silica gel,
Wakogel C-300 was obtained from Wako Pure Chemi-
cal Industries, Ltd. Mass and IR spectra were recorded
on a JEOL JMS-D300 and a Shimadzu model FTIR
8600PC, respectively. GC-Mass spectra were measured
with a Shimadzu model GCMS-QP5000. NMR spectra
/
/
(Msꢂ, 4.8), 59 (Coꢂ, 22.9). 1H-NMR (500 MHz,
CDCl3, vs. Me4Si) d 5.50 (5H, Cp), 3.98 (s, 3H,
OMe), 3.87 (s, 3H, OMe), 2.96 (s, 3H, Me). 13C-NMR
(125 MHz, CDCl3, vs. Me4Si) d 170.4, 165.4, 161.9,
155.5, 80.8, 56.6, 52.8, 42.2. UVꢁVis (CH2Cl2) lmax (o)
/
552 (6900), 361 (4100), 291 (32 000). IR (KBr) 1701,
1612, 1434, 1317, 1259, 1146 cmꢃ1. Anal. Calc for
C12H14CoNO5S3: C, 35.38; H, 3.46; N, 3.44. Found: C,
35.49; H, 3.54; N, 3.44%.
were measured with a JEOL LA500 spectrometer. UVꢁ
/
vis were recorded on a Hitachi model UV-2500PC.
Elemental analyses were determined by using a Shi-
madzu PE2400-II instrument. Melting points were
measured by a Yanaco Micro melting point apparatus.
3.2.2. Reactions of imido-bridged cobaltadithiolene
complexes with trivalent phosphorus iodide, PI3
3.2. Reactions of imido-bridged cobaltadithiolene
complexes with trivalent phosphorus halides, PX3
A solution of complex 1a (50 mg, 0.1 mmol) and PI3
(82 mg, 0.2 mmol) in benzene (10 ml) was refluxed for 1
h. After the solvent was removed under reduced
pressure, the residue was separated by column chroma-
tography (Wako-gel C300). In eluent dichloromethane,
3.2.1. Reactions of imido-bridged cobaltadithiolene
complexes with trivalent phosphorus chloride, PCl3
A solution of complex 1a (50 mg, 0.1 mmol) and PCl3
(17.5 ml, 0.2 mmol) in benzene (10 ml) was refluxed for 1
h. After the solvent was removed under reduced
pressure, the residue was separated by column chroma-
tography (Wako-gel C300, eluent dichloromethane).
Products 2a and 4 were obtained in 4 (2.0 mg, 0.004
mmol) and 39% (13 mg, 0.039 mmol) yields, respec-
product 4 was separated. In eluent dichloromethaneꢁ
/
ethyl acetateꢀ10:1, product 3a was separated. Products
/
3a and 4 were obtained in 14 (6.6 mg, 0.014 mmol) and
77% (25.5 mg, 0.077 mmol) yields, respectively. Purple
solid (3a); m.p. 222ꢁ
/
223 8C (dec.), Mass (EIꢂ, 1.3 kV)
m/z (rel. intensity) 469 (Mꢂ, 12.8), 314 (Mꢂꢃ
/Ts, 7.7),
299 (Mꢂꢃ
/
NHTs, 15.4), 188 (
CpCoSꢂ2 ; 73.1), 124
/
tively. Purple solid (2a); m.p. 254ꢁ
/
255 8C (dec.), Mass
(CpCoꢂ, 84.6), 91 (C6H4Meꢂ, 100), 59 (Coꢂ, 55.1).
