Reaction of aminocarbene complexes of chromium with alkynes 10. From large to small cyclic amines: Single versus double alkyne insertions

Article abstract of DOI:10.1016/S0022-328X(98)00671-8

For the purpose of comparing the reaction of various aminocarbene complexes of chromium with alkynes and to ascertain several points of the mechanism of their interaction, a series of complexes derived from large cyclic amines, HN(CH₂)_n (n≥6) and from a small cyclic amine (n=2) was synthesized. In the case of the larger amines, all the complexes examined herein, led to the expected bridgehead lactams 12 as the major product, providing strong evidence for a concerted rearrangement of an intermediate nitrogen-ylid complex such as 4. The X-ray structure of the lactam complex 12d (n=12) has been established in order to confirm the ring opening and the migration of the twelve carbon-atom alkyl chain from nitrogen to the γ-carbon. Interestingly, the last possibility, the migration from nitrogen to oxygen in 4, which had so far not been observed but which according to calculations should also be possible, took place in the case of complex 10b (n=7), giving rise, yet in low yield, to an alkoxypyrrole 14. Minor products resulting from annulation reactions without CO insertions, were also observed. For aminocarbene complexes derived from methylaziridine (n=2), important results, which substantiate previous observations, have been obtained especially as far as the mechanism of the insertion reaction is concerned: the regioselectivity of the ring-opening reaction could be established by X-ray crystallography on two isomeric complexes 25 and 26, the timing of the various steps could be determined by the examination of the reactivity of vinyl-aziridinyl carbene complexes 31 and 35 which led surprisingly to aziridinyl phenols 33 and 36. Finally, an unexpected product, the structure of which could also be established by X-ray crystallography as 27, and resulting from the oxidation at the α position of the carbonyl in complexes 25 or 26 was isolated during the interaction of complex 23 with diphenylacetylene.

Full text of DOI:10.1016/S0022-328X(98)00671-8

Journal of Organometallic Chemistry 567 (1998) 83–100
Reaction of aminocarbene complexes of chromium with alkynes 10.
From large to small cyclic amines: single versus double alkyne
insertions
Sophie Lafolle´e-Bezzenine a, Andre´e Parlier a, Henri Rudler a,*, Jacqueline Vaissermann b,
Jean-Claude Daran c
a Laboratoire de Synthe`se Organique et Organome´tallique UMR 7611, Uni6ersite´ P. et M. Curie, Tour 44–45, 4 place Jussieu,
75252 Paris Cedex 5, France
b Laboratoire de Chimie des Me´taux de Transition URA 419, Uni6ersite´ P. et M. Curie, Tour 44–45, 4 place Jussieu, 75252 Paris Cedex 5, France
c Laboratoire de Chimie de Coordination du CNRS, UPR 8241, 205 Route de Narbonne, 31077 Toulouse Cedex, France
Received 16 October 1997; received in revised form 5 January 1998
Abstract
For the purpose of comparing the reaction of various aminocarbene complexes of chromium with alkynes and to ascertain
several points of the mechanism of their interaction, a series of complexes derived from large cyclic amines, HN(CH2)n (n]6) and
from a small cyclic amine (n=2) was synthesized. In the case of the larger amines, all the complexes examined herein, led to the
expected bridgehead lactams 12 as the major product, providing strong evidence for a concerted rearrangement of an intermediate
nitrogen-ylid complex such as 4. The X-ray structure of the lactam complex 12d (n=12) has been established in order to confirm
the ring opening and the migration of the twelve carbon-atom alkyl chain from nitrogen to the k-carbon. Interestingly, the last
possibility, the migration from nitrogen to oxygen in 4, which had so far not been observed but which according to calculations
should also be possible, took place in the case of complex 10b (n=7), giving rise, yet in low yield, to an alkoxypyrrole 14. Minor
products resulting from annulation reactions without CO insertions, were also observed. For aminocarbene complexes derived
from methylaziridine (n=2), important results, which substantiate previous observations, have been obtained especially as far as
the mechanism of the insertion reaction is concerned: the regioselectivity of the ring-opening reaction could be established by
X-ray crystallography on two isomeric complexes 25 and 26, the timing of the various steps could be determined by the
examination of the reactivity of vinyl–aziridinyl carbene complexes 31 and 35 which led surprisingly to aziridinyl phenols 33 and
36. Finally, an unexpected product, the structure of which could also be established by X-ray crystallography as 27, and resulting
from the oxidation at the h position of the carbonyl in complexes 25 or 26 was isolated during the interaction of complex 23 with
diphenylacetylene. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Alkyne insertions; Aminocarbenes; Chromium; Nitrogen-containing heterocycles
1. Introduction
their use as starting material together with alkynes for
the synthesis of elaborate heterocyclic compounds, has
been observed [1–5].
At the same time, a thorough examination of the
mechanism of the depicted transformations has been
successfully undertaken. Most of the details of the
mechanism depicted in Scheme 1 could be deduced
from the insertion of diphenylacetylene into piperidine-
substituted aminocarbene complexes 1. The key step is
Although the chemistry of aminocarbene complexes
and especially their use as synthons in organic chem-
istry had been neglected for a long time, in contrast to
alkoxycarbene complexes, a fairly rapid progress in
* Corresponding author. Tel.: +33 44276197; fax: +33 44277089;
e-mail: rudler@ccr.jussieu.fr
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00671-8

84
S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
Scheme 1.
the formation of a stable nitrogen ylid intermediate 4
resulting from the successive insertion of the alkyne and
CO, leading via a new carbene complex 2, to a ketene
complex 3 bearing in k with respect to the electrophilic
central carbon atom of the ketene, a tertiary amine.
This favorable geometry induces the formation of a
zwitterionic intermediate 4, the rearrangement of which
leads mostly to a bridgehead lactam 5. Almost all the
steps of this insertion reaction could firmly be
established.
Fig. 1. Cameron projection of compound 12d with the atom number-
ing scheme.
The most probable mechanism for the rearrange-
ment, in agreement with theoretical work, is likely to be
a series of concerted (1,5) migrations of alkyl groups
from nitrogen to carbon. In the case of the smaller
cyclic amine methylaziridine, it has been found that the
course of the reaction was different since two series of
products were observed [6]. In the first one, the prod-
ucts are independent of the presence of the alkyne. In
the second one, a double insertion of alkyne, and a
single insertion of CO were observed: no ketene was
however formed (Scheme 2). Several mechanisms which
will be discussed, could account for the structure of the
end products.
The purpose of this paper is thus to further the
possibilities of these reactions, to provide more evi-
dence for the concertedness of the rearrangement reac-
tion, by the examination of the insertion of
diphenylacetylene into aminocarbene complexes derived
from large cyclic amines: if concerted, the reaction
should lead to bridgehead lactams in fairly good yields,
whatever the size of the cyclic amines may be. In the
case of aziridine-substituted complexes, experiments are
provided to establish that the ring-opening reaction is
regiospecific and that it probably takes place at the very
end of the transformation, and at least after the inser-
tion of one or two alkyne units.
2. Results and discussion
2.1. Aminocarbene complexes deri6ed from large cyclic
amines: intermolecular insertion of diphenylacetylene
The aminocarbene complexes 10a–d were synthesized
either by direct aminolysis of the alkoxycarbene com-
plexes according to Fischer, [7] or from the correspond-
ing amides by the use of the method of Hegedus, [8]
and isolated in respectively 59% (n=6), 90% (n=7),
80% (n=8), and 63% (n=12) yields as yellow solids.
The physical data of these new complexes agree with
those of previously described aminocarbene complexes
(see the experimental section).
2.2. Reaction with diphenylacetylene
When complex 10a was heated in refluxing benzene
in the presence of an excess of diphenylacetylene, com-
plete disappearance of the starting material was ob-
served after 24 h together with the formation of several
new complexes. Silica gel chromatography allowed the
separation of the main product of the reaction (47.3%)
as a yellow solid, m.p. 176°C. The physical data of this
complex agreed with those of the expected bridgehead
lactam complex 11a with an IR absorption at 1690cm−
1, two typical multiplets for the protons of the NCH2
1
group, at l 4.04 and 3.33 ppm in the H-NMR spec-
trum, and in the 13C-NMR spectrum, a signal for the
carbonyl group at l 180.0 ppm. Treatment of further
fractions of the chromatography with pyridine, in order
to remove the metal, and for the sake of simplicity,
allowed the separation of three products, the pyrrole
Scheme 2.

S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
85
Table 1
Table 1 (Continued)
Crystal data for 26
C44H31O4NCr
689.7
16.809(7)
12.183(3)
18.702(5)
90.
109.40(3)
90.
Crystal data for 20b
C22H21NO5Cr
431.4
16.856(4)
12.167(5)
21.154(7)
90.
94.62(2)
90.
4324(3)
8
Fw
a (A)
b (A)
c (A)
Fw
a (A)
b (A)
c (A)
˚
˚
˚
˚
˚
˚
h(°)
i(°)
k(°)
h(°)
i(°)
k(°)
3
˚
3
˚
V (A )
3612(36)
4
V (A )
Z
Z
Crystal system
Monoclinic
P21/a
3.49
1.27
Crystal system
Monoclinic
P21/a
5.45
Space group
Space group
Linear absorption coefficient v (cm−1
)
Linear absorption coefficient v (cm−1
)
Density z (g cm−3
Diffractometer
Radiation
)
Density z (g cm−3
Diffractometer
Radiation
)
1.33
CAD4 Enraf–Nonius
Mo–Kh (u=0.71069
CAD4 Enraf–Nonius
Mo–Kh (u=0.71069
˚
˚
A)
A)
Scan type
ꢀ/2q
Scan type
ꢀ/2q
Scan range (°)
q Limits (°)
0.8+0.345 tg q
1–25
Scan range (°)
q Limits (°)
0.8+0.345 tg q
1–25
Temperature of measurement
Octants collected
Nb of data collected
Nb of unique data collected
Nb of unique data used for refinement
Rint
Room temperature
−19,18; 0,14; 0,22
Temperature of measurement
Octants collected
Room temperature
0,20; 0,14; −25,25
8275
6992
6338
Number of data collected
Number of unique data collected
7586
1295 (Fo)2\3|(Fo)2
Number of unique data used for refinement 4515(Fo)2\3|(Fo)2
0.064
0.090
0.096
No
201
−0.40
0.40
Rint
0.0424
0.0617
0.0735
843
525
−0.29
0.65
R=ꢀꢁFoꢂ−ꢂFcꢁ/ꢀꢂFoꢂ
Rw=[ꢀ w(ꢂFoꢂ−ꢂ−ꢂFcꢂ)2/ꢀ wFo2]1/2
Extinction parameter
Nb of variables
R=ꢀꢁFoꢂ−ꢂFcꢁ/ꢀꢂFoꢂ
Rw=[ꢀ w(ꢂFoꢂ−ꢂ−ꢂFcꢂ)2/ꢀ wFo2]1/2
Extinction parameter
Nb of variables
−3
˚
˚
−3
˚
˚
Dzmin (e A
)
)
Dzmin (e A
)
)
−3
−3
Dzmax (e A
Dzmax (e A
Crystal data for 25
C44H3104NCr
689.7
13.216(12)
28.684(13)
Crystal data for 17d
C33H39
449.7
8.595(7)
23.163(11)
13.515(10)
N
Fw
a (A)
b (A)
Fw
a (A)
b (A)
˚
˚
˚
˚
˚
˚
c (A)
11.098(6)
c (A)
h(°)
i(°)
k(°)
90
100.66(8)
90
4134
h(°)
i(°)
k(°)
90
103.65(7)
90
2615(3)
3
˚
3
˚
V (A )
V (A )
Z
4
Z
4
Crystal system
Monoclinic
P21/n
3.05
Crystal system
Monoclinic
P21/a
0.60
1.14
Space group
Space group
Linear absorption coefficient v (cm−1
)
Linear absorption coefficient v (cm−1
)
Density z (g cm−3
Diffractometer
Radiation
)
1.11
Density z (g cm−3
Diffractometer
Radiation
)
Philips PW 1100
Mo–Kh(u=0.71069
CAD4 Enraf–Nonius
Mo–Kh (u=0.71069
˚
˚
A)
A)
Scan type
ꢀ/2q
Scan type
ꢀ/2q
Scan range (°)
q Limits (°)
0.8+0.345 tg q
2–25
Scan range (°)
q Limits (°)
0.8+0.345 tg q
1.5–22
Temperature of measurement
Octants collected
Nb of data collected
Nb of unique data collected
Nb of unique data used for refinement
Rint
Room temperature
−13,13; 0,30; 0,11
Temperature of measurement
Octants collected
Room temperature
0,9; 0,24; −14,13
3562
5520
5069
Number of data collected
Number of unique data collected
3196
1632 (Fo)2\3|(Fo)2
Number of unique data used for refinement 1238 (Fo)2\3|(Fo)2
0.059
0.124
0.127
No
241
−1.06
1.38
Rint
0.0118
0.135
0.136
No
138
−0.45
0.82
R=ꢀꢁFoꢂ−ꢂFcꢁ/ꢀꢂFoꢂ
Rw=[ꢀ w(ꢂFoꢂ−ꢂ−ꢂFcꢂ)2/ꢀ wFo2]1/2
Extinction parameter
Nb of variables
R=ꢀꢁFoꢂ−ꢂFcꢁ/ꢀꢂFoꢂ
Rw=[ꢀ w(ꢂFoꢂ−ꢂ−ꢂFcꢂ)2/ꢀ wFo2]1/2
Extinction parameter
Nb of variables
−3
˚
˚
−3
˚
˚
Dzmin (e A
)
)
Dzmin (e A
)
)
−3
−3
Dzmax (e A
Dzmax (e A

