Reactions of cobaltadithiolene complexes with aryl azides. Formations of metal chelate rings containing nitrogen atoms by substitution reactions via nitrene

Article abstract of DOI:10.1016/S0022-328X(03)00599-0

In the reactions of cobaltadithiolene complexes [CpCo(S₂ C₂Z₂)] (Z = CN, COOMe, Ph, Me) with aryl azides, two types of substitution reactions occurred. One is the replacements of the sulfur of cobaltadithiolene by arylimid

Full text of DOI:10.1016/S0022-328X(03)00599-0

Journal of Organometallic Chemistry 681 (2003) 180Á188
/
www.elsevier.com/locate/jorganchem
Reactions of cobaltadithiolene complexes with aryl azides
Formations of metal chelate rings containing nitrogen atoms by
substitution reactions via nitrene
Mitsushiro Nomura *, Asuka Kawakita, Hideaki Katsuta, Chikako Takayama 1,
Toru Sugiyama, Yasuo Yokoyama, Masatsugu Kajitani *
Faculty of Science and Technology, Department of Chemistry, Sophia University, 7-1, Kioi-cho, Chiyoda-ku, Tokyo 102-8554, Japan
Received 21 May 2003; received in revised form 18 June 2003; accepted 24 June 2003
Abstract
In the reactions of cobaltadithiolene complexes [CpCo(S2C2Z2)] (Zꢀ
substitution reactions occurred. One is the replacements of the sulfur of cobaltadithiolene by arylimido groups and the other is the
CZ moiety of cobaltadithiolene. The product of latter reaction was also formed by the reactions of the
/CN, COOMe, Ph, Me) with aryl azides, two types of
replacements of the SÃ
/
CZÄ
/
metal cluster complex [Cp4Co4S6] with aryl azides. The azides with electron-donating substituents gave these products in higher
yields than those with electron-withdrawing substituents. In these reactions, arylnitrenes as intermediates were predictable. The
reactions of [CpCo(dmit)] (dmitꢀ
dmit ligand by imido groups to give novel imine complexes [CpCo(S2C2S2CÄ
# 2003 Elsevier B.V. All rights reserved.
/
C3S5) with phenyl azide and tosyl azide led to the replacements of the terminal sulfur (CÄ
/
S) of the
/
NR)] (RꢀPh, Ts).
/
Keywords: Cobaltadithiolene; Azide; Sulfur replacement; Nitrene; 1,3-Dipole
1. Introduction
An azide also causes unique reactions to metal
complexes [5]. The reactions of azides with metal
complexes are mainly classified into two categories.
The first category is the reaction of azide as a 1,3-dipole:
Organic azides (RN3) are very important nitrogen
sources [1]. It forms three nitrogens-containing five-
membered heterocycles. An azide is one example of a
1,3-dipole like a diazo compound or an isocyanate. In
for example, [2ꢁ
[6b] and CoÃC and RhÃ
second category is the reaction of nitrene formed by an
azide: for example, the imido insertions into PtÃH [8],
MÃ(CO) (MꢀPd, Pt) [9], VÃV [10], and the replace-
/
3] cycloadditions to GeÄ
/
C [6a], WÄ
/
C
/
/
C [7] bond by an azide. The
general, 1,3-dipoles lead to [2ꢁ3] cycloadditions to an
unsaturated moiety [2]. However, 1,4-(P,N) and 1,3-
/
/
(P,N) dipolar cycloadditions of phosphorus azide to
/
/
/
MeO2CCÅ/CCO2Me (dimethyl acetylenedicarboxylate)
ment of coordinated halogen [11] or carbonyl [12] by an
imido group. In other reactions, N2 transfer [13] was
also reported. The most interesting point in the reactions
of metal complexes with azides is the fixing of an
unstable species. If a compound is unstable, the
compound is possibly to be stabilized by fixing to a
metal complex. An unstable nitrene fixing is one of such
examples. The phenylnitrene formed by phenyl azide
reacts with [MoCl4(PR3)2] [14] to give the stable imido
metal complex following oxidation of the metal center.
In addition, the tetraazadiene iron complex
[Fe(CO)3(N4Me2)] was reported to be formed by the
reaction of [Fe2(CO)9] with MeN3 [12]. In general, a
were reported [3]. On the other hand, an azide can be
converted to a nitrene (:NR) [4] as an unstable and
reactive nitrogen species by thermolysis and photolysis.
A nitrene is one of the important imido sources, because
it leads to an alkene aziridination and an amination due
to an addition and a CÃ
/
H insertion, respectively [4].
* Corresponding authors. Tel.:
32383361.
E-mail address: m-nomura@sophia.ac.jp (M. Nomura).
ꢁ/
81-3-32383366; fax:
ꢁ/81-3-
1
Current address: Department of Chemistry, University of British
Columbia, Vancouver, BC, Canada V6T 1Z1.
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00599-0

M. Nomura et al. / Journal of Organometallic Chemistry 681 (2003) 180Á
/188
181
tetraazadiene is unstable species; however, it stabilizes
by fixing to a metal complex. Other tetraazadiene
complexes were also reported in the reactions of
[CpCo(CO)2] [15a], [Ni(1,5-COD)2] [15b], [Pt(PPh3)4]
and [Pt(PPh3)2(C2H4)] [15c] with azides.