(EIꢂ, 1.3 kV) m/z (rel. intensity) 483 (Mꢂ, 68.7), 328
1H-NMR (500 MHz, CDCl3, vs. Me4Si) d 9.67 (broad,
(Mꢂꢃ
/
Ts, 77.1), 188 (/
CpCoSꢂ2 ; 100), 155 (Tsꢂ, 10.8),
1H, NH), 8.01 (d, Jꢀ
/
8.00 Hz, 2H, Ar), 7.32 (d, Jꢀ8.00
/
124 (CpCoꢂ, 51.8), 91 (C6H4Meꢂ, 53.0), 59 (Coꢂ,
Hz, 2H, Ar), 5.49 (5H, Cp), 3.79 (s, 3H, OMe), 2.43 (s,
3H, Me). 13C-NMR (125 MHz, CDCl3, vs. Me4Si) d
165.0, 162.7, 160.9, 160.7, 144.9, 135.6, 129.5, 128.7,
30.1). 1H-NMR (500 MHz, CDCl3, vs. Me4Si) d 7.56 (d,
Jꢀ
/
8.08 Hz, 2H, Ar), 7.16 (d, Jꢀ8.08 Hz, 2H, Ar), 5.50
/
(5H, Cp), 3.93 (s, 3H, OMe), 3.76 (s, 3H, OMe), 2.39 (s,
3H, Me). 13C-NMR (125 MHz, CDCl3, vs. Me4Si) d
170.0, 165.4, 161.7, 155.7, 142.9, 138.2, 129.0, 127.1,
81.2, 53.4, 21.7. UVꢁvis (CH2Cl2) lmax (o) 554 (6800),
/
363 (4500), 292 (34 000). IR (KBr) 3113, 1713, 1680,
1429, 1339, 1273, 1155 cmꢃ1. Anal. Calc. for C17H16Co-
NO5S3: C, 43.49; H, 3.44; N, 2.98; S, 20.49. Found: C,
43.43; H, 3.29; N, 3.03; S, 20.33%.
A solution of complex 1b (42 mg, 0.1 mmol) and PI3
(82 mg, 0.2 mmol) in benzene (10 ml) was refluxed for 1
h. After the solvent was removed under reduced
pressure, the residue was separated by column chroma-
tography (Wako-gel C300). In eluent dichloromethane,
80.8, 56.7, 52.7, 21.5. UVꢁvis (CH2Cl2) lmax (o) 554
/
(6900), 363 (4200), 292 (32 000). IR (KBr) 1699, 1601,
1433, 1319, 1259, 1157 cmꢃ1. Anal. Calc. for C18H18Co-
NO5S3: C, 44.72; H, 3.75; N, 2.90; S, 19.90. Found: C,
44.73; H, 3.72; N, 2.95; S, 19.68%
A solution of complex 1a (250 mg, 0.5 mmol) and
PCl3 (87.5 ml, 1.0 mmol) in the presence of water (9.0 ml,
0.5 mmol) was reacted under refluxing benzene (50 ml)
for 1 h. The reaction mixture was separated by column
product 4 was separated. In eluent dichloromethaneꢁ
/
ethyl acetateꢀ10:1, product 3b was separated. Products
/

70
M. Nomura et al. / Journal of Organometallic Chemistry 674 (2003) 63ꢁ72
/
3b and 4 were obtained in 9 (3.5 mg, 0.009 mmol) and
78% (25.7 mg, 0.078 mmol) yields. Purple solid (3b);
2a and 2a? (6.1 mg), the mixture of products 4 and
[CpCo{S2C2(COOEt)2}] (355 mg) were obtained. The
formation ratio of complexes 2a to 2a? was about 2:3,
m.p. 221ꢁ
222 8C (dec.), Mass (EIꢂ, 1.3 kV) m/z (rel.
/
intensity) 393 (Mꢂ, 9.7), 314 (Mꢂꢃ
/
Ms, 4.2), 188 (/
and the formation ratio of complexes
4
to
[CpCo{S2C2(COOEt)2}] was about 1:25, according to
CpCoSꢂ2 ; 34.7), 124 (CpCoꢂ, 93.1), 79 (Msꢂ, 37.5),
1
59 (Coꢂ, 100). H-NMR (500 MHz, CDCl3, vs. Me4Si)
1H-NMR spectra. Purple solid (2a?); Mass (EIꢂ, 1.3 kV)
d 9.2 (broad, 1H, NH), 5.53 (5H, Cp), 3.92 (s, 3H,
OMe), 3.40 (s, 3H, Me). 13C-NMR (125 MHz, CDCl3,
vs. Me4Si) d 164.7, 163.0, 162.6, 160.6, 81.2, 53.5, 41.3.