86
S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
Table 1 (Continued)
Structure 13 could be assigned to the less polar
product on the grounds of its physical data. The high
resolution mass spectrum, the IR, and the 13C-NMR
spectra confirmed the absence of oxygen but confirmed
also the presence of a single NCH2 group (l 4.03 and
41.6 ppm), and agreed with that of a pyrrole resulting
from the migration from nitrogen to the carbonyl-car-
bon in the intermediate ylid complex of the type 4,
followed by the elimination of oxygen. Similar products
had already been obtained during previous investiga-
tions [4].
Crystal data for complex 27
Crystal parameters
Fw(g)
Shape (color)
Size, mm
[C44H35N1O5Cr]2
1419.5
Box(red)
0.27, 0.17, 0.13
Orthorhombic
Pbca
12.155(1)
33.375(4)
35.694(5)
14480
8
5909
1.302
3.523
Crystal system
Space group
˚
a, A
˚
b, A
˚
c, A
3
˚
V A
Complex 10b had a slightly different behaviour: in-
deed, besides the expected complex 11b (yellow solid,
32.6%), its metal-free analog 12b (white solid, 10%), the
pyrrole 13b (0.6%), the indanone 15 (23%), and the
amine 16b (3.9%), a new compound was isolated yet in
low yield (1.5%) as a white solid. Although the mass
spectrum indicated the presence of all the elements of
the bridgehead lactam, and especially oxygen, no car-
bonyl was present either in the IR, or in the 13C-NMR
spectra.
Z
F(000)
z (calc.), g cm−3
v (Mo–Kh) cm−1
Data collection
Diffractometer
Monochromator
Radiation
IPDS Stoe
Graphite
Mo–Kh (u=0,71073)
100
Detector distance, mm
Scan mode
f Range, deg
f Incr., deg
Exposure time, mn
2q range, deg
No. of reflections collected
No. of independent reflections (Rm)
Reflections used, (I\2|(I))
Refinement
ƒ
0BƒB200
1.4
8
2.3B2qB42
56911
7623(0.081)
3712
1
Both the H- and 13C-NMR spectra agreed however
with the presence of a single NCH2 group with signals
respectively at l 3.85 and 39.96 ppm, very close to
those observed in the pyrrole 13b (l 4.13 and 44.36
ppm). Surprisingly, a deshielded signal appeared also in
1
the H- and 13C-NMR spectra, at respectively l 3.96
R
Rw
0.0437
0.0397
Chebyshev
3.01, −0.457, 2.70
1.20
ppm (for 2 protons) and at l 74.71 ppm (for a
methylene group): these observations are in agreement
with the presence of an OCH2 group. Taken together,
all these data fit with a structure such as 14, a result
which confirms that migration from nitrogen to oxygen
can take place during the rearrangement of the interme-
diate nitrogen ylid complexes.
Weighting scheme
Coefficient Ar
GOF
No. of variable parameters
461
13a (0.7%), the bridgehead lactam 12a, and the known
diphenylindanone 15.
Complexes 10c and 10d gave, in almost similar yields

S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
87
Fig. 2. Cameron projection of compound 17d with the atom numbering scheme.
compounds 11c,d. However, as for n=6, no products
derived from a nitrogen to oxygen migration could be
detected. The structure of the bridgehead lactam 12d
containing a 15-membered lactam could be ascertained
by an X-ray diffraction study. Its CAMERON projection
appears in Fig. 1, with the most important bond distances
and bond angles gathered in Table 2.
In the case of 10d, the structure of the annulation
product 17d has been established by X-ray in order to
locate the carbon–carbon double bond: Fig. 2 confirms
the allylic nature of the amine. The most important bond
distances and bond angles can be found in Table 3.
The formation of compounds 15, 16 and 17 can be
pictured as in Scheme 3: these compounds are the result
of annulation reactions without CO insertions, followed
by hydrogen migrations, respectively (1,3) for 17, and
(1,5) for 15 and 16 [3,9–11].
All the results observed herein confirm that even with
large cyclic amines the course of the reaction is what one
would expect for a concerted migration from nitrogen to
carbon: whatever the size of the ring in the starting
aminocarbene complexes, the main product of the reac-
tion is due to a migration, from nitrogen to the k–carbon.
2.3. Aminocarbene complexes deri6ed from large cyclic
amines: attempts to carry out intramolecular 6reactions
The successful insertion of diphenylacetylene into
aminocarbene complexes derived from large amines
prompted us to attempt the intramolecular version of this
reaction by incorporating the triple bond into the cyclic
amines. Previous results of this laboratory have indeed
demonstrated that alkynes, tethered to aminocarbene
complexes, can lead, upon insertion, to interesting poly-
cyclic systems [3,5]. Similar results might be expected, at
least on paper, starting for example from aminocarbene
complexes of structure 21.
Table 2
˚
Selected interatomic distances (A) and bond angles for 12d
O(1)ꢀC(16)
N(1)ꢀC(2)
C(1)ꢀC(14)
C(15)ꢀC(16)
1.23(1)
1.44(1)
1.33(1)
1.52(1)
N(1)ꢀC(1)
N(1)ꢀC(16)
C(14)ꢀC(15)
1.42(1)
1.35(1)
1.53(1)
C(1)ꢀN(1)ꢀC(2)
126.6(8)
C(1)ꢀN(1)ꢀC(16)
N(1)ꢀC(1)ꢀC(14)
C(14)ꢀC(15)ꢀC(16) 100.7(7)
O(1)ꢀC(16)ꢀC(15) 126.4(9)
108.9(8)
111.8(8)
C(2)ꢀN(1)ꢀC(16) 124.5(8)
C(1)ꢀC(14)ꢀC(15) 108.8(8)
O(1)ꢀC(16)ꢀN(1) 123.9(9)
N(1)ꢀC(16)ꢀC(15) 109.6(9)
For that purpose, cyclodecynylamine which is readily
available from decalone, was synthesized, [12] and used
to prepare two new complexes 21a and 21b (R=Et, Ph).
In order to have an idea about the geometry, and

88
S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
Scheme 3.
especially the orientation of the triple bond with respect
to the metal, which is fundamental for the insertion
reaction, an X-ray analysis was undertaken on complex
20b (R=Ph). The most important bond distances and
bond angles are found in Table 4. As it appears on the
ORTEP projection of Fig. 3, the phenyl group and the
ten-membered ring system are Z, a geometry which is
unfavorable for the insertion reaction since it moves the
triple bond away from the metal.
obtained. It is likely that, due to the distance of the
triple bond from the metal center, intermolecular reac-
tions prevail, leading exclusively to polymers.
2.4. Aminocarbene complexes deri6ed from small cyclic
amines: case of methyl aziridine
In a previous publication, [6] the insertion of alkynes
into aziridinylcarbene complexes was described. Several
conclusions had already been reached as far as their
reactivity and the mechanism of the insertion were
concerned.
Table 3
˚
Selected interatomic diatances (A) and bond angles (°) for 17d
N(1)ꢀC(1)
C(1)ꢀC(5)
C(3)ꢀC(4)
C(4)ꢀC(9)
C(6)ꢀC(7)
C(8)ꢀC(9)
1.47(2)
1.54(2)
1.48(2)
1.39(2)
1.40(2)
C(1)ꢀC(2)
C(2)ꢀC(3)
C(4)ꢀC(5)
C(5)ꢀC(6)
C(7)ꢀC(8)
1.57(2)
1.32(2)
1.40(2)
1.38(2)
1.37(2)
1.41(2)
N(1)ꢀC(1)ꢀC(2)
C(2)ꢀC(1)ꢀC(5)
C(2)ꢀC(3)ꢀC(4)
C(3)ꢀC(4)ꢀC(9)
C(1)ꢀC(5)ꢀC(4)
C(4)ꢀC(5)ꢀC(6)
C(6)ꢀC(7)ꢀC(8)
C(4)ꢀC(9)ꢀC(8)
111.4(13)
101.3(13)
111.2(14)
130.8(16)
108.8(15)
122.1(17)
123.8(19)
117.9(17)
N(1)ꢀC(1)ꢀC(5)
C(1)ꢀC(2)ꢀC(3)
C(3)ꢀC(4)ꢀC(5)
C(5)ꢀC(4)ꢀC(9)
C(1)ꢀC(5)ꢀC(6)
C(5)ꢀC(6)ꢀC(7)
C(7)ꢀC(8)ꢀC(9)
116.9(13)
110.1(13)
108.6(14)
120.5(16)
128.8(16)
115.8(18)
119.3(19)
Alkylation was nevertheless attempted on complexes
20a,b: it led to the yellow complexes 21a,b in 53% yield.
2.3.1. Thermolysis of complexes 21a,b
Heating of 21a or 21b in boiling benzene induced a
fast disappearance of the starting complexes. However,
only an intractable black mixture of products was