Scheme 1 and Table 1. All reactions were complicated
and various products were formed. Although the yields
of products 2Á4 were low yields in all cases, the products
/
were obtained as main ones. In this work, other
products could not be identified. The azides with
electron-donating substituent gave these products in
higher yields than those with electron-withdrawing
substituents. Although the reaction rate of complex 1
with FNPA was slow, the products of this reaction were
formed by the reaction after a sufficiently long time. The
reactions of p-nitrophenyl azide and FNPA with com-
plex 1 gave complexes 2c, 2d, 3c and 3d by the
replacement of sulfur by arylimido groups, however,
these reactions did not give the corresponding com-
In previous work, we focused on the fixation of an
S moiety of cobaltadithiolene
imido group to the CoÃ
/
complexes, because an imido complex is one of the
reagents for azirizination and amidation [16]. Although
the cobaltadithiolene ring has pseudo-aromaticity [17]
because of having 6p electrons, it also has unsaturation
between Co and S bond. An addition reaction can be led
to the CoÃ/S moiety of cobaltadithiolene ring. Various
adduct formations of cobaltadithiolene have been re-
ported: the alkylidene adduct [18], the alkene adduct [19]
and the norbornene adduct [20], which were formed by
the reactions with diazo compounds alkynes and quad-
ricyclane, respectively. Likewise, the reactions of cobal-
tadithiolene complex with sulfonyl azides (RSO2N3) give
plexes 4c and 4d by the elimination of the SÃ
moiety.
The reactions of other cobaltadithiolene complexes
[CpCo(S2C2Z2)] (ZꢀCOOMe, Ph, Me) with FNPA
/
CZÄ/CZ
/
were investigated. These reactions only gave complex
4d. According to the results of Table 1, the cobalta-
dithiolene complexes with electron-withdrawing substi-
tuents gave complexes 2d and 3d in higher yields than
those with electron-donating substituents, and the
cobaltadithiolene complex with an electron-donating
substituent gave complex 4d in higher yield than those
with electron-withdrawing substituents. In other reac-
tion, the reaction of complex 2a with phenyl azide gave
complexes 3a (10%) and 4a (10%). Similarly, we assume
that complex 3a was formed by the replacement of
sulfur with arylimido groups and complex 4a was
the
imido-bridged
cobaltadithiolene
COOMe, Rꢀ
adduct
C6H4Me,
[CpCo(S2C2Z2)(NSO2R)] (Zꢀ
/
/
Me) [21] due to addition reaction. It is assumed that this
imido-addition reaction is a 1,3-dipole reaction rather
than a nitrene reaction, because this reaction efficiently
occurs under refluxing benzene (80 8C), and this tem-
perature is lower than the decomposition temperature of
tosyl azide (155 8C) [22].
In this work, we focused on the reactions of cobalta-
dithiolene complexes with aryl azides, which generate
nitrene species under relatively low temperature [23]. In
this paper, we report the replacements of sulfur by
formed by the replacement of NPhÃ
/
CZÄ/CZ moiety.
arylimido groups and the replacements of the SÃ
/
CZÄ
/
The ORTEP drawings of complexes 4a and 4d are
shown in Figs. 1 and 2. These complexes have coordi-
natively unsaturated and penta-coordinated metal cen-
ter. The bond lengths between Co and S of complexes 4a
CZ moiety of cobaltadithiolene ring. (These results were
partially reported in a previous communication [24].) In
addition, the reactions of [CpCo(dmit)] (dmitꢀC3S5)
/
˚
(2.134 A) and 4d (2.150 A) were almost identical to that
˚
having five sulfur atoms with tosyl azide and phenyl
azide were also investigated.
of a typical cyclopentadienyl cobaltadithiolene complex
˚
(2.1 A) [26]. On the other hand, the bond lengths
˚
between Co and N of complexes 4a (1.80 A) and 4d
˚
2. Results and discussion
(1.796 A) were shorter than that of the CoÃ
/
S bond. The
five-membered metallacycles of these complexes re-
mained almost planar. The cyclopentadienyl ring and
the five-membered metallacycle of these complexes were
perpendicular to each other.
2.1. Reactions of cobaltadithiolene complexes with aryl
azides
The reaction of
[CpCo(S2C2Z2)] (Zꢀ
a cobaltadithiolene complex
CN; 1) with five equivalents
/
2.2. Nitrene trapping
of phenyl azide under refluxing xylene gave
three products [CpCo{(NPh)SC2(CN)2}] (2a), [CpCo-
{(NPh)2C2(CN)2}] (3a) and [CpCo{(NH)S(C6H4)}] (4a)
[24,25]. We assume that complexes 2a and 3a were
formed by the replacement of sulfur by phenylimido
group, and complex 4a was formed by the elimination of
A nitrene trapping experiment was performed. Cy-
clooctene as a nitrene scavenger and a solvent was added
into the mixture of complex 1 and FNPA, and then this
solution was made to react under the conditions
described in Scheme 1. If the corresponding nitrene
species is generated, aziridine due to an addition and the
the SÃ
/
CZÄ/CZ moiety of complex 1. The reactions of
complex 1 with other aryl azides, p-methylphenyl azide,
p-nitrophenyl azide and 3-fluoro-4-nitrophenyl azide
(FNPA) were investigated. These results are shown in
secondary amine due to a CÃ
formed. According to GCÁMS data, the mass number
of the corresponding aziridine or secondary amine, m/
/H insertion should be
/

182
M. Nomura et al. / Journal of Organometallic Chemistry 681 (2003) 180Á188
/
Table 1
Reactions of cobaltadithiolene complexes [CoCo(S2C2Z2)] with aryl azides (five equivalents)
Aryl azides
Time (h)
Z
Yield of 2 (%)
Yield of 3 (%)
Yield of 4 (%)
Recovery (%)
PhN3
5
5
CN
CN
12
17
2
6
3
1
6
0
0
0
3
4
0
0
5
6
7
11
10
10
27
10
33
49
p-MeC6H4N3
p-NO2C6H4N3
FNPA
5
CN
CN
24
24
24
24
9
FNPA
FNPA
FNPA
COOMe
Ph
Me
0
0
0
zꢀ
/
264, was detected. The mass numbers of the
the reactions of thiophene or 2,6-dimethylthiophene
with ethyl azidoformate (N3COOEt); such reactions
form N-carbetoxypyrroles [27]. This reaction reveals
that nitrene undergoes 1,4-addition to the thiophene
ring (Scheme 2). The formations of complexes 2 and 3
can also be explained by the similar case of thiophene.