m/z (rel. intensity) 511 (Mꢂ, 42.7), 356 (Mꢂꢃ
/
Ts, 32.9),
188 (
56.1), 91 (C6H4Meꢂ, 70.7), 59 (Coꢂ, 26.8). H-NMR
(500 MHz, CDCl3, vs. Me4Si) d 7.55 (d, Jꢀ8.20 Hz,
2H, Ar), 7.15 (d, Jꢀ8.20 Hz, 2H, Ar), 5.49 (5H, Cp),
4.37 (q, Jꢀ7.24 Hz, 2H, OCH2), 4.20 (q, Jꢀ7.24 Hz,
2H, OCH2), 2.38 (s, 3H, Me), 1.30 (t, Jꢀ7.24 Hz, 3H,
Me), 1.29 (t, Jꢀ
7.24 Hz, 3H, Me). HR-Mass (EIꢂ, 70
/
CpCoSꢂ2 ; 100), 155 (Tsꢂ, 12.2), 124 (CpCoꢂ,
1
UVꢁ
(31 000). IR (KBr) 3105, 1715, 1697, 1423, 1332, 1258,
1150 cmꢃ1
Anal. Calc. for C11H12NO5S3Co×1/
/
vis (CH2Cl2) lmax (o) 553 (6400), 366 (4200), 292
/
/
.
/
/
/
2(CH2Cl2): C, 31.69; H, 3.01; N, 3.21. Found: C,
31.82; H, 2.89; N, 3.26%.
/
/
eV) Calcd for C20H22CoNO5S3: 510.9992, Found:
510.9992.
3.2.3. Reaction of imido-bridged cobaltadithiolene
complex with trivalent phosphorus bromide, PBr3
A mixture of complex 1a (50 mg, 0.1 mmol) and 10
equivalents of [CpCo{S2C2(COOEt)2}] (358 mg, 1.0
mmol) was made to react with PI3 (82 mg, 0.2 mmol)
in refluxing benzene (10 ml) for 1 h. After the solvent
was removed under reduced pressure, the residue was
separated by column chromatography (Wako-gel C300).
In eluent dichloromethane, products 4 and [CpCo{S2C2-
(COOEt)2}]) were separated. In eluent dichloro-
A solution of complex 1a (50 mg, 0.1 mmol) and PBr3
(19 ml, 0.2 mmol) in benzene (10 ml) was refluxed for 1 h.
After the solvent was removed under reduced pressure,
the residue was separated by column chromatography
(Wako-gel C300). In eluent dichloromethane, products
2a and 4 were separated. In eluent dichloromethaneꢁ
/
ethyl acetateꢀ10:1, product 3a was separated. Products
/
2a, 3a and 4 were obtained in trace amount, 10 (4.7 mg,
0.01 mmol) and 61% (20 mg, 0.061 mmol) yields,
respectively.
methaneꢁ
/
ethyl acetateꢀ10:1, products 3a and 3a?
/
were separated. The mixture of products 3a and 3a?
(8.8 mg), the mixture of products 4 and [CpCo{S2C2-
(COOEt)2}] (362 mg) were obtained. The formation
ratio of complexes 3a to 3a? was about 1:2, and the
3.3. Reactions of imido-bridged cobaltadithiolene
complex with pentavalent phosphorus chlorides and Lewis
acids
formation ratio of complexes
4 to [CpCo{S2C2-
(COOEt)2}] was about 2:25, according to 1H-NMR
spectra. Purple solid (3a?); Mass (EIꢂ, 1.3 kV) m/z (rel.
A solution of complex 1a (50 mg, 0.1 mmol) and PCl5
(42 mg, 0.2 mmol) in benzene (10 ml) was refluxed for 1
h. After the solvent was removed under reduced
pressure, the residue was separated by column chroma-
tography (Wako-gel C300, eluent dichloromethane).
Product 4 was obtained in a trace amount.
intensity) 483 (Mꢂ, 9.0), 328 (Mꢂꢃ
/Ts, 6.4), 188 (/
CpCoSꢂ2 ; 62.8), 124 (CpCoꢂ, 60.3), 91 (C6H4Meꢂ,
100), 59 (Coꢂ, 50.0). H-NMR (500 MHz, CDCl3, vs.