S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
89
Fig. 3. Cameron projection of complex 20b with the atom numbering scheme.
“ aziridinyl carbene complexes 6 do not behave like
other aminocarbene complexes since two main reac-
tions are observed: a reaction without insertion of
the alkyne leading, after destruction of the aziridine
ring-system, to nitriles and propene. (Scheme 2)
“ a double insertion of the alkyne together with the
cleavage of the three membered ring and CO inser-
tion. No products containing the intact aziridine
were however observed. On a mechanistic point of
view, it appears clearly that no ketene was formed
during the insertion.
determination of their exact structure, since crystals
suitable for an X-ray analysis could only be obtained
from one isomer. Thus, new attempts were made to
solve this problem by the introduction of a phenethyl
group on the carbene–carbon. Complex 22, prepared in
50% yield from Cr(CO)6 and the corresponding lithium
derivative PhCH2CH2Li followed by alkylation at oxy-
gen, reacted with methylaziridine to give the yellow
complex 23 as a mixture of E, Z isomers, in 90% yield.
Heating of complex 23 in refluxing benzene in the
presence of a two-fold excess of diphenylacetylene gave
six products which were separated by silica gel chro-
matography: the nitrile 24 (50% yield) resulting from
the thermal decomposition of the carbene complex,
without insertion of the alkyne (Scheme 5, path A), two
2.4.1. Regioselecti6ity of the ring-opening: X-ray struc-
ture of two isomeric complexes 25 and 26
For all the reactions examined so far two isomeric
complexes were obtained but no decisive information
was available from their physical data allowing the

90
S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
Fig. 4. Cameron Projection of complex 25 with the atom numbering scheme.
complexes, in respectively 30.7 and 6.6% yields, as red
solids; a slightly more polar third complex as a red solid,
in 1.8% yield, and finally two organic products. To the
two first complexes were assigned structures 25 and 26,
the Cr(CO)3 complexes of substituted tetrahydroindolizi-
dones. The physical data of these two products, which
are very close to those observed for similar complexes
prepared previously in this laboratory differ only slightly:
structure of this product was finally assessed by an X-ray
analysis which showed surprisingly the presence of a
hydroxyl group geminated to the methyl group. Its
Cameron projection is given in Fig. 6 and the bond
distances and bond angles in Tables 6 and 7. The mass
spectrum confirmed also the presence of a tertiary
alcohol, since an ion due to the loss of water is observed.
The origin of this complex is subject to speculation:
although the h position with respect to such a ketone is
easily oxidized, the result is unexpected, since the inser-
tion reactions were run by careful exclusion of oxygen.
Moreover, when the reaction was carried out under an
atmosphere of oxygen or in the presence of water, the
insertion reaction took place nevertheless, giving com-
plexes 25, 26, and 27: however no increase in the yield
of the last complex was observed.
To the last isolated products were assigned respec-
tively, structure 29, tetraphenylcyclopentadienone, a
common product to most insertion reactions, and 28, a
substituted pyridine. It originates from the tetrahydroin-
dolizidones 25 or 26, which are in fact substituted
dihydropyridines, as the result of the thermal cleavage of
a carbon–carbon and a carbon–nitrogen bond and the
formation of a carbon–nitrogen bond.
1
in their H- and 13C-NMR spectra: indeed the methyl
groups give doublets at respectively 1.46 and 1.85 ppm
1
in the H-NMR spectrum, and signals at l 12.82 and
17.41 ppm in the 13C-NMR spectrum.
The structure of the two isomers could finally be
established by X-ray crystallography. The ORTEP pro-
jections appear in Figs. 4 and 5, with the most important
bond distances and bond angles in Table 5. It follows
clearly that in both complexes the methyl group is in h
to the carbonyl group in the five-membered ring, and that
the difference originates from the orientation of the
methyl group with respect to the Cr(CO)3 group, being
trans in the main product of the reaction. All other
structural features are similar to those of the previously
described complexes of this type [6].
Finally, to the last complex, obtained in very low yield
as tiny red crystals was given structure 27: in contrast to
The important result of these investigations is the fact
that the three-membered ring is opened in a regioselective
manner, by cleavage at the more substituted carbon
atom. This result is akin to the ring-opening of substi-
tuted N-acylaziridines by nucleophiles which also takes
place at the more substituted carbon [13]. It is thus likely
1
the other complexes, its H-NMR spectrum disclosed a
singlet for the methyl group at l 2.25 ppm. Moveover,
the protons of the NCH2 group gave a set of two
doublets, at l 3.56 and 3.35 ppm. It results that the
methyl group must now be on a tertiary carbon. The

S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
91
Fig. 5. Cameron projection of complex 26 with the atom numbering scheme.
that a nucleophilic ring-opening also takes place during
the insertion of the alkynes into 23 to give 25 and 26. Its
nature will be established by the following experiences.
benzannulation reaction, and also its analog, the vinylan-
nulation reaction (Scheme 4) [14,15].
In previous work, we demonstrated however, that for
phenyl-substituted aziridinylcarbene complexes (6, R=
Ph), no benzannulation reaction was observed: only the
phenyl-substituted tetrahydroindolizidone complexes (9,
R=Ph) were formed. This result is probably linked to
the prefered cis relationship between the aziridine ring-
system and the metal, in the intermediate carbene com-
plex (Scheme 5) [6]. Such a preference might be avoided
by using less demanding substituents, such as the vinyl
group.
2.5. Insertion of diphenylacetylene in 6inyl
(aziridinyl) carbene complexes 31 and 35: formation
of aziridinyl-substituted phenols
The question that might be asked is whether the
aziridine-ring system will survive during an alkyne inser-
tion reaction, as in path B. A known reaction in which
the heteroatom-containing moiety of carbene complexes
is not directly involved in the alkyne insertion is the
For that reason, the synthesis of complexes 31 and 35
was undertaken via complexes 30 and 34 and isolated as
yellow crystals, in both cases in 57% yield.

92
S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
Thermolysis of 31 in boiling benzene, in the presence
of an excess of diphenylacetylene, did not lead to the
expected tetrahydroindolizidone complexes (9,
RꢁCHꢁCHPh) but gave, as in the previous cases, the
nitrile 32, in 53% yield, but also the aziridinyl-substi-
tuted phenol 33 in 19.4% yield, the product expected
from an annulation reaction with insertion of CO. Its
structure was established on the grounds of its combus-
1
tion analysis and its spectroscopic data: the H-NMR
spectrum confirmed the presence of 16 aromatic pro-
tons, a proton for the OH group at l 4.98 ppm, and all
the protons of the aziridinyl ring system. Complex 35
behaved almost similarly, the nitrile, methylacryloni-
trile, being lost during work-up. A single product, the
phenol 36 was isolated in 15.4% yield and characterized
by its physical data.
The important observation of this set of reactions is
the survival of the aziridine ring during the alkyne
insertion reaction, although a second reaction, during
which destruction of the ring takes place, is again
observed.(31“32)
Two mechanisms could account for the first set of
experimental observations:
“ a mechanism in which the first step of the reaction,
the ring-opening of the aziridine common to the two
observed products 7 and 9, is followed either by a
double alkyne insertion reaction (Scheme 5, path A)
Fig. 6. Cameron projection of complex 27 with the atom numbering
scheme (the phenyl groups have been omitted for sake of simplicity).
or by the elimination of propene giving a nitrile
complex.
“ a mechanism in which the aziridine ring remains as
such until at least the first insertion of the alkyne or
almost until the end of the insertion reaction (path
B).
Table 4
˚
Selected interatomic distances (A) and bond angles (°) for 20b
The latter set of results involving the vinyl aziridinyl
carbene complexes is rather in support of path B: two
independent reactions can thus take place, the first one
Cr(l)ꢀC(1)
N(1)ꢀC(111)
2.100(4) N(1)ꢀC(1)
1.307(5)
1.620(8)
1.442(9)
1.478(9)
1.462(8)
1.49(1)
1.492(6) C(111)ꢀC(112)
1.475(8) C(112)ꢀC(113)
1.47(1) C(114)ꢀC(115)
1.158(7) C(116)ꢀC(117)
1.47(1) C(118)ꢀC(119)
1.52(1)
C(111)ꢀC(120)
C(113)ꢀC(114)
C(115)ꢀC(116)
C(117)ꢀC(118)
C(119)ꢀC(120)
Cr(2)ꢀC(2)
Table 5
˚
Selected interatomic distances (A) and bond angles (°) for 25
2.086(4) N(2)ꢀC(2)
1.304(5)
1.555(7)
1.493(8)
1.488(7)
1.456(8)
1.532(9)
Cr(1)ꢀN(1)
Cr(1)ꢀC(8)
Cr(l)ꢀC(10)
N(1)ꢀC(1)
N(1)ꢀC(7)
C(1)ꢀC(21)
C(4)ꢀC(5)
C(6)ꢀC(7)
2.11(1)
2.28(2)
2.21(2)
1.41(2)
1.51(2)
1.50(2)
1.54(3)
1.55(2)
1.41(2)
Cr(l)ꢀC(1)
Cr(l)ꢀC(9)
O(1)ꢀC(6)
N(1)ꢀC(3)
C(1)ꢀC(10)
C(3)ꢀC(4)
C(4)ꢀC(6)
C(7)ꢀC(8)
C(9)ꢀC(10)
C(22)ꢀC(23)
C(1)ꢀN(1)ꢀC(7)
N(1)ꢀC(1)ꢀC(10) 116.0(13)
C(10)ꢀC(1)ꢀC(21) 125.4(14)
C(3)ꢀC(4)ꢀC(5)
C(5)ꢀC(4)ꢀC(6)
O(1)ꢀC(6)ꢀC(7)
N(1)ꢀC(7)ꢀC(6)
C(6)ꢀC(7)ꢀC(8)
C(8)ꢀC(9)ꢀC(10)
2.15(2)
2.18(2)
1.21(2)
1.50(2)
1.39(2)
1.57(2)
1.51(2)
1.52(2)
1.44(2)
1.51(2)
118.6(13)
N(2)ꢀC(211)
1.487(5) C(211)ꢀC(212)
1.509(7) C(212)ꢀC(213)
1.500(8) C(214)ꢀC(215)
1.173(7) C(216)ꢀC(217)
1.513(8) C(218)ꢀC(219)
1.526(8)
C(211)ꢀC(220)
C(213)ꢀC(214)
C(215)ꢀC(216)
C(217)ꢀC(218)
C(219)ꢀC(220)
C(1)ꢀN(1)ꢀC(111)
N(1)ꢀC(111)ꢀC(112)
C(112)ꢀC(111)ꢀC(120) 110.6(5) C(111)ꢀC(112)ꢀC(113) 118.3(5)
C(112)ꢀC(113)ꢀC(114) 125.2(8) C(113)ꢀC(114)ꢀC(115) 112.8(6)
C(114)ꢀC(115)ꢀC(116) 168.0(6) C(115)ꢀC(116)ꢀC(117) 169.5(6)
C(116)ꢀC(117)ꢀC(118) 113.2(5) C(117)ꢀC(118)ꢀC(119) 120.8(7)
C(118)ꢀC(119)ꢀC(120) 118.5(5) C(111)ꢀC(120)ꢀC(119) 109.9(5)
C(2)ꢀN(2)ꢀC(211)
N(2)ꢀC(211)ꢀC(212)
C(212)ꢀC(211)ꢀC(220) 114.8(4) C(211)ꢀC(212)ꢀC(213) 118.7(4)
C(212)ꢀC(213)ꢀC(214) 119.2(5) C(213)ꢀC(214)ꢀC(215) 111.9(5)
C(214)ꢀC(215)ꢀC(216) 169.1(5) C(215)ꢀC(216)ꢀC(217) 168.2(5)
C(216)ꢀC(217)ꢀC(218) 111.2(4) C(217)ꢀC(218)ꢀC(219) 115.1(5)
C(218)ꢀC(219)ꢀC(220) 117.1(4) C(211)ꢀC(220)ꢀC(219) 113.9(4)
128.5(4) Cr(l)ꢀC(1)ꢀN(1)
110.9(4) N(1)ꢀC(111)ꢀC(120)
123.5(3)
108.2(5)
C(8)ꢀC(9)
C(21)ꢀC(22)
C(1)ꢀN(1)ꢀC(3)
C(3)ꢀN(1)ꢀC(7)
N(1)ꢀC(1)ꢀC(21)
N(1)ꢀC(3)ꢀC(4)
C(3)ꢀC(4)ꢀC(6)
O(1)ꢀC(6)ꢀC(4)
C(4)ꢀC(6)ꢀC(7)
N(1)ꢀC(7)ꢀC(8)
C(7)ꢀC(8)ꢀC(9)
C(1)ꢀC(10)ꢀC(9)
1.57(2)
122.8(13)
111.9(12)
118.1(14)
99.4(13)
102.8(15)
124.7(17)
112.6(14)
101.7(12)
115.7(14)
119.5(14)
112.5(15)
114.1(15)
122.7(17)
97.5(13)
115.9(13)
120.0(15)
129.4(3) Cr(2)ꢀC(2)ꢀN(2)
108.5(4) N(2)ꢀC(211)ꢀC(220)
124.4(3)
108.0(4)
C(1)ꢀC(21)ꢀC(22) 109.8(14)
C(21)ꢀC(22)ꢀC(23) 109.5(14)