Nitrene leads to addition reactions to the Co and the C
of cobaltadithiolene ring, and then the sulfur atom of
cobaltadithiolene is eliminated. These are the thiophene-
like reactions of cobaltadithiolene ring as an aromatic
heterocycle. Proposed mechanisms for the formation of
complexes 2 and 4 are shown in Scheme 3. On the other
hand, we consider that nitrene formed from aryl azide
azobenzene analogue due to a nitrene dimmerization
and the primary amine due to a hydrogen abstraction
were also detected at m/zꢀ
Therefore, the formations of complexes 2Á
/
308 and 156, respectively.
4 can be
/
explained by a nitrene reaction. In the reactions of
cobaltadithiolene complexes with aryl azides, the reac-
tions were complicated and the low yields of products
were obtained. The reason can be assumed by the strong
reactivity of a nitrene. When the reaction was performed
under refluxing benzene (80 8C), which was a milder
condition than refluxing xylene (140 8C), complexes 2Á4
/
were not obtained at all. The reason is that aryl azides
do not thermally decompose in refluxing benzene.
In the thiophene compound, a similar replacement
reaction of sulfur and imido group has been observed in
˚
Fig. 2. ORTEP drawing of 4d. Selected bond lengths (A): Co1Ã
/
S1,
˚
Fig. 1. ORTEP drawing of 4a. Selected bond lengths (A): Co1Ã
/
S1,
2.150(3); Co1Ã
C6, 1.44(1). Selected bond angles (8): S1Ã
C6, 99.5(3); Co1ÃN1ÃC1, 123.6(7); N1ÃC1Ã
114.6(7).
/
N1, 1.796(8); S1Ã
/
C6, 1.708(10); N1Ã
Co1ÃN1, 87.4(3); Co1Ã
C6, 114.8(9); S1ÃC6Ã
/
C1, 1.35(1); C1Ã
S1Ã
C1,
/
2.134(8); Co1Ã
1.41(2). Selected bond angles (8): S1Ã
99.5(6); Co1ÃN1ÃC1, 122(1); N1ÃC1Ã
/
N1, 1.80(1); S1Ã
/
C6, 1.76(2); N1Ã
Co1ÃN1, 87.8(5); Co1Ã
C6, 116(1); S1ÃC6Ã
/
C1, 1.37(2); C1Ã
/
C6,
C6,
/
/
/
/
/
/
/
S1Ã
/
/
/
/
/
/
/
/
/
/
/
/
/
C1, 113(1).
Scheme 1.

M. Nomura et al. / Journal of Organometallic Chemistry 681 (2003) 180Á
/188
183
FNPA. The formations of complexes 4aÁ/4c involve the
elimination of the alkene moiety of cobaltadithiolene.
Therefore, we conclude that only the units of Cp, Co
and S are necessary in the formations of complexes 4aÁ
/
4c. This cobalt cluster is known as a precursor of
cobaltadithiolene complexes and this cluster reacts with
alkynes to give cobaltadithiolene complexes [30]. In this
work, we found new synthetic methods of complexes
Scheme 2.
leads to the addition reaction to the CoÃ
cobaltadithiolene, because the CoÃS bond has unsatura-
tion [18Á21]. However, the expected adduct was not
/S bond of
/
4aÁ4c by the reaction of [Cp4Co4S6] with aryl azides.
/
/
formed at all. We have reported that cobaltadithiolene
complex reacts with sulfonyl azides as 1,3-dipoles to give
the imido-bridged cobaltadithiolene adducts [21]. These
results suggest that aryl azides as 1,3-dipoles do not
react with cobaltadithiolene complexes, if anything, the
arylnitrenes formed by the thermolysis of aryl azides
react with cobaltadithiolene complexes.
In another case, the replacements of CpCo moiety by
imido group have been reported in the reactions of
cyclopentadienyl cobaltacyclopentadiene complexes
with azides. This is one of the synthetic methods of
highly substituted pyrroles [28]. However, in the reac-
tions of cyclopentadienyl cobaltadithiolene complexes
with azides, the expected replacements of CpCo moiety
by imido group were not confirmed.
2.4. Reactions of CpCo(dmit) with azides
The reactions of [CpCo(dmit)] (5) with phenyl azide
and tosyl azide led to the replacement of terminal sulfur
by imido groups and these reactions gave the novel
imine complexes [CpCo(S2C2S2CÄ
and RꢀTs (6b), Scheme 5). In the IR spectra of
complexes 6a and 6b, the signals of CÄN stretching
/
NR)] (Rꢀ
/Ph (6a)
/
/
vibrations appeared at 1576 and 1472 cmꢂ1, respec-
tively. These results reveal that complexes 6a and 6b
have the phenylimine and the tosylimine moieties,
respectively. Complex 6b was formed in refluxing
benzene, and this temperature is lower than the decom-
position temperature of tosyl azide. Therefore, complex
6b can be formed without generating any nitrene species.
The analogous products [CpCo(dmiCN)] [31] and
2.3. Reactions of metal cluster complex with aryl azides
[CpCo{S2C2S2CÄ
/
C(COOMe)2}] [32] have already been
When the metal cluster complex [Cp4Co4S6] [29] was
made to react with aryl azides under refluxing xylene,
obtained in the reactions of complex 5 with tetracya-
noethylene oxide (TCNEO) and diazomalonate, respec-
tively. These complexes have a more elongated p system
(complex 6a: 688 nm; complex 6b: 648 nm; [CpCo(d-
complexes 4aÁ
reactions, the azide with an electron-donating substitu-
ent gave higher yield of complexes 4aÁ4c than that with
/4c were formed (Scheme 4). In these
/
miCN)]: 669 nm [31], [CpCo{S2C2S2CÄ
686 nm [32]) than a typical dithiolene complex (e.g.