1
Me4Si) d 9.8 (broad, 1H, NH), 7.81 (d, Jꢀ
Ar), 7.31 (d, Jꢀ7.91 Hz, 2H, Ar), 5.48 (5H, Cp), 4.29
(q, Jꢀ7.20 Hz, 2H, OCH2), 2.42 (s, 3H, Me), 1.27 (t,
Jꢀ
7.20 Hz, 3H, Me). HR-Mass (EIꢂ, 70 eV) Calc. for
/7.91 Hz, 2H,
/
/
In the cases of OÄ/PCl3, AlCl3 and TiCl4 instead of
/
PCl5, the reactions were performed by under the same
conditions. The product 4 was obtained in 26 (8.6 mg,
C18H18CoNO5S3: 482.9679, Found: 482.9669.
0.026 mmol, OÄ
/
PCl3), 38% (12.5 mg, 0.038 mmol,
3.4.2. Reactions of imido-bridged cobaltadithiolene
complex with trivalent phosphorus chloride in the presence
of carbonyl compounds
AlCl3) and a trace amount (TiCl4), respectively.
3.4. Crossover experiment
A mixture of complex 1a (50 mg, 0.1 mmol) and 10
equivalents of carbonyl compounds (benzaldehyde,
acetophenone, benzophenone, 3-pentanone, methyl
benzoate, acetylferrocene) were reacted with PCl3 (17.5
ml, 0.2 mmol) in refluxing benzene (10 ml) for 1 h. After
the solvent was removed under reduced pressure, the
residue was separated by column chromatography
(Wako-gel C300, eluent dichloromethane). Products 2a
and 4 were obtained. The yields of complexes 2a and 4
are as follows: using benzaldehyde; 2a (2.0 mg, 0.004
mmol, 4%) and 4 (15.5 mg, 0.047 mmol, 47%), using
acetophenone; 2a (1.5 mg, 0.003 mmol, 3%) and 4 (14.2
3.4.1. Reactions of imido-bridged cobaltadithiolene
complex with trivalent phosphorus halides in the presence
of [CpCo{S2C2(COOEt)2}]
A mixture of complex 1a (50 mg, 0.1 mmol) and 10
equivalents of [CpCo{S2C2(COOEt)2}] (358 mg, 1.0
mmol) was made to react with PCl3 (17.5 ml, 0.2
mmol) in refluxing benzene (10 ml) for 1 h. After the
solvent was removed under reduced pressure, the residue
was separated by column chromatography (Wako-gel
C300, eluent dichloromethane). The mixture of products

M. Nomura et al. / Journal of Organometallic Chemistry 674 (2003) 63ꢁ
/72
71
mg, 0.043 mmol, 43%), using benzophenone; 2a (2.0 mg,
0.004 mmol, 4%) and 4 (13.5 mg, 0.041 mmol, 41%),
using 3-pentanone; 2a (2.4 mg, 0.005 mmol, 5%) and 4
(13.5 mg, 0.041 mmol, 41%), using methyl benzoate; 2a
(2.1 mg, 0.004 mmol, 4%) and 4 (14.5 mg, 0.044 mmol,
44%), using acetylferrocene; 2a (1.5 mg, 0.003 mmol,
3%) and 4 (21.5 mg, 0.065 mmol, 65%).
radiation, and the measurement of complex 3a was
made on a Rigaku MERCURY diffractometer with
graphite-monochromated MoꢁKa radiation. Each
/
structure was solved by direct methods and expanded
Fourier techniques. The non-hydrogen atoms were
refined anisotropically. Idealized positions of complexes
2a and 2b were used for the teXsan, and idealized
positions of complex 3a were used for the CRYSTAL
STRUCTURE crystallographic software package of
Molecular Structure Corp.
For trace analysis of the corresponding imine pro-
ducts, the GC-Mass spectrum instrument was used in
the reaction mixture before column separation. The GC-
Mass spectral data of the corresponding imine com-
pounds are as follows: (EIꢂ, 1.3 kV) m/z (rel. intensity);
using benzaldehyde 259 (Mꢂ, 9.0), 155 (Tsꢂ, 44.9), 104
4. Supplementary material
(Mꢂꢃ
using acetophenone 273 (Mꢂ, 6.4), 155 (Tsꢂ, 43.6), 118
(MꢂꢃTs, 14.1), 91 (C6H4Meꢂ, 100), 77 (Phꢂ, 34.6),
Ts, 100),
/
Ts, 12.8), 91 (C6H4Meꢂ, 100), 77 (Phꢂ, 14.1),
Crystallographic data (excluding structure factors) for
the structures in this paper have been deposited with the
Cambridge Crystallographic Data Centre, CCDC no.