S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
93
Table 6
3. Conclusion
˚
Selected interatomic distances (A) and bond angles (°) for 26
A striking difference in the reactivity of aminocar-
bene complexes derived from large and from small
cyclic amines resulted from these investigations:
whereas the former complexes lead in most cases essen-
tially, via the classical insertion-rearrangement reac-
tions to bridgehead lactams, the latter complexes
undergo a double alkyne insertion reaction without
formation of intermediate ketenes and a regioselective
ring-opening followed by the insertion of CO. Side
products due to benzannulation reactions without in-
sertion of CO also took place in the case of the large
cyclic amines, whereas vinyl-substituted aziridinyl car-
bene complexes led to annulation products with inser-
tion of CO.
Cr(1)ꢀN(1)
Cr(1)ꢀC(8)
Cr(1)ꢀC(10)
N(1)ꢀC(1)
N(1)ꢀC(7)
C(1)ꢀC(21)
C(4)ꢀC(5)
C(6)ꢀC(7)
2.14(2)
2.32(2)
2.21(2)
1.39(2)
1.56(2)
1.59(2)
1.59(3)
1.50(3)
1.40(2)
Cr(1)ꢀC(1)
Cr(1)ꢀC(9)
O(1)ꢀC(6)
N(1)ꢀC(3)
C(1)ꢀC(10)
C(3)ꢀC(4)
C(4)ꢀC(6)
C(7)ꢀC(8)
C(9)ꢀC(10)
C(22)ꢀC(23)
C(1)ꢀN(1)ꢀC(7)
N(1)ꢀC(1)ꢀC(10) 121.2(18)
C(10)ꢀC(1)ꢀC(21) 120.7(18)
C(3)ꢀC(4)ꢀC(5)
C(5)ꢀC(4)ꢀC(6)
O(1)ꢀC(6)ꢀC(7)
N(1)ꢀC(7)ꢀC(6)
C(6)ꢀC(7)ꢀC(8)
C(8)ꢀC(9)ꢀC(10)
2.11(2)
2.25(2)
1.23(2)
1.50(2)
1.39(2)
1.50(3)
1.57(2)
1.55(2)
1.45(2)
1.55(3)
120.6(15)
C(8)ꢀC(9)
C(21)ꢀC(22)
C(1)ꢀN(1)ꢀC(3)
C(3)ꢀN(1)ꢀC(7)
N(1)ꢀC(1)ꢀC(21)
N(1)ꢀC(3)ꢀC(4)
C(3)ꢀC(4)ꢀC(6)
O(1)ꢀC(6)ꢀC(4)
C(4)ꢀC(6)ꢀC(7)
N(1)ꢀC(7)ꢀC(8)
C(7)ꢀC(8)ꢀC(9)
C(1)ꢀC(10)ꢀC(9)
1.59(3)
124.8(16)
108.5(15)
118.0(16)
103.8(16)
104.1(17)
123.3(19)
110.3(17)
100.6(14)
118.8(18)
116.4(18)
116.0(18)
109.6(17)
126.0(18)
95.4(16)
113.9(17)
121.8(18)
4. Experimental
C(1)ꢀC(21)ꢀC(22) 107.8(16)
C(21)ꢀC(22)ꢀC(23) 105.7(16)
General methods: 1H- and 13C-NMR spectra were
recorded respectively at 200 or 400 and 50 or 100 MHz.
IR spectra were recorded as solutions. Mass spectra are
m/z. Column chromatography was performed with
Merck silica gel (70–230 mesh) using various ratios of
ethyl acetate (EtOAc)/light petroleum ether (PE) or
dichloromethane/light petroleum ether as eluent. All
reagents were obtained from commercial suppliers and
used as received. Reactions were performed under an
argon atmosphere in carefully dried glassware. Solvents
were dried by distillation from a drying agent: THF
and Et2O from Na/benzophenone; CH2Cl2 from CaH2
and P2O5.
the driving force of which is the relief of ring strain, via
path A, gives nitriles, the second one, via path B, gives
an intermediate alkylidene complex 38, after a single or
a double alkyne insertion: nucleophilic attack of the
nitrogen atom at the alkylidene carbon would then lead
to the N-ylid 39, a well established reaction from this
laboratory [16]. Finally, an intramolecular nucleophilic,
and regioselective ring-opening would lead to the
metallacycle 40 which upon cyclocarbonylation can
give the observed complexes 9. Conversely, sigmatropic
and electrocyclic rearrangements of 37 or 38 could lead
to the same intermediate 40.
All the steps outlined in the above mechanism are
known from the literature. The exact reason for the
double alkyne insertion is not clear: it might be due to
a steric interaction between the substituted aziridine
and the metal, which inhibits the coordination of the
nitrogen to the metal, and thus the insertion of a CO
group.
4.1. Pentacarbonyl (N-hexamethylene) benzylidene
chromium (0) 10a
This
complex
was
obtained
from
(CO)5
CrꢁC(OEt)Ph and hexamethylene imine (1.45 ml, 12.9
mmol) in diethyl ether (150 ml) at 0°C. Evaporation of
the solvent under vacuum gave complex 10a as a yellow
solid (2.38 g, 58.7%); m.p. 71–72°C. IR(CHCl3) 2040,
1
1960, 1915 cm−1; H-NMR (CDCl3, 400 MHz) l 7.39
(2H, t, J=6Hz, Ar), 7.16 (1H, t, J=7.6 Hz, Ar), 6.74
(2H, dd, J=8.5 and 1.3 Hz, Ar), 4.45 (2H, t, J=6 Hz,
NCH2), 3.58 (2H, t, J=6.3 Hz, NCH2), 2.13–2.09
(2H, m, NCH2CH2), 1.82–1.78 (2H, m, NCH2
CH2), 1.68–1.64 (2H, m, NCH2CH2CH2), 1.58–
1.54 (2H, m, NCH2CH2CH2); 13C-NMR (CDCl3,
100 MHz) l 274.17 (CrꢁC), 224.35, 217.56 (CO),
153.20, 128.53, 125.57, 118.73 (Ar), 62.94, 56.96
(NCH2), 29.18, 28.03 (NCH2CH2), 26.48, 26.34
(NCH2CH2CH2). Anal. found (%): C, 56.87; H, 4.53,
N, 3.66. Calc. for C18H17NO5Cr: C, 56.99; H, 4.49; N,
3.69.
Scheme 4.

94
S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
Scheme 5.
4.2. Pentacarbonyl (N-heptamethyleneimine)
benzylidene chromium (0) 10b
4.4. Pentacarbonyl (N-dodecamethyleneimine)
benzylidene chromium (0) 10d
This was obtained from the corresponding amide
PhCON(CH2)7 according to the method of Hegedus
from Na2Cr(CO)5, TMSCl and Al2O3 as a yellow solid
This complex was obtained from the corresponding
amide according to the method of Hegedus as a yellow
oil in 63% yield. IR (CHCl3) 2040, 1965, 1910 cm−1
;
(89.6%); m.p. 80°C; IR (CHCl3) 2040, 1970, 1920cm−1
;
1H-NMR (CDCl3, 400 MHz,) l 7.37–6.73 (5H, m, Ar),
4.28 (2H, t, NCH2), 3.38 (2H, t, NCH2), 2.06 (2H, m),
1.63–1.19 (18H, m); 13C-NMR (CDCl3, 50 MHz) l
273.72 (CrꢁC), 224.26, 217.60 (CO), 153.24, 128.41,
125.51, 118.90 (Ar), 60.02, 54.48 (NCH2), 26.99, 26.07,
25.97, 25.56, 25.20, 24.89, 24.39, 23.26 (CH2). HRMS
found (M+ꢀ5CO): 323.1705. Calc. for C19H29NCr:
323.1706.
1H-NMR (CDCl3, 100 MHz) l 7.38 (2H, t, J=7.6 Hz,
Ar), 7.14 (1H, t, J=7.4 Hz, Ar), 6.74 (2H, d, J=7 Hz,
Ar), 4.40 (2H, t, J=5.8 Hz, NCH2), 3.64 (2H, t, J=6.1
Hz, NCH2), 2.18–2.12 (2H, m, CH2), 1.84–1.80 (2H,
m, CH2) 1.65–1.40 (6H, m, CH2); 13C-NMR (CDCl3,
100 MHz) l 275.23 (CrꢁC), 224.47, 217.50 (CO),
153.43, 128.36, 125.55, 118.94 (Ar), 63.96 (NCH2),
56.36 (NCH2), 27.17, 26.57, 25.28, 23.79 (CH2). Anal.
found (%): C, 58.00; H, 4.84; N, 3.47. Calc. for
C19H19NO5Cr: C, 58.01; H, 4.83; N, 3.56.
4.5. Reaction of complex 10a with diphenylacetylene
A solution of complex 10a (2.38 g, 6.28 mmol) in
benzene (85 ml) was refluxed in the presence of
diphenylacetylene (1.34 g, 7.53 mmol) for 22 h. After
evaporation of the solvent under vacuum, the residue
was chromatographed on silica gel. Elution with PE/
CH2Cl2 (80/20) then with PE/AcOEt (95/5) gave a
series of fractions containing mixtures of non-polar
complexes and organic products. Elution with PE/
AcOEt (90/10) first gave fractions containing 12a
(0.19g, 7.6%) as a white solid; m.p. 134–135 °C; IR
4.3. Pentacarbonyl (N-octamethyleneimine) benzylidene
chromium (0) 10c
This was obtained as above from the corresponding
1
amide as a yellow solid (80.6%); m.p. 77°C; H-NMR
(CDCl3, 400 MHz) l 7.38 (2H, t, J=7.7 Hz, Ar), 7.14
(1H, t, J=7.4 Hz, Ar), 6.77 (2H, d, J=7.7 Hz, Ar),
4.44 (2H, t, J=5.4 Hz, NCH2), 3.68 (2H, t, J=5 Hz,
NCH2), 2.28–2.26 (2H, m, NCH2CH2), 1.97–1.95 (2H,
m, NCH2CH2) 1.66–1.59 (8H, m, CH2);
1
(CHCl3) 1692 cm−1; H-NMR (CDCl3, 400 MHz) l
13C-NMR (CDCl3, 100 MHz) l 276.67 (CrꢁC),
224.48, 217.48 (CO), 153.95, 133.28, 128.49, 125.42,
118.84 (Ar), 64.10, 57.53 (NCH2), 27.61, 27.34, 27.20,
26.99, 26.39, 26.09 (CH2). Anal. found (%): C, 58.89;
H, 5.10; N, 3.57. Calc. for C20H21NO5Cr: C, 58.97; H,
5.16; N, 6.06.
7.4–6.86 15H, m, Ar), 4.08–4.02 (1H, m, NCHH),
3.39–3.35 (1H, m, CHH), 2.76 (1H, dd, J=13 and 7.4
Hz, ArCHH), 2.38 (1H, t, J=12 Hz, Ar CCHH),
1.97–1.83 (2H, m, CH2), 1.80–1.58 (4H, m, CH2),
1.49–1.29 (2H, m, CH2); 13C-NMR (CDCl3, 100 MHz)
l 183.22 (CO), 141.73, 138.71, 133.96, 128.76, 128.66,