[CpCo{S2C2(CN)2}]: 572 nm [26]).
In the reactions of TCNEO with cobaltadithiolene
complexes, two other types of reactions have already
been observed [33]. One is the reaction of cobaltadithio-
lene complexes bearing phenyl or ester groups
/C(COOMe)2}]:
an electron-withdrawing substituent. This substituent
effect is similar to that in the reactions of cobaltadithio-
lene complexes with aryl azides. However, the reaction
of [Cp4Co4S6] with FNPA did not give the desired
product 4d. This result may be because of the very low
reactivity of 3-fluoro-4-nitrophenylnitrene formed from
Scheme 3.

184
M. Nomura et al. / Journal of Organometallic Chemistry 681 (2003) 180Á188
/
Scheme 4.
[CpCo(S2C2Z2)] (Zꢀ
give the dicyanomethylene-bridged cobaltadithiolene
complexes due to the unsaturation of the CoÃS bond.
The other is the reaction of cobaltadithiolene complex
bearing 4-pyridyl groups [CpCo{S2C2(4-py)2}]; this
reaction gives the cobaltadithiolene complexes having
pyridinium dicyanomethylide groups. These three types
of reactions can be explained by the electrophilicity of
TCNEO [34].
/
Ph or COOMe). These reactions
arylimido groups, which is a thiophene-like reaction via
an arylnitrene [27]. This is one of the reactions due to the
aromaticity of the cobaltadithiolene ring. In other cases,
the electrophilic substitution and radical substitution
due to the aromaticity of cobaltadithiolene ring have
been reported [17]. We can synthesize the five-membered
metal chelate ring containing a nitrogen group by the
reactions of cobaltadithiolene complexes with arylni-
trenes. The second type of reaction to afford complexes
/
On the other hand, an azide is one example of a
nucleophile [1]. We assume that these azides lead to the
nucleophilic attack to the carbon of thiocarbonyl group,
and then the thiatriazoline moiety is formed via 1,3-
dipolar cycloaddition. In addition, complexes 6a and 6b
are formed by a desulfurization and molecular nitrogen
elimination. A plausible mechanism is shown in Scheme
5. A similar reaction has been reported in an organic
sulfur compound. The reaction of phenyl azide with
thioketone bearing hinder groups gives the correspond-
ing phenyl imine via an intermediate thiatriazoline [35].
4aÁ
moiety of [CpCo(S2C2Z2)] via an arylnitrene. Complexes
4aÁ4d could also be formed by the reactions of the metal
cluster complex [Cp4Co4S6] with aryl azides. This metal
cluster complex consisted of only Cp, Co and S units.
Therefore, in this reaction we conclude that only the
units of Cp, Co and S are necessary. The third type of
reaction we found was the replacement reaction of the
/
4d we found was the elimination of the SÃ
/
CZÄ
/
CZ
/
terminal sulfur (CÄ
/
S) of [CpCo(dmit)] by imido groups.
In this case, azides as 1,3-dipoles reacted with [CpCo(d-
mit)]. In this work, we found novel desulfurization
reactions by the reactions of sulfur-containing cobalt
complexes with azides.
2.5. Conclusion
Cobaltadithiolene complex [CpCo(S2C2Z2)] (Zꢀ
/
3. Experimental
COOMe) reacts with tosyl azide as a 1,3-dipole to give
the imido-bridged cobaltadithiolene complex due to the
unsaturation of the cobaltadithiolene ring [21]. In this
work, we found three other types of reactions in the
3.1. General remarks
reactions of [CpCo(S2C2Z2)] (Zꢀ
Me) and [CpCo(dmit)] with azides. The first was the
replacement reaction of sulfur of [CpCo(S2C2Z2)] by
/
CN, COOMe, Ph,
All reactions were carried out under argon atmo-
sphere by means of standard Schlenk techniques. The
cobaltadithiolene complexes [CpCo(S2C2Z2)] (ZꢀCN,
/
Scheme 5.

M. Nomura et al. / Journal of Organometallic Chemistry 681 (2003) 180Á
/188
185
COOMe, Ph, Me) [36] and [CpCo(dmit)] [37] were
prepared by the literature methods. The solvents of
reactions were purified by ketyl distillation before use.
The aryl azides were synthesized by known procedures;
the reactions of arylhydrazine hydrochloride with so-
dium nitrite. FNPA, silica gel and Wakogel C-300 were
obtained from Wako Pure Chemical Industries, Ltd.
Thin-layer chromatography plate filled silica gel 60 (20
solid (4a): m.p. 164 8C. Mass (EIꢁ, 70 eV) m/z (rel.
intensity) 247 ([Mꢁ], 100), 182 ([Mꢁ Ã
Cp], 34), 124
([CpCoꢁ], 9), 123 ([Mꢁ ÃCpCo], 7) ppm. 1H-NMR (500
MHz, CDCl3 vs. TMS) d 11.3 (broad, 1H, NH), 7.66 (d,
/
/
Jꢀ8.42 Hz, 1H, Ar), 7.39 (m, 2H, Ar), 6.97 (m, 1H,
/
Ar), 5.28 (s, 5H, Cp) ppm. 13C-NMR (125 MHz, CDCl3
vs. TMS) d 163.6, 148.7, 130.2, 124.7, 118.8, 118.7, 77.4
ppm. UVÁVis (CH2Cl2) lmax (o) 793 (1000), 571
/
cmꢃ
/
20 cm, 0.25 mm in thick) was obtained from
(14 600), 274 (19 300), 241 (15 000). IR (KBr disk)
3305, 3050, 1651, 1558, 1539, 1508, 1454, 756, 729
cmꢂ1. Anal. Calcd. for C11H10NSCo: C, 53.45; H, 4.08;
N, 5.67. Found: C, 53.64; H, 4.03; N, 5.70%.