199248, 199247, 199246 for compounds 2a, 2b, 3a.
Copies of the data may be obtained free of charge
from The Director, CCDC, 12 Union Road, Cambridge
/
using benzophenone 335 (Mꢂ, 7.7), 180 (Mꢂꢃ
/
155 (Tsꢂ, 17.9), 91 (C6H4Meꢂ, 67.9), 77 (Phꢂ, 84.6),
using 3-pentanone 239 (Mꢂ, 5.1), 155 (Tsꢂ, 65.4), 91
(C6H4Meꢂ, 100), using methyl benzoate 289 (Mꢂ, 7.7),
155 (Tsꢂ, 11.5), 134 (MꢂꢃTs, 6.4), 91 (C6H4Meꢂ,
/
CB2 1EZ, UK (Fax: ꢂ44-1223-336033 or e-mail:
/
100), 77 (Phꢂ, 14.1), using acetylferrocene 381 (Mꢂ,
deposit@ccdc.cam.ac.uk or www: http://www.ccdc.
cam.ac.uk).
59.0), 316 (Mꢂꢃ
/
Cp, 5.1), 226 (Mꢂꢃ
Ts, 14.1), 185
/
(Fcꢂ, 100), 155 (Tsꢂ, 10.3), 91 (C6H4Meꢂ, 26.9).
3.5. X-ray diffraction study
Acknowledgements
Crystal data are shown in Table 2. The measurements
of complexes 2a and 2b were made on a Rigaku AFC 5S
The present work was supported by a grant-in-aid for
Scientific Research No. 14740369 and grants-in-aid on
Priority Area-Researches on ‘Interelement’ No.
diffractometer with graphite-monochromated MoꢁKa
/
Table 2
Crystallographic data for compounds 2a, 2b and 3a
2a
18H18CoNO5S3
483.46
2b
3a
Empirical formula
Formula weight (g molꢃ1
T (K)
C
C12H14CoNO5S3
407.36
296
C17H16CoNO5S3
469.43
296
)
296
Purple
Crystal color
Crystal habit
Crystal system
Space group
Purple
Purple
Platelet
Prismatic
Monoclinic
P21/c (#14)
13.877(2)
6.982(2)
21.389(3)
102.72(1)
2021.5(8)
4
Prismatic
Monoclinic
P21/c (#14)
13.259(4)
7.162(4)
17.509(4)
93.99(2)
1658.7(9)
4
Monoclinic
P21/c (#14)
9.3528(10)
7.6109(6)
27.459(3)
102.732(5)
1906.6(3)
4
˚
a (A)
˚
b (A)
˚
c (A)
b (8)
3
˚
V (A )
Z
Dcalc (g cmꢃ3
)
1.588
11.89
1.631
14.31
1.635
12.58
m (Moꢁ
/
Ka) (cmꢃ1
Crystal size (mm)
)
0.10ꢄ/0.13ꢄ/0.37
0.10ꢄ
/0.20ꢄ/0.30
0.20ꢄ
/
0.03ꢄ0.12
/
2umax (8)
55.0
55.0
55.0
Unique data (Rint
Observations
Variables
)
4638 (0.022)
1909
271
3911 (0.025)
1453
213
4285 (0.039)
3164
308
R1, wR2 (all data)
Goodness-of-fit on F2
Largest difference peak and hole (e A
0.043, 0.050
1.11
0.048, 0.054
1.17
0.039, 0.027
1.24
ꢃ3
˚
)
0.42, ꢃ0.42
/
0.36, ꢃ0.40
/
0.30, ꢃ0.38
/

72
M. Nomura et al. / Journal of Organometallic Chemistry 674 (2003) 63ꢁ72
/
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,
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,
22.5), 91
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