S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
95
127.67, 127.53, 123.60 (C=C, Ar), 61.54 (CPh), 41.75
(NCH2), 35.68 (NCH2), 25.77, 25.57, 25.21, 20.05
(CH2). HRMS calc. for C28H27NO (M+): 393.2091.
Found: 393.2092. Then fractions containing complex
11a (1.57 g, 47.3%) as yellow crystals; m.p. 176°C, IR
4.99 (5H, m, ArCr), 4.01–3.97 (1H, m, NCH), 3.25–
3.16 (1H, m, NCH), 2.66 (1H, dd, J=13.8 and 7.8 Hz,
PhCꢀCH), 2.30 (1H, t, J=12.5 Hz, PhCꢀCH), 2.06–
1.85 (2H, m, CH2), 1.71–1.28 (8H, m, CH2); 13C-NMR
(CDCl3, 100 MHz) l 232.78 (CO), 178.53 (CO), 144.44,
134.65, 130.22, 129.86, 129.25, 128.87, 128.68, 128.48,
127.77, 127.19, 126.95, 126.26, 119.50, 111.03 (CꢁC,
Ar), 93.44, 93.34, 92.77, 91.07, 90.93 (PhCR), 58.05
(PhC(CH2)), 41.59 (NCH2), 40.19, (PhC(CH2)), 27.09,
23.33, 22.10, 21.03, 20.36 (CH2). HRMS found (M+
ꢀ3CO): 459.1654. Calc. for C32H29NO4 Cr 459.1654.
The first fractions of the chromatography were gath-
ered and treated with pyridine. A second chromatogra-
phy of the residue first gave with PE/CH2Cl2 (85/15) the
pyrrole 13b (12 mg, 0.6%) as a white solid; m.p. 142°C;
1H-NMR (CDCl3, 200 MHz) l 7.26–6.81 (15H, m, Ar),
4.13 (2H, t, J=5.9 Hz, NCH2), 2.73 (2H, t, J=5.4 Hz,
CꢁCꢀCH2), 1.85–1.22 (10H, m, CH2). 13C-NMR
(CDCl3, 50 MHz) l 136.88–124.66 (CꢁC, Ar), 44.36
(NCH2), 30.63, 30.12, 29.74, 27.06, 26.92, 20.30 (CH2).
HRMS found (M+): 391.2299. Calc. for C29H29N:
391.2299. Elution with PE/CH2Cl2 (80/20) gave pyrrole
14 (31 mg, 1.5%) as a solid; m.p. 51°C; 1H-NMR
(CDCl3, 200 MHz) l 7.34–6.92 (15H, m, Ar), 3.96 (2H,
t, J=5.3 Hz, OCH2), 3.85 (2H, m, NCH2), 1.64–1.49
(10H, m, CH2). 13C-NMR (CDCl3, 50 MHz) l 143.71–
119.94, 104.42 (CꢁC, Ar), 74.71 (OCH2), 39.96 (NCH2),
29.73, 27.83, 26.84, 24.92, 23.29 (CH2). HRMS found
(M+) 407.2249. Calc. for C29H29NO: 407.2249. Then
the amine 17b (75 mg, 3.9%) as a white solid; m.p.
1
(CHCl3) 2010, 1930, 1690 cm−1; H-NMR (CDCl3, 400
MHz) l 7.34–6.99 (10H, m, Ar), 5.65–5.04 (5H, m,
Ar), 4.06–4.00 (1H, m, CHH), 3.36–3.29 (1H, m,
NCH), 2.68(1H, dd, J=13.5 and 7 Hz, Ar CꢀCH), 2.24
(1H, t, J=12 Hz, ArCꢀCH), 1.98–1.88 (2H, m, CH2),
1.69–1.52 (4H, m, CH2), 1.38–1.18 (2H, m, CH2).
13C-NMR (CDCl3, 100 MHz) l 232.86 (CO), 180.00
(CO), 143.08, 134.28, 130.10, 129.69, 128.86, 128.66,
128.54, 127.15, 120.88, 109.94 (CꢁC, Ar), 93.74, 93.05,
90.43 (ArꢀCr), 58.37 (PhC(CH2)), 42.22 (NCH2), 40.42
(PhC(CH2)) 26.22, 25.74, 25.44, 21.53 (CH2). HRMS
found (M+ꢀ3CO): 445.1496. Calc. for C28H27NOCr
(M+3CO): 445.1498. The less polar fraction of the first
chromatography were treated with pyridine. Evapora-
tion of pyridine under vacuum, followed by chromatog-
raphy of the residue gave first with PE/CH2Cl2 (80/20)
the pyrrole 13a (16 mg, 0.7%) as an oil; 1H-NMR
(CDCl3, 400 MHz) l 7.56–6.87 (15H, m, Ar), 4.04–
4.03 (2H, m, NCH2), 2.78–2.76 (2H, m, CꢁCꢀCH2),
1.83–1.28 (8H, m, 4 CH2); 13C-NMR (CDCl3, 100
MHz) l 136.91–119.99 (CꢁC, Ar), 41.59, (NCH2),
33.22, 31.52, 26.18, 24.14, 23.92 (CH2). HRMS calc. for
C28H27N. Found: 377.2143. Elution with PE/AcOEt
(95/5) gave fractions containing diphenylindanone 15
1
(0.17 g, 9.7%) as an oil; IR(CHCl3) 1705 cm−1; H-
1
38°C; H-NMR (CDCl3, 400 MHz), l 7.69–7.02 (14H,
NMR (CDCl3, 400 MHz) l 7.94–7.14 (m, 14H, Ar),
4.62 (1H, d, COCHPh), 3.85 (1H, d, CHPh); 13C-NMR
(CDCl3, 100 MHz) l 205.4 (CO), 156.3–123.9 (Ar),
64.7 (COCHPh), 53.82 (CHPh).
m, Ar), 5.01 (1H, s, CH), 2.73 (4H, m, 2 NCH2),
1.75–1.21 (10H, m, 5 CH2); 13C-NMR (CDCl3, 100
MHz) l 144.94–120.44(CꢁC, Ar), 74.73 (CH), 52.02
(2CH2), 28.53, 27.89, 25.03 (CH2). HRMS found (M+)
379.2299. Calc. for C28H29N: 379.2299.
4.6. Reaction of complex 10b with diphenylacetylene
4.7. Reaction of complex 10c with diphenylacetylene
The reaction was carried out as above with complex
10b (2 g, 5.09 mmol) and diphenylacetylene (1.1 g, 6.11
mmol). A first chromatography of the residue gave with
PE/CH2Cl2 fractions containing both organic products
and complexes. Elution with PE/AcOEt (95/5) gave
diphenylindanone 15 (0.42 g, 23%); elution with PE/
AcOEt (90/10) gave 12b (0.3 g, 14.7%) as a white solid;
The reaction was carried out as above with complex
10c (2.0 g, 4.91 mmol) and diphenylacetylene (1.0 g,
5.89 mmol). Silica gel chromatography as above first
gave complex 18c (0.15 g, 5.8%) as a yellow solid; m.p.
;
140°C; IR (CHCl3) 1960, 1885 cm−1 1H-NMR
(CDCl3, 200 MHz) l 7.4–7.1 (9H, m, Ar), 6.15–5.05
(6H, m, ArCr), 2.75 (4H, m, 2 NCH2), 1.8–1.05 (12H,
m, 6CH2); 13C-NMR (CDCl3,100 MHz) l 233.56 (CO),
146,5–114.17, (CꢁC, Ar), 92.8–86.76 (ArCr) 73 27
(CH), 49.8 (2 NCH2), 26.4, 24.9, 22.2 (6CH2). HRMS
found (M+): 529.1709. Calc. for C32H31NO3Cr:
529.1706. Then the amine 17c (88 mg, 4.6%) as a solid;
1
m.p. 60°C; IR (CHCl3) 1698 cm−1; H-NMR (CDCl3,
400MHz) l 7.36–6.77 (15H, m, Ar), 3.95–3.80 (1H, m,
NCH
m, PhCCHH
6
H), 3.23–3.10 (1H, m, NCHH
6
), 2.64–2.54 (1H,
), 1.68–1.25
6
), 2.44–2.34 (1H, m, PhCCHH
6
(10H, m, 5 CH2); 13C-NMR (CDCl3, 100 MHz) l
181.70 (CO), 142.82–123.41 (CꢁC, Ar), 61.33 (CPh),
41.41 (NCH2), 33.91, 27.17, 23.43, 22.44, 20.68, 20.30
(CH2). HRMS found (M+): 407.2249. Calc. for
C29H29NO: 407.2249. Elution with PE/AcOEt (70/30)
gave complex 11b (0.9 g, 32.6%) as a yellow solid, m.p.
1
m.p. 102°C. H-NMR (CDCl3, 400 MHz) l 7.73–6.97
(14H, m, Ar), 5.07 (1H, s, CH), 2.75–2.60 (4H, m,
2NCH2), 1.50–0.92 (12H, m, 6CH2); 13C-NMR
(CDCl3, 100 MHz) l 146.01–120.49 (Ar, CꢁC), 72.95
(NCH), 50.04 (2 NCH2), 26.63, 25.05, 22.26 (6CH2).
HRMS found (M+): 393.2456. Calc. for C29H31N:
67°C; IR(CHCl3) 2008, 1930, 1690cm−1
.
1H-NMR
(CDCl3, 400 MHz) l 7.38–7.00 (10H, m, Ar), 5.96–