Merck Japan Ltd. HPLC was performed using model
LC-908 produced by Japan Analytical Industry Co.
Mass and IR spectra were recorded on a JEOL JMS-
D300 and a Shimadzu model FTIR 8600PC, respec-
tively. GCÁ
GCMS-QP5000. NMR spectra were measured with a
JEOL LA500 spectrometer. UVÁVis spectra were re-
corded on Hitachi model UV-2500PC. Elemental ana-
lyses were determined by using a Shimadzu PE2400-II
instrument. Melting points were measured by Yanaco
model Micro melting point apparatus.
/
MS were measured with a Shimadzu model
3.2.2. Reaction of cobaltadithiolene complex 1 with p-
methylphenyl azide
/
A solution of complex 1 (80 mg, 0.3 mmol) and p-
methylphenyl azide (1.5 mmol) in xylene (20 ml) was
refluxed for 5 h. After the solvent was removed under
reduced pressure, the residue was separated by column
chromatography (Wakogel C-300) and then the product
was further separated by HPLC. Products 2b, 3b and 4b
were obtained in 17% (17.2 mg, 0.051 mmol), 3% (3.7
mg, 0.0090 mmol) and 4% (3.1 mg, 0.012 mmol) yields,
respectively. Purple solid (2b): Mass (EIꢁ, 70 eV) m/z
3.2. Reactions of cobaltadithiolene complex with aryl
azides
3.2.1. Reaction of cobaltadithiolene complex 1 with
phenyl azide
(rel. intensity) 337 ([Mꢁ], 100), 267 ([Mꢁ Ã
/
SCCN], 17),
C6H4Me], 22). H-NMR (500 MHz, CDCl3
vs. TMS) d 7.57 (d, Jꢀ7.94 Hz, 2H, Ar), 7.36 (d, Jꢀ
1
246 ([Mꢁ Ã
/
A solution of complex 1 (80 mg, 0.3 mmol) and
phenyl azide (1.5 mmol) in xylene (20 ml) was refluxed
for 5 h. After the solvent was removed under reduced
pressure, the residue was separated by column chroma-
tography (Wakogel C-300) and then the product was
further separated by HPLC. Products 2a, 3a and 4a were
obtained in 12% (11.6 mg, 0.036 mmol), 6% (6.9 mg,
0.018 mmol) and 3% (2.2 mg, 0.0089 mmol) yields,
respectively. Purple solid (2a): m.p. 167 8C. Mass (EIꢁ,
/
/
7.94 Hz, 2H, Ar), 5.08 (s, 5H, Cp), 2.50 (s, 3H, Me)
ppm. 13C-NMR (125 MHz, CDCl3 vs. TMS) d 156.6,
139.9, 137.9, 129.6, 123.7, 120.5, 118.3, 111.2, 80.1, 21.3
ppm. UVÁVis (CH2Cl2) lmax (o) 570 (10 400), 305
/
(18 200), 259 (16 400), 237 (19 400). IR (KBr disk)
3112, 3037, 2920, 2362, 2193, 1654, 1540, 1507, 1446,
1345, 1229, 1142, 1053, 838, 526, 518 cmꢂ1. HR-Mass
(EIꢁ, 70 eV) Calcd. for C16H12N3S1Co: 337.0084,
70 eV) m/z (rel. intensity) 323 ([Mꢁ], 100), 253 ([Mꢁ Ã
/
Found: 337.0090. Purple solid (3b): m.p. ꢀ300 8C.
/
SCCN], 28), 232 ([Mꢁ Ã
/
NPh], 36), 124 ([CpCoꢁ], 16).
Mass (EIꢁ, 70 eV) m/z (rel. intensity) 410 ([Mꢁ],
100), 91 ([C6H4Meꢁ], 46). 1H-NMR (500 MHz,
CDCl3 vs. TMS) d 7.64 (m, 4H, Ar), 7.32 (m, 6H,
Ar), 4.58 (s, 5H, Cp), 2.45 (s, 6H, Me). 13C-NMR (125
MHz, CDCl3 vs. TMS) d 154.5, 137.2, 129.5, 123.3,
1H-NMR (500 MHz, CDCl3 vs. TMS) d 7.68 (m, 3H,
Ar), 7.57 (m, 2H, Ar), 5.08 (s, 5H, Cp) ppm. 13C-NMR
(125 MHz, CDCl3 vs. TMS) d 158.8, 139.8, 129.1, 128.0,
124.0, 120.7, 118.2, 112.1, 80.1 ppm. UVÁVis (CH2Cl2)
/
lmax (o) 568 (5800), 376 (5100), 290 (21 000), 236
(11 800). IR (KBr disk) 3105, 2360, 2198, 1635, 1523,
121.8, 113.4, 78.5, 21.3 ppm. UVÁVis (CH2Cl2) lmax (o)
/
529 (10 300), 358 (16 500), 308 (14 400), 268 (16 000), 235
(15 500). IR (KBr disk) 3114, 3030, 2950, 2920, 2203,
1654, 1540, 1506, 1457, 1375, 1113, 797 cmꢂ1. HR-Mass
(EIꢁ, 70 eV) Calcd. for C23H19N4Co: 410.0943, Found:
410.0945. Purple solid (4b): Mass (EIꢁ, 70 eV) m/z (rel.
1508, 1489, 1053, 729 cmꢂ1
. Anal. Calcd. for
C15H10N3SCo: C, 55.73; H, 3.12; N, 13.00. Found: C,
55.80; H, 3.16; N, 13.21%. Purple solid (3a): Mass (EIꢁ,
70 eV) m/z (rel. intensity) 382 ([Mꢁ], 100), 129
([NPhCCNꢁ], 89), 124 ([CpCoꢁ], 6). 1H-NMR (500
MHz, CDCl3 vs. TMS) d 7.75 (m, 4H, Ar), 7.53 (m, 6H,
Ar), 4.59 (s, 5H, Cp) ppm. 13C-NMR (125 MHz, CDCl3
vs. TMS) d 156.8, 129.0, 127.4, 123.5, 121.9, 113.3, 78.6
intensity) 261 ([Mꢁ], 100), 196 ([Mꢁ Ã
NMR (500 MHz, CDCl3 vs. TMS) d 11.3 (broad, 1H,
NH), 7.43 (s, 1H, Ar), 7.27 (d, Jꢀ7.93 Hz, 1H, Ar), 6.83
/
Cp], 18). 1H-
/
(d, Jꢀ7.93 Hz, 1H, Ar), 5.22 (s, 5H, Cp), 1.83 (s, 3H,
/
ppm. UVÁ/Vis (CH2Cl2) lmax (o) 530 (13 000), 355
Me) ppm. 13C-NMR (125 MHz, CDCl3 vs. TMS) d
162.0, 149.3, 130.5, 128.9, 126.7, 118.5, 77.2, 21.8 ppm.
(19 000), 304 (16 300), 265 (17 000), 234 (17 400). IR
(KBr disk) 3062, 2206, 1635, 1589, 1508, 1485, 1419, 741
cmꢂ1. Anal. Calcd. for C21H15N4Co: C, 65.98; H, 3.95;
N, 14.65. Found: C, 66.05; H, 4.03; N, 14.84%. Purple
UVÁVis (CH2Cl2) lmax (o) 797 (1100), 578 (15 200), 276
/
(21 400), 241 (17 800). IR (KBr disk) 3307, 3094, 2917,
1654, 1636, 1617, 1577, 1559, 1540, 1457, 1350, 1193,

186
M. Nomura et al. / Journal of Organometallic Chemistry 681 (2003) 180Á188
/
1108, 1004, 809 cmꢂ1. HR-Mass (EIꢁ, 70 eV) Calcd.
for C12H12N1S1Co: 261.0023, Found: 261.0028.
(20 ml) was refluxed for 24 h. After the solvent was
removed under reduced pressure, the residue was
separated by thin-layer chromatography (silica gel 60)
and then the product was further separated by HPLC.
Product 4d was obtained in 5% (1.7 mg, 0.0055 mmol,
3.2.3. Reaction of cobaltadithiolene complex 1 with
p-nitrophenyl azide
A solution of complex 1 (80 mg, 0.3 mmol) and p-
nitrophenyl azide (1.5 mmol) in xylene (20 ml) was
refluxed for 5 h. After the solvent was removed under
reduced pressure, the residue was separated by column
chromatography (Wakogel C-300) and then the product
was further separated by HPLC. Products 2c and 3c
were obtained in 2% (2.2 mg, 0.0060 mmol) and 1% (1.4
mg, 0.0030 mmol) yields, respectively. Purple solid (2c):
Mass (EIꢁ, 70 eV) m/z (rel. intensity) 368 ([Mꢁ], 100),
Zꢀ
7% (2.4 mg, 0.0077 mmol, Zꢀ
Purple solid (4d): m.p. 171Á
172 8C. Mass (EIꢁ, 70 eV)
m/z (rel. intensity) 310 ([Mꢁ], 100), 264 ([Mꢁ Ã
NO2],
34), 124 ([CpCoꢁ], 55), 59 ([Coꢁ], 19). H-NMR (500
MHz, CDCl3 vs. TMS) d 7.47 (dd, Jꢀ9.77, 9.16 Hz,
/
COOMe), 6% (2.0 mg, 0.0065 mmol, Zꢀ
/
Ph) and
/Me) yields, respectively.
/
/
1
/
1H, Ar), 6.95 (dd, Jꢀ9.77, 4.58 Hz, 1H, Ar), 5.36 (s,
/
5H, Cp). 13C-NMR (125 MHz, CDCl3 vs. TMS) d
161.3, 149.6, 147.5, 140.8, 131.0, 129.0, 78.4. 19F-NMR
338 ([Mꢁ Ã
MHz, CDCl3 vs. TMS) d 8.50 (d, Jꢀ
7.87 (d, Jꢀ9.16 Hz, 2H, Ar), 5.15 (s, 5H, Cp). UVÁ
/
NO], 8.6), 124 ([CpCoꢁ], 36). 1H-NMR (500
9.16 Hz, 2H, Ar),
Vis
(376 MHz, CDCl3 vs. CFCl3) d ꢂ
Hz, 4.58) ppm. UVÁVis (CH2Cl2) lmax (o) 565 (11 200),
277 (15 200). IR (KBr disk) 3466, 1535, 1333, 1246
cmꢂ1 HR-Mass (EIꢁ, 70 eV) Calcd. for
/
132.9 (dd, Jꢀ/9.16
/
/
/
/
(CH2Cl2) lmax (o) 572 (2900), 293 (7500), 235 (6000).
HR-Mass (EIꢁ, 70 eV) Calcd. for C15H9N4O2S1Co:
367.9778, Found: 367.9775. Purple solid (3c): Mass
(EIꢁ, 70 eV) m/z (rel. intensity) 472 ([Mꢁ], 100), 124
([CpCoꢁ], 14). 1H-NMR (500 MHz, CDCl3 vs. TMS) d
.
C11H8N2O2F1S1Co: 309.9622, Found: 309.9611.