96
S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
Table 7 (Continued)
Table 7
Selected bond angles (°) and interatomic distances for complex 27
Molecule 1
Molecule 1
Cr(1)ꢀC(4)
C(10)ꢀO(10)
C(20)ꢀO(20)
C(30)ꢀO(30)
N(1)ꢀC(1)
N(1)ꢀC(5)
N(1)ꢀC(8)
C(1)ꢀC(2)
C(1)ꢀC(11)
C(2)ꢀC(3)
C(2)ꢀC(21)
C(3)ꢀC(4)
C(3)ꢀC(31)
C(4)ꢀC(5)
C(4)ꢀC(41)
C(5)ꢀC(6)
C(5)ꢀC(51)
C(6)ꢀC(7)
C(6)ꢀO(1)
C(7)ꢀC(8)
C(7)ꢀO(7)
C(7)ꢀC(71)
C(11)ꢀC(12)
C(12)ꢀC(13)
2.291(4)
1.163(5)
1.170(6)
1.170(6)
1.400(6)
1.509(5)
1.474(6)
1 393(6)
1.512(6)
1.440(6)
1.502(6)
1.405(6)
1.483(7)
1 539(6)
1.498(7)
1.522(7)
1.531(7)
1.549(7)
1.198(5)
1.529(7)
1.426(6)
1 499(8)
1.526(7)
1.511(7)
Bond angles
C(10)ꢀCr(1)ꢀC(20)
C(10)ꢀCr(1)ꢀC(30)
C(20)ꢀCr(l)ꢀC(30)
C(10)ꢀCr(1)ꢀN(1)
C(20)ꢀCr(1)ꢀN(1)
C(30)ꢀCr(1)ꢀN(1)
C(10)ꢀCr(1)ꢀC(1)
C(20)ꢀCr(1)ꢀC(1)
C(30)ꢀCr(l)ꢀC(1)
Cr(1)ꢀC(10)ꢀO(10)
Cr(1)ꢀC(20)ꢀO(20)
Cr(l)ꢀC(30)ꢀO(30)
Cr(1)ꢀN(1)ꢀC(5)
C(1)ꢀN(1)ꢀC(5)
Cr(1)ꢀN(1)ꢀC(8)
C(1)ꢀN(1)ꢀC(8)
C(5)ꢀN(1)ꢀC(8)
N(1)ꢀC(1)ꢀC(2)
Cr(1)ꢀC(1)ꢀC(11)
N(1)ꢀC(1)ꢀC(11)
C(2)ꢀC(1)ꢀC(11)
C(1)ꢀC(2)ꢀC(3)
Cr(1)ꢀC(2)ꢀC(21)
C(1)ꢀC(2)ꢀC(21)
C(3)ꢀC(2)ꢀC(21)
C(2)ꢀC(3)ꢀC(4)
Cr(1)ꢀC(3)ꢀC(31)
C(2)ꢀC(3)ꢀC(31)
C(4)ꢀC(3)ꢀC(31)
Cr(1)ꢀC(4)ꢀC(5)
C(3)ꢀC(4)ꢀC(5)
Cr(l)ꢀC(4)ꢀC(41)
C(3)ꢀC(4)ꢀC(41)
C(5)ꢀC(4)ꢀC(41)
N(1)ꢀC(5)ꢀC(4)
N(1)ꢀC(5)ꢀC(6)
C(4)ꢀC(5)ꢀC(6)
N(1)ꢀC(5)ꢀC(51)
C(4)ꢀC(5)ꢀC(51)
C(6)ꢀC(5)ꢀC(51)
C(5)ꢀC(6)ꢀC(7)
C(5)ꢀC(6)ꢀO(1)
C(7)ꢀC(6)ꢀO(1)
C(6)ꢀC(7)ꢀC(8)
C(6)ꢀC(7)ꢀO(7)
C(8)ꢀC(7)ꢀO(7)
C(6)ꢀC(7)ꢀC(71)
C(8)ꢀC(7)ꢀC(71)
O(7)ꢀC(7)ꢀC(71)
N(1)ꢀC(8)ꢀC(7)
C(1)ꢀC(11)ꢀC(12)
C(11)ꢀC(12)ꢀC(13)
86.3(2)
89.8(2)
83.3(2)
106.3(2)
167.3(2)
97.7(2)
143.8(2)
129.5(2)
90.0(2)
176.9(5)
174.0(5)
176.1(5)
96.0(2)
122.4(3)
127.5(3)
122.0(4)
110.1(3)
117.4(4)
128.3(3)
119.1(4)
123.6(4)
119.5(4)
133.0(3)
119.0(4)
121.4(4)
120.6(4)
132.6(3)
118.7(4)
120.5(4)
89.1(3)
393.2456. Then the enamine 16c (0.10 g, 5.2%) as a
solid; m.p. 114°C. 1H-NMR (CDCl3, 200 MHz) l
7.6–7.0 (14H, m, Ar) 4.76 (1H, s, CH), 3.21 (4H, m,
2 NCH2), 1.8–1.45 (12H, m, 6 CH2); 13C-NMR
(CDCl3, 50 MHz) l 148.25–120.5 (Ar), 57.3 (CH),
51.5 (2NCH2), 27.5, 25.6, 23.0 (6CH2). HRMS found
(M+): 393.2456. Calc. for C29H31N: 393.2456. Then
diphenylindanone 15 (0.10 g, 8%) and then complex
11c (1.02 g, 37,4%) as a yellow solid; m.p. 148°C; IR
118.1(4)
129.1(3)
119.0(4)
119.2(4)
103.0(3)
97.0(3)
(CHCl3) 1965, 1885, 1685 cm−1 1H-NMR (CDCl3,
.
200 MHz) l 7.5–7.0 (10H, m, Ar), 6.2–4.8 (5H, m,
ArCr), 4.2 (1H, dt, J=14 and 4 Hz, NCH), 3.3 (1H,
115.3(4)
115.0(4)
115.4(4)
109.6(4)
110.3(4)
126.5(5)
123.1(5)
103.1(4)
107.8(4)
105.3(4)
113.3(5)
114.8(5)
111.8(5)
104.4(4)
114.2(4)
110 2(4)
dt, J=14 and
4 Hz, NCH), 2.6–2.3 (2H, m,
PhꢀCꢀCH2), 1.9–1.1 (12H, m, 6CH2). 13C-NMR
(CDCl3, 100 MHz) l 232.8 (CO), 178.48 (CO),
143.57–111.58, (CꢁC, Ar), 94.11–90.6 (ArCr), 57.92
(PhꢀC), 41.56 (NCH2), 40.28 (PhꢀCꢀCH2), 26.92,
26.59, 26.37, 24.43, 23.38, 23.12 (6CH2). HRMS
found (M+ꢀ3CO): 473.1811. Calc. for C30H31NO:
473.1811. And finally 12c (0.21 g, 11%) as a white
solid; m.p. 173–174°C; IR (CHCl3) 1696 cm−1 1H-
.
NMR (CDCl3, 200 MHz) l 7.4–6.59 (15H, m, Ar),
4.07 (1H, dt, J=14 and 4 Hz, NCH), 3.06 (1H, dt,
J=14 and 4 Hz, NCH), 2.6–2.3 (2H, m, PhꢀCꢀCH2),
1.7–1.0 (12H, m, 6CH2). 13C-NMR (CDCl3, 50 MHz)
l 181.55 (CO), 141.87–123.48, (CꢁC, Ar), 41.28
(NCH2), 32.70 (PhCCH2), 26.83, 26.65, 26.56, 24.71,
23.06, 21.56 (6CH2). HRMS found (M+) 421.2404.
Calc. for C30H31NO: 421.2405.
˚
Interatomic distances (A)
Cr(1)ꢀC(10)
Cr(1)ꢀC(20)
Cr(1)ꢀC(30)
Cr(1)ꢀN(1)
Cr(1)ꢀC(1)
Cr(l)ꢀC(2)
1.828(6)
1.806(6)
1.807(6)
2.135(4)
2.154(4)
2.183(5)
2.229(4)
Cr(1)ꢀC(3)

S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
97
4.8. Reaction of complex 10d (n=12) with
diphenylacetylene
cm−1
NH), 4.87–4.75 (1H, m, NCH), 2.26 (3H, s, Me),
2.65–2.53 (1H, m, CHꢀCHH), 2.36–2.23 (2H, m,
CꢁCꢀCHH), 2.18–2.10 (2H, m, CꢁCꢀCHH), 1.96–1.60
;
1H-NMR (CDCl3, 400 MHz,) l 8.48 (1H, s,
6
The reaction was carried out as above starting from
complex 10d (2 g, 4.32 mmol) and diphenylacetylene
(0.9 g, 20% excess). Silica gel chromatography of the
residue gave with PE as eluent the amine 17d (37 mg,
6
6
(8H, m, 4 CH2), 1.57–1.47 (1H, m); 13C-NMR (CDCl3,
100MHz) l 277.78 (CꢁCr), 223.0, 218.17 (CO), 85.57,
84.05 (CꢂC), 56.39 (NCH), 35.31 (Me), 34.60, 31.21,
24.92, 24.37, 23.99, 18.61, 18.49 (CH2). Anal. calc. for
C17H19NO5Cr (%): C, 55.28; H, 5.15; N, 3.79. Found:
C, 55.13; H, 5.20; N, 3.67.
1
1.9%) as a solid; m.p. 166°C; H-NMR (CDCl3, 400
MHz) l 7.59–7.08 (14H, m, Ar), 5.01 (1H, s, NCH),
2.55–2.51 (2H, m, NCH2), 2.36–2.32 (2H, m, NCH2),
1.38–1.08 (20H, m, CH2); 13C-NMR (CDCl3, 100
MHz), l 145.85–120.51 (CꢁC, Ar), 69.40 (NCH), 50.97
(NCH2), 27.33, 26.59, 25.94, 25.45, 25.21 (CH2).
HRMS found (M+): 449.3082. Calc. for C33H39NO:
449.3082. Elution with PE/CH2Cl2 (95/5) gave complex
18d (0.31 g, 12.3%) as an orange solid; m.p. 136°C; IR
4.10. Pentacarbonyl (N-methyl-cyclodecynylamine)
propylidene chromium (0) 21a
This complex was obtained upon alkylation of com-
plex 20a as above with methyl iodide in the presence of
LDA. Work up as usual gave complex 21a as a yellow
solid in 53.5% yield; m.p. 60°C; IR (CHCl3) 2040, 1960,
.
(CHCl3) 1960, 1880 cm−1 1H-NMR (CDCl3, 400
MHz) l 7.40–7.22 (10H, m, Ar), 6.09–5.26 (5H,m,
ArCr and NCH), 2.67–2.35 (4H,m, NCH2), 1.47–1.19
(20H, m, 10 CH2); 13C-NMR (CDCl3, 100 MHz) l
233.57 (CO), 146.28–127.88, 116.74, 114.14 (CꢁC, Ar),
92.83, 91.53, 90.62, 89.97, 86.81 (ArCr), 70.05 (NCH),
50.82 (NCH2), 27.21, 26.47, 25.82, 25.39, 25.22 (CH2).
HRMS found (M+): 585.2333. Found for
C36H39NO3Cr: 585.2335. Elution with PE/CH2Cl2 (90/
20) first gave diphenyl indanone (0.14 g, 11.3%) then
diphenyl indenone (0.047 g, 3.9%). Elution with PE/
CH2Cl2 (95/5) gave complex 11d (0.82 g, 31%) as
orange crystals; m.p. 178°C; IR (CHCl3) 1975, 1900,
1
1915 cm−1; H-NMR (CDCl3, 400 MHz) l 5.26–5.21
(1H, m, NCH), 3.51 (3H, s, Me), 3.43–3.34 (1H, m),
3.25–3.16 (1H, m), 2.33–2.19 (2H, m), 2.19–2.04 (2H,
m), 1.97–1.89 (1H, m), 1.81–1.58 (8H, m), 1.08 (3H t,
J=7.6 Hz, Me); 13C-NMR (CDCl3, 100 MHz) l
280.09 (CrꢁC), 223.75, 218.55 (CO), 85.64, 83.78 (CꢂC),
61.44 (NCH), 44.99 (NMe), 44.57, 32.74, 29.22, 26.41,
24.17, 23.78, 18.89, 18.16, 11.11 (CH2). Anal. calc. for
C19H23NO5Cr (%): C, 57.43; H, 5.79; N, 3.53. Found:
C, 57.26; H, 5.84; N, 3.49.
1
1697 cm−1; H-NMR (CDCl3, 400 MHz) l 7.45–6.99
4.11. Pentacarbonyl (N-cyclodecynylamine) benzylidene
chromium (0) 20b
(10H, m, Ar), 6.18–4.92 (5H, m, ArCr), 4.08–4.05 (1H,
m, NCH), 3.27–3.22 (1H, m, NCH), 2.40–2.34 (2H, m,
PhCCH2), 1.57–1.09 (20H, m, CH2); 13C-NMR
(CDCl3, 100 MHz) l 232.79 (CO), 177.72 (CO),
143.45–110.82 (CꢁC, Ar), 93.91, 93.69, 90.80, 90.24
(ArCr), 57.79 (PhC(CH2)), 41.72 (NCH2), 41.11
(PhC(CH2)), 28.76, 28.38, 27.51, 27.17, 26.88, 26.71,
26.26, 25.84, 25.69 (CH2). HRMS found (M+):
613.2284. Calc. for C37H39NO4 Cr: 613.2284. Data for
This complex was obtained as above by aminolysis of
complex 19b with the corresponding amine as a yellow
1
solid in 41% yield; m.p. 110°C; H-NMR (CDCl3, 400
MHz) l 8.72 (1H, s, NH), 8.08–6.86 (5H, m, Ar),
4.34–4.24 (1H, m, NCH), 2.42–2.34 (1H, m), 2.13–
2.07 (1H, m), 1.95–1.50 (10H, m), 1.49–1.40 (1H, m),
1.23–1.12 (1H, m); 13C-NMR (CDCl3, 100 MHz) l
279.34 (CꢁCr), 223.53, 217.52 (CO), 149.76, 129.64,
128.51, 126.93 (Ar), 85.13, 83.54 (CꢂC), 59.78 (NCH),
35.47, 31.65, 24.94, 24.21, 23.93, 18.34, 18.06 (CH2).
Anal. calc. for C22H21NO5Cr (%): C, 61.25; H, 4.87; N,
3.25. Found: C, 61.14; H, 4.94; N, 3.26.
12d white solid; m.p. 161°C; IR (CHCl3) 1688 cm−1
;
1H-NMR (CDCl3, 400 MHz) l 7.38–6.69 (15H,m, Ar),
3.77–3.71 (1H, m, NCH), 3.01–2.94 (1H, m, NCH),
2.49–2.42 (1H,m, PhCCH), 2.11–2.06 (1H, m,
PhCCH), 1.64–1.14 (20H, m, CH2); 13C-NMR (CDCl3,
100 MHz) l 180.89 (CO), 141.73–122.44 (CꢁC, Ar),
60.44 (PhCCH2), 41.63 (NCH2), 34.43, 28.93, 28.51,
27.66, 27.23, 27.11, 26.65, 26.57, 26.38, 26.04, 24.50
(CH2). HRMS found (M+): 477.3032. Calc. for
C34H39NO: 477.3032.
4.12. Pentacarbonyl (N-methyl-cyclodecynylamine)
benzylidene chromium (0) 21b
This complex was obtained upon methylation of 20b
as above with methyl iodide in the presence of LDA as
a yellow solid; m.p. 125°C; IR (CHCl3) 2040, 1970,
4.9. Pentacarbonyl (N-cyclodecynylamine) ethylidene
chromium (0) 20a
1
1920 cm−1; H-NMR (CDCl3, 400 MHz) l 7.41–6.74
This complex was obtained upon aminolysis of com-
plex 19a with cyclodecynylamine as yellow crystals in
56% yield; m.p. 102°C; IR (CHCl3) 2045, 1965, 1915
(5H, m, Ar), 4.88–4.81 (1H, m, NCH), 3.78 (3H, s,
Me), 2.27–2.19 (1H, m), 2.08–2.01 (1H, m), 1.91–1.52
(10H, m), 1.52–1.45 (1H, m), 1.38–1.29 (1H, m); 13C-

98
S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
NMR (CDCl3, 50 MHz) l 275.18 (CrꢁC), 220.44,
217.66 (CO), 128.44, 128.14, 125.91, 120.20, 118.75
(Ar), 84.87, 83.16 (CꢂC), 66.14 (NCH), 43.56 (NMe),
32.62, 29.30, 25.91, 23.95, 23.36, 18.59, 17.68 (CH2).
Anal. calc. for C23H23NO5Cr (%): C, 62.02; H, 5.17; N,
3.15. Found: C, 61.82; H, 5.39; N, 3.12.
4.15. Pentacarbonyl (2-methylaziridinyl) phenyl-3-
propenylidene chromium (0) 31
This complex was obtained as above from the corre-
sponding ethoxycarbene complex (2.7 g, 1.6 mmol) and
methyl-2-aziridine (0.52 g, 9.10 mmol) as red crystals
(1.56 g, 57%); m.p. 82°C; IR (CHCl3) 2045, 1968, 1923
1
cm−1; H-NMR (CDCl3, 400 MHz) l 7.49–7.08 (14H,
4.13. Pentacarbonyl (ethoxy) phenyl-3-propenylidene
chromium (0) 22
m, Ar, CHꢁCH, two E, Z isomers), 3.41 (1H, m,
NCH), 3.21 (2H, m, NCH), 2.83 (2H, m, NCH2), 2.49
(1H, m, NCH), 1.74 (3H, d, J=5.7 Hz, Me), 1.51 (3H,
d, J=5.6 Hz, Me); 13C-NMR (CDCl3, 100 MHz) l
258.82 (CrꢁC), 223.43, 218.46 (CO), 143.69, 142.69
(CHꢁCHPh), 136.31, 135.35 (CHꢁCHPh), 130.19,
130.08, 129.10, 128.14 (Ar), 37.71 (NCH), 35.0 (NCH),
33.38 (NCH2), 32.53 (NCH2), 17.75(Me), 17.43 (Me).
Anal calc. for C17H13NO3Cr (%): C, 56.19; H, 3.58; N,
3.85. Found: C, 56.30; H, 3.69; N, 3.84.
This was obtained from Cr(CO)6 (4.4 g, 20 mmol) in
a diethyl ether (125 ml) at −78°C, and PhCH2CH2Li
prepared from PhCH2CH2I (4.64 g, 20 mmol) in a
mixture of diethyl ether (80 ml) and pentane (125 ml)
and by reaction with t-BuLi (40 mmol, 1.7 M in
hexanes). After heating to room temperature, the sol-
vent was evaporated under vacuum. Water (100 ml)
was then added to the residue, then Et3OBF4 until the
solution was acid. After extraction with diethyl ether,
the solution was dried on MgSO4. Evaporation of the
solvent followed by filtration of the residue on silica
gel, gave complex 22 as an orange oil (3.5 g, 49.5%). IR
4.16. Pentacarbonyl (2-methylaziridinyl) methyl-2-
propenylidene chromium (0) 35
This complex was obtained as above by treatment of
complex 34 (2.5 g, 8.6 mmol) with methyl-2-aziridine
(0.59 g, 10 mmol) in Et2O, and isolated, after silica gel
chromatography as a yellow oil (1.49 g, 57.3%). IR
1
(CHCl3) 2027, 1998, 1945 cm−1; H-NMR (CDCl3, 400
MHz) l 7.41–7.23 (5H, m, Ar), 5.16 (2H, q, J=7.6 Hz,
OCH2), 3.67 (2H, t, J=7.8 Hz, CH2CH2Ph), 2.86 (2H,
t, J=7.8 Hz, CH2CH2Ph), 1.32 (3H, t, J=7.6 Hz,
Me); 13C-NMR (CDCl3, 100 MHz) l 358.56 (CrꢁC),
223.09, 223.27, 216.51 (CO), 140.32, 128.71, 128.47,
126.45 (Ar), 78.12 (OCH2), 64.46 (CH2CH2Ph), 32.42
(CH2CH2Ph), 15.03 (Me). Anal. calc. for C16H14O6Cr
(%): C, 54.23; H, 3.95. Found: C, 54.32; H, 4.04.
1
(CHCl3) 2045, 1970, 1915 cm−1; H-NMR (CDCl3, 200
MHz) l 4.74 (2H, m, ꢁCH
CHH), 3.44 (1H, m, NCH), 3.13 (2H, m, NCH and
NCHH), 2.74 (2H, m, NCH2), 2.31 (1H, m, NCHH),
6 H), 4.47–4.43 (2H, m,
6
6
6
1.95 (6H, 2Me), 1.71 (3H, d, NꢀCHꢀMe), 1.46 (3H, d,
NꢀCHꢀMe); 13C-NMR (CDCl3, 100 MHz) l 271.14,
270.03 (CrꢁC), 223.65, 223.61, 217.91, 217.83 (CO),
155.97, 155.38, (MeCꢁC), 105.43, 105.12 (ꢁCH2), 37.31
(NCH), 35.29 (NCH), 32.39 (NCH2), 32.30 (NCH2),
20.53 (Me), 17.53 (NꢀCHꢀMe), 17.03 (NꢀCHꢀMe).
Anal. calc. for C12H11NO3Cr (%): C, 47.84; H, 3.65; N,
4.65. Found: C, 47.80; H, 3.73; N, 4.55.
4.14. Pentacarbonyl(2-methylaziridinyl)phenyl-3-
propylidene chromium (0) 23
To a solution of (CO)5CrꢁC(OEt)(CH2)2Ph (3.4 g,
9.6 mmol) in Et2O (125 ml), at −40°C, was added
2-methylaziridine (0.8 ml). The solution was kept at this
temperature overnight, then the solvent was evaporated
under vacuum to give complex 23 as yellow crystals
(3.12 g, 88%); m.p. 78°C; IR (CHCl3) 2020, 1963, 1915
4.17. Reaction of complex 23 with diphenylacetylene
Heating of complex 23 (2.5 g, 6.8 mmol), in the
presence of diphenylacetylene (2.4 g, 13.7 mmol), in
benzene (50 ml) for 12 h gave after evaporation of the
solvent a residue which was chromatographed on silica
gel. Elution with PE/AcOEt (95/5) first gave te-
traphenylacyclopentadienone 29 (47 mg), then phenyl-
propionitrile 24 (0.45 g, 50%) as an oil; 1H-NMR
(CDCl3, 200 MHz) l 7.29 (4H, m, Ar), 2.94 (2H, t,
J=7.3 Hz, CH2CN), 2.62 (2H, t, J=7.3 Hz, CH2Ph).
13C-NMR (CDCl3, 50 MHz) l 138.02, 128.79, 128.22,
127.13 (Ar), 119.15 (CN), 31.45 (CH2CN), 19.25
(CH2Ph). MS found (M+): 131. Calc. for C9H9N: 131.
Elution with PE/AcOEt (90/10) gave compound 28
(0.15 g) as a white solid; m.p. 138°C; 1H-NMR (CDCl3,
200 MHz) l 7.4–6.72 (25H, m, Ph), 3.05 (4H, s,
1
cm−1; H-NMR (CDCl3, 400 MHz) l (two E, Z iso-
mers), 7.37–7.23 (10H, m, Ar), 3.40–3.30 (2H, m,
PhCH2CHH), 3.28–3.22 (2H, m, NCH de Z), 3.13–
2.94 (7H, m, NCHH, CH2Ph, PhCH2CH
m, NCHH), 2.51–2.45 (1H, m, NCH), 2.36 (1H, m,
NCHH), 1.55 (3H, d, J=5.7 Hz, Me), 1.48 (1H, m,
NCHH
), 1.4 (3H, d, J=5.7 Hz, Me); 13C-NMR
6 H), 2.70 (1H,
6
6
6
(CDCl3, 100 MHz) l 271.09, 267.93 (CrꢁC), 223.09,
223.02, 218.33, 218.23 (CO), 140.67, 140.56, 129.06,
128.85,
128.8,
126.63
(Ar),
55.67,
55.25
(CꢀCH2CH2Ph), 37.53 (NCH), 39.11 (NCH), 33.66,
33.11 (PhCH2), 32.74, 32.38 (NCH2), 17.29 (Me), 16.89
(Me). Anal. calc. for C17H13NO3Cr (%): C, 55.89; H,
4.10; N, 3.83. Found: C, 55.93; H, 4.11; N, 3.90.