3.2.5. Nitrene trapping
A solution of complex 1 (30 mg, 0.11 mmol) and
FNPA (101 mg, 0.55 mmol) in cyclooctene (20 ml) was
8.31 (d, Jꢀ
/
8.93 Hz, 4H, Ar), 7.57 (d, Jꢀ8.93 Hz, 4H,
/
Ar), 4.67 (s, 5H, Cp). HR-Mass (EIꢁ, 70 eV) Calcd. for
C21H13N6O4Co: 472.0331, Found: 472.0324.
refluxed for 5 h. The GCÁ/MS of the reaction mixture
was measured.
3.2.4. Reactions of cobaltadithiolene complexes with
FNPA
3.2.6. Reactions of [Cp4Co4S6] with aryl azides
A solution of [Cp4Co4S6] (86 mg, 0.12 mmol) and aryl
A solution of complex 1 (29 mg, 0.11 mmol) and
FNPA (101 mg, 0.55 mmol) in xylene (20 ml) was
refluxed for 24 h. After the solvent was removed under
reduced pressure, the residue was separated by thin-
layer chromatography (silica gel 60) and then the
product was further separated by HPLC. Products 2d
and 3d were obtained in 9% (3.8 mg, 0.0098 mmol) and
6% (3.4 mg, 0.0067 mmol) yields, respectively. Purple
solid (2d): Mass (EIꢁ, 70 eV) m/z (rel. intensity) 386
([Mꢁ], 87), 124 ([CpCoꢁ], 50), 59 ([Coꢁ], 100). 1H-
NMR (500 MHz, CDCl3 vs. TMS) d 8.53 (m, 1H, Ar),
7.94 (m, 1H, Ar), 7.56 (m, 1H, Ar), 5.19 (s, 5H, Cp). 13C-
NMR (125 MHz, CDCl3 vs. TMS) d 235.0, 232.4, 227.0,
224.6, 218.3, 207.1, 131.0, 122.2, 119.6, 119.4, 80.3 ppm.
azides, PhN3, p-MeÃ
/
C6H4N3 or p-NO2Ã
/
C6H4N3 (2.5
mmol) in xylene (20 ml) was refluxed for 5 h. After the
solvent was removed under reduced pressure, the residue
was separated by column chromatography (Wakogel C-
300). Products 4a, 4b and 4c were obtained in 8% (9.5
mg, 0.038 mmol), 10% (12.5 mg, 0.048 mmol) and 5%
(7.0 mg, 0.024 mmol) yields, respectively. Purple solid
(4c): m.p. 218 8C. Mass (EIꢁ, 70 eV) m/z (rel. intensity)
292 ([Mꢁ], 100), 246 ([Mꢁ Ã
20). 1H-NMR (500 MHz, CDCl3 vs. TMS) d 11.3
(broad, 1H, NH), 8.62 (d, Jꢀ2.24 Hz, 1H, Ar), 7.82
/
NO2], 18), 124 ([CpCoꢁ],
/
(dd, Jꢀ
/
2.24, 9.16 Hz, 1H, Ar), 7.33 (d, Jꢀ9.16 Hz, 1H,
/
Ar), 5.42 (s, 5H, Cp) ppm. 13C-NMR (125 MHz, CDCl3
vs. TMS) d 167.0, 146.1, 138.4, 126.2, 120.2, 117.1, 78.4
UVÁ
/
Vis (CH2Cl2) lmax (o) 572 (6200), 292 (12 300). HR-
ppm. UVÁVis (CH2Cl2) lmax (o) 793 (750), 585 (11 400),
/
Mass (EIꢁ, 70 eV) Calcd. for C15H8N4O2F1S1Co:
385.9684, Found: 385.9698. Purple solid (3d): Mass
(EIꢁ, 70 eV) m/z (rel. intensity) 508 ([Mꢁ], 58), 192
([C6H3F(NO2)NCCNꢁ], 100), 124 ([CpCoꢁ], 38), 59
([Coꢁ], 6). 1H-NMR (500 MHz, CDCl3 vs. TMS) d 8.58
(m, 2H, Ar), 7.98 (m, 2H, Ar), 7.53 (m, 2H, Ar), 4.73 (s,
5H, Cp). 13C-NMR (125 MHz, CDCl3 vs. TMS) d
175.1, 163.0, 152.7, 136.6, 135.2, 133.7, 129.5, 123.2,
403 (5200), 284 (12 200), 236 (10 500). IR (KBr disk)
3335, 3109, 3088, 3081, 1577, 1570, 1559, 1540, 1496,
1483, 1473, 1453, 1121, 1054, 1041, 1007, 891, 843, 831,
813 cmꢂ1. Anal. Calcd. for C11H9N2O2SCo: C, 45.22;
H, 3.10; N, 9.59. Found: C, 45.28; H, 3.28; N, 9.69%.
3.2.7. Reaction of [CpCo(dmit)] with phenyl azides
A solution of complex 5 (105 mg, 0.33 mmol) and
phenyl azides (180 ml, 1.64 mmol) in xylene (20 ml) was
refluxed for 5 h. After the solvent was removed under
reduced pressure, the residue was separated by column
chromatography (Wakogel C-300) and then the product
was further separated by HPLC. Product 6a was
77.5 ppm. UVÁVis (CH2Cl2) lmax (o) 544 (2400), 361
/
(3100), 296 (3900). HR-Mass (EIꢁ, 70 eV) Calcd. for
C21H11N6O4F2Co: 508.0142, Found: 508.0136.
A solution of [CpCo(S2C2Z2)] (Zꢀ/COOMe, Ph, Me)
(0.11 mmol) and FNPA (101 mg, 0.55 mmol) in xylene

M. Nomura et al. / Journal of Organometallic Chemistry 681 (2003) 180Á
/188
187
obtained in 7% (8.8 mg, 0.023 mmol) yield. Green solid
(6a): Mass (EIꢁ, 70 eV) m/z (rel. intensity) 379 ([Mꢁ],
100), 276 ([CpCoS2C2S2ꢁ], 79), 212 ([CpCoS2C2ꢁ], 8),
200 ([CpCoS2Cꢁ], 32), 188 ([CpCoS2ꢁ], 36), 168
([CpCoSCꢁ], 62), 65 ([Cpꢁ], 15). 1H-NMR (500
MHz, CDCl3 vs. TMS) d 7.37 (m, 2H, Ar), 7.17 (m,
1H, Ar), 7.00 (m, 2H, Ar), 5.35 (s, 5H, Cp) ppm. 13C-
NMR (125 MHz, CDCl3 vs. TMS) d 173.2, 154.6, 154.3,
Table 2
Crystallographic data for compounds 4a and 4d
4a
4b
Formula
C
247.20
11H10NSCo
C11H8N2O2FSCo
310.19
purple
Formula weight (g molꢂ1
Crystal color
Crystal habit
)
purple
prismatic
prismatic
Crystal size (mm3)
0.13ꢃ
/0.13ꢃ
/
0.13ꢃ
0.47
monoclinic
/
0.17ꢃ
/
150.5, 129.8, 129.7, 129.5, 125.3, 120.0, 78.8 ppm. UVÁ
/
0.47
Crystal system
Space group
orthorhombic
Fdd2 (No. 43)
23.493(9)
Vis (CH2Cl2) lmax (o) 688 (15 700), 424 (2900). IR (KBr
disk) 1576 cmꢂ1. HR-Mass (EIꢁ, 70 eV) Calcd. for
C14H10N1S4Co: 378.9028, Found: 378.9026.
P21/n (No. 14)
7.495(2)
18.222(1)
8.403(1)
92.58(1)
1146.4(3)
4
˚
a (A)
˚
b (A)
28.611(5)
6.058(8)
˚
c (A)
b (8)
3
˚
V (A )
4072(5)
16
3.2.8. Reaction of [CpCo(dmit)] with tosyl azides
A solution of complex 5 (64 mg, 0.2 mmol) and tosyl
azides (31 ml, 0.2 mmol) in benzene (20 ml) was refluxed
for 2 h. After the solvent was removed under reduced
pressure, the residue was separated by column chroma-
tography (Wakogel C-300) and then the product was
further separated by HPLC. Product 6b was obtained in
37% (34 mg, 0.074 mmol) yield. Green solid (6b): m.p.
Z
Dcalc (g cmꢂ3
)
1.613
18.45
296
1.797
16.85
m(MoÁ
/
Ka) (cmꢂ1
)
T (K)
2umax (8)
Unique data (Rint
296
55.0
55.0
)
1277 (0.108)
591
113
2631 (0.044)
1098
171
Number of observations
Number of variables
R1, wR2 (all data)
Goodness-of-fit on F2
0.059, 0.067
1.58
0.060, 0.074
1.72
266Á
267 8C. Mass (EIꢁ, 70 eV) m/z (rel. intensity) 457
/
Largest difference peak and hole 0.50, ꢂ
/
0.47
0.56, ꢂ0.52
/
([Mꢁ], 100), 276 ([CpCoS2C2S2ꢁ], 29), 212
([CpCoS2C2ꢁ], 4), 200 ([CpCoS2Cꢁ], 7), 188 ([CpCoS2ꢁ],
], 20), 155 ([Tsꢁ], 23), 124 ([CpCoꢁ], 61), 91
([C6H4Meꢁ], 70), 65 ([Cpꢁ], 22), 59 ([Coꢁ], 7). 1H-
ꢂ3
˚
(e A
)
4. Supplementary material
NMR (500 MHz, CDCl3 vs. TMS) d 7.88 (d, Jꢀ8.44
/
Crystallographic data (excluding structure factors) for
the structures in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplemen-
tary publication Nos. CCDC 202772 (4a) and 202773
(4d). Copies of the data can be obtained free of charge
on application to The Director, CCDC, 12 Union Road,
Hz, 2H, Ar), 7.32 (d, Jꢀ8.44 Hz, 2H, Ar), 5.48 (s, 5H,
/
Cp), 2.44 (s, 3H, Me) ppm. 13C-NMR (125 MHz, CDCl3
vs. TMS) d 193.2, 171.1, 165.7, 144.5, 136.8, 129.8,
127.3, 79.4, 21.8 ppm. UVÁVis (CH2Cl2) lmax (o) 648
/
(11 800), 347 (10 000). IR (KBr disk) 1472, 1302, 1150,
1086 cmꢂ1. Anal. Calcd. for C15H12NO2S5Co: C, 39.38;
H, 2.64; N, 3.06. Found: C, 39.33; H, 2.58; N, 3.03%.
Cambridge CB2 1EZ, UK (Fax: ꢁ44-1223-336-033 or e-
/
mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.
ac.uk).
3.2.9. X-ray diffraction study
Measurements of complexes 4a and 4d were made on
a Rigaku AFC 5S diffractometer with graphite-mono-
Acknowledgements
chromated MoÁ
orientation matrix for data collection were obtained by
using 25 carefully centered reflections. The data were
/
Ka radiation. Cell constants and an
This work was supported by the Sasakawa Scientific
Research Grant, a grant-in-aid for Scientific Research
No. 14740369, and grants-in-aid on Priority-Area Re-
searches on ‘Interelements’ No. 09239246 and 11120251
from the Ministry of Education, Science, Sports and
Culture, Japan.
collected using the v Á2u scan technique to a maximum
/
2u value of 55.08. An empirical absorption correction
based on azimuthal scans of several reflections was
applied. The data were corrected for Lorentz and
polarization effects. Each structure was solved by direct
methods and expanded Fourier techniques. The non-
hydrogen atoms were refined anisotropically. The final
cycle of full-matrix least-squares refinement was based
on observed reflections and variable parameters (see
Table 2). Complexes 4a and 4d of idealized positions
were used for the teXsan crystallographic software
package of Molecular Structure Corp.
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