S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
99
CH2ꢀCH2); 13C-NMR (100 MHz, CDCl3) l 149.67–
125.76 (Ar), 38.42 (CH2ꢀCH2Ph). HRMS found (M+):
487.2299. Calc. for C37H29N: 487.2299. Elution with
PE/AcOEt (80/20) gave complex 25 (1.45 g, 30.7%) as red
crystals; m.p. 130°C; IR (CHCl3) 1947, 1880, 1845, 1760
(400 MHz, CDCl3) l 7.44 (5H, m, Ph), 7.4 (1H, t,
J=16.7 Hz, CHCN), 5.89 (1H, d, J=16.7 Hz, CHPh);
13C-NMR (100 MHz, CDCl3) l 150.69 (CHꢀPh), 133.63,
131.36, 129.26, 127.52 (Ar), 118.35 (CN), 96.24
(CHꢀCN). IR (CHCl3) 2210 (CN), 1673 cm−1. Then
with PE/AcOEt (90/10) the phenol 33 (0.96 g, 19.4%) as
1
cm−1. H-NMR (CDCl3, 400 MHz) l 7.55–6.50 (25H,
1
m, Ar), 3.65 (1H, m, CH
NCHH), 3.23 (1H, t, J=8 Hz, NCHH
PhꢀCHH), 2.46 (1H, m, PhCHH), 2.17 (1H, m, Ph-
CH2CHH), 1.84 (1H, m, PhꢀCH2CHH), 1.46 (3H, d,
6
CH3), 3.58 (1H, t, J=8 Hz,
a white solid; m.p. 94°C; H-NMR (400 MHz, CDCl3)
6
6
), 2.99 (1H, m,
l 7.7–7 (16H, m, Ar) 4.98 (1H, s, OH), 2.0–1.83 (2H,
m, NCH2), 1.78 (1H, m NCH), 0.64, 3H, d, J=5.3 Hz,
Me). 13C-NMR (100 MHz, CDCl3) l 146.02, 144.93,
138.32–121.9 (Ar), 37.37 (NCH), 35.93 (NCH2), 17.61
(Me). IR (CHCl3): 3575, 3530 cm−1. Anal. calc. for
C28H25NOCl2(C27H23NO+CH2Cl2) (%): C, 72.72; H,
5.41; N, 3.03. Found: C, 72.85; H, 5.52; N, 2.85.
6
6
6
6
J=6.84 Hz, Me). 13C-NMR (CDCl3, 100 MHz) l
235–230 (CO), 208.43 (CO), 139.44–104.74 (CꢁC, Ar),
79.96 (NꢀCꢀCO), 53.63 (NCH2), 43.41 (CHCO), 34.21,
32.76 (CH2CH2Ph), 12.82 (Me). HRMS found (M+
ꢀ3CO): 609.2125. Found for C41H35NOCr: 609.2124.
Then complex 26 (0.31 g, 6.6%) as red crystals; m.p.
4.20. Reaction of complex 35 with diphenylacetylene
125°C; IR (CHCl3) 1955, 1890, 1845, 1770 cm−1. H-
1
NMR (CDCl3, 400 MHz) l 7.60–6.57 (25H, m, Ar), 3.73
Refluxing complex 35 (1.57 g, 5.2 mmol) in benzene
(50 ml) in the presence of diphenylacetylene (1.85 g, 10.43
mmol) for 15 h, gave after evaporation of the solvent and
silica gel chromatography, compound 36 (0.25 g, 15.4%)
(1H, t, J=8 Hz, NCH
NCHH), 2.82 (1H, m, COCH), 2.53 (2H, m, Ph CHH
Ph CH2CHH), 2.24–2.17 (1H, m, PhꢀCH2CHH), 1.85
6 H), 3.18–3.01 (2H, m, PhꢀCH6 H;
6
6 ,
6
6
(3H, d, J=8 Hz, Me); 13C-NMR (CDCl3, 100 MHz) l
203 (CO), 139.72–123.58 (Ar, CꢀCH2 CH2Ph), 117.22,
92.91 (CꢁCꢀPh), 83.26 (NꢀCꢀCO), 53.08 (NCH2), 40.88
(CHCO), 35.17, 33.39 (CH2CH2Ph), 17.41 (Me). Anal.
calc. for C44H35NO4Cr (%): C, 76.19; H, 5.05; N, 2.02.
Found: C, 76.06; H, 5.04; N, 1.99. And finally with the
same mixture of eluents complex 27 (85 mg, 1.8%) as red
as a solid; m.p. 67°C; IR (CHCl3) 3585, 3520 cm−1
;
1H-NMR (CDCl3, 400 MHz) l 7.28–6.83 (11H, m, Ar),
5.31 (1H, s, OH), 2.44 (3H, s, ArꢀMe), 1.83 (1H, m,
NCH), 1.77, 1.73 (2H, m, NCH2), 0.8 (3H, d, J=5.4 Hz,
NCHCH6
3). 13C-NMR (CDCl3, 100 MHz) l 146.48,
142.96 (CꢁCꢀOH, CꢁCꢀNH), 137.91–115.84 (Ar), 37.63
(NCH), 37.31 (NCH2), 18.24 (PhꢀMe), 16.40
1
crystals; H-NMR (CDCl3, 400 MHz) l 7.89–6.52 (H,
(NCHCH6 3
). HRMS found (M+): 315.1623. Calc. for
m, Ar), 3.56 (1H, t, J=10.9 Hz, NCH
J=10.9 Hz, NCHH), 3.05–2.98 (1H, m, PhꢀCH
NCHH), 2.45–2.32 (2H, m, PhCHH, Ph CH2CHH), 2.25
(3H, s, Me), 2.08–1.98 (1H, m, Ph CH2CHH).
6
H), 3.35 (1H, t,
C22H21NO: 315.1624.
6
6
H;
6
6
6
4.20.1. Structure solution and refinement
6
For complexes 12d, 17d, 20b, 25 and 26: accurate
cell dimensions and orientation matrices were ob-
tained by least-squares refinements of 25 accurately
centered reflections. No significant variations were ob-
served in the intensities of two checked reflections
during data collection. Complete data and collection
parameters are listed in Table 1. The data corrected
for Lorentz and polarization effects. Computations
were performed by using the PC version of CRYS-
TALS.[17] Scattering factors and corrections for
anomalous absorption were taken from [18]. The
structures were solved by Fo–Patterson technique or
direct method (SHELXS [19] for 17d. Refinements
were carried out by full-matrix least-squares. For 12d
and 20b all non-hydrogen atoms were anisotropically
refined, hydrogen atoms were introduced in calculated
positions except on nitrogen atoms for 20b and ex-
cept on the carbon atoms with high value of u(iso)
for 12d. For 17d, 25, and 26, the measured diffraction
intensities were very weak, due to the small size of
the crystals. Therefore, only the Cr(CO)3 fragment in
25 was anisotropically refined and for 17d and 26 all
atoms were left isotropic and hydrogen atoms were
4.18. Reaction of complex 27 with pyridine
Refluxing of complex 27 in pyridine for 12 h gave, after
evaporation of the solvent and filtration through silica
gel, compound 27a as a solid; m.p. 80°C; 1H-NMR
(CDCl3, 400 MHz) l 7.67–6.57 (30H, m, Ar), 4.14 (1H,
d, J=9,9 Hz, NCH
2.71–2.65 (1H, m, PhꢀCH
PhCHH), 2.42–2.35 (1H, m, Ph CH2 CH
(1H, m, Ph CH2CHH
), 1.49 (3H, s, Me). 13C-NMR
6
H), 4.08 (1H, d, J=9,9 Hz, NCHH
H), 2.52–2.45 (1H, m,
H), 2.01–1.94
6 ),
6
6
6
6
(CDCl3, 100 MHz) l 215.97 (CO), 143.68–118.68 (Ar,
CꢁC), 76.54 (HOꢀCꢀMe), 72.63 (NꢀCꢀCO), 58.44
(NCH2), 34.25, 32.04 (CH2CH2Ph), 25.10 (Me). HRMS
found (M+): 555.2562. Calc. for C41H35NO2: 555.2561.
4.19. Reaction of complex 31 a with diphenylacetylene
Complex 31 (1.8 g) was refluxed in benzene (50 ml) for
10 h in the presence of diphenylacetylene (1.76 g).
Evaporation of the solvent followed by silica gel chro-
matography of the residue gave first with PE/AcOEt
(95/5) phenylacrylonitrile 32 (0.34 g, 53.3%); H-N
1
.
MR

100
S. Lafolle´e-Bezzenine et al. / Journal of Organometallic Chemistry 567 (1998) 83–100
not [H1]included. This led to higher values of the
reliability factor for these three compounds.
Recherche Scientifique and MENRT (grant to S.
Lafolle´e-Bezzenine).
For complex 27, data were collected at room temper-
ature on a Stoe diffractometer imaging plate diffraction
system (IPDS) equipped with a graphite oriented
monochromator utilizing Mo–Kh radiation (u=
0.71073). The asymetric unit is built up of two indepen-
dent molecules. Only one of these molecules (1) is
represented in Fig. 5. The final unit cell parameters were
derived from the least-squares refinement of 2000 se-
lected reflections. The structure was solved by direct
methods (SIR92) [21] and refined by least-squares proce-
dures on Fobs. H atoms were introduced in calculation
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˚
in idealized positions (d(CH)=0.96 A) and their atomic
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[17] D.J. Watkin, C.K. Prout, J.R. Carruthers and P.W. Betteridge,
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versity of Oxford, UK, 1966.
Fractional atomic coordinates, anisotropic thermal
parameters for non-hydrogen atoms, atomic coordi-
nates for H atoms, complete lists onf bond distances
and bond angles have been deposited at the Cambridge
Crystallographic Data Center. Copies of the data free
of charge can be obtained on application to the Direc-
tor, CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK.
[18] D.T. Cromer, International Tables for X-ray Crystallography,
vol. IV. Kynoch Press, Birmingham, UK, 1974.
[19] G.M. Sheldrick, SHELXS-86, Program for Crystal Structure
Solution. University of Goˆttingen, 1986.
Acknowledgements
[20] D.J. Watkin, C.K. Prout and L.J. Pearce, Cameron. Crystallog-
raphy Laboratory, University of Oxford, UK, 1996.
[21] A. Altamore, G. Cascarano, C. Giacovazzo, A. Guagliardi,
M.C. Burla, G. Polidori, M. Camalli, J. Appl. Crystallogr. 27
(1994) 435.
This research was supported by the Commission of
the European Communities (DGSRD, International
Scientific Cooperation), Centre National de la
.
.