Electrochemical reduction of some [(η5-Cyclopentadienyl) (η6-arene) iron(II)][PF6] complexes bearing an imine or a nitrone function in benzylic position of the arene ligand

Article abstract of DOI:10.1016/S0022-328X(97)00627-X

The electrochemical reduction in basic hydro-organic media of mixtures of [(η⁵-Cp) (η⁶-benzophenone-N-(aryl)nitrone) Fe]⁺ 1a-d and [(η⁵-Cp) (η⁶-benzophenone anil) Fe]⁺ complexes 1′a-d led to the corresponding [(η⁵-Cp) (η⁶-α-(arylamino)diphenylmethane) Fe]⁺ cations 2a-d with good yields (85-90%). In a similar manner, various [(η⁵-Cp) (η⁶-9-(arylamino)fluorene) Fe]⁺ cations 4a-i were synthesized (70-88% yield) in acidic hydro-organic media from the corresponding [(η⁵-Cp) (η⁶-fluorenone anil) Fe]⁺ 3a-i or the [(η⁵-Cp) (η⁶-fluorenone-N-(2′-methoxycarbonyl phenyl)nitrone) Fe]⁺ derivative 3′i. According to ¹H NMR chemical shifts, the exo isomer is formed in the majority (exo:endo ca. 75:25) during electrosynthesis of compounds 4a-i. We could explain these unexpected results by an epimerization in the electrolysis media. The amines 4a,b were re-oxidized by oxygen into the starting imine 3a,b under very mild Al₂O₃-catalysis conditions (77-80% yield).

Full text of DOI:10.1016/S0022-328X(97)00627-X

Ž
.
Journal of Organometallic Chemistry 553 1998 253–267
5
6
wž
/ ž
/
Electrochemical reduction of some h -Cyclopentadienyl h -arene
ž /xw x
iron II PF6 complexes bearing an imine or a nitrone function in
benzylic position of the arene ligand
a
a
b
c
Fabrice Pierre a,), Andrea Stricker , Claude Moinet , Sourisak Sinbandhit , Loıc Toupet
¨
a
Laboratoire: Electrochimie et Organometalliques, UMR CNRS No 6509, UniÕersite de Rennes 1, Campus de Beaulieu,
F-35042 Rennes Cedex, France
Centre de Mesures Physique de l’Ouest, UniÕersite de Rennes 1, Campus de Beaulieu, F-35042 Rennes Cedex, France
´
´
b
´
c
Laboratoire de Physique Cristalline, UniÕersite de Rennes 1, Campus de Beaulieu, F-35042 Rennes Cedex, France
´
Received 25 June 1997; received in revised form 18 August 1997
Abstract
5
6
wŽ
. Ž
Ž
.
.
xq
The electrochemical reduction in basic hydro-organic media of mixtures of h -Cp h -benzophenone-N- aryl nitrone Fe 1a–d
X
wŽ
xq
and h -Cp h -benzophenone anil Fe complexes 1 a–d led to the corresponding h -Cp h -a- arylamino diphenylmethane Fe
. Ž
.
xq
wŽ
. Ž
Ž
.
.
.
5
6
5
6
5
6
Ž
.
wŽ
. Ž
Ž
.
xq
.
cations 2a–d with good yields 85–90% . In a similar manner, various h -Cp h -9- arylamino fluorene Fe cations 4a–i were
5
6
Ž
.
Ž
wŽ
. Ž
xq
synthesized 70–88% yield in acidic hydro-organic media from the corresponding h -Cp h -fluorenone anil Fe 3a–i or the
h -Cp h -fluorenone-N- 2 -methoxycarbonyl phenyl nitrone Fe derivative 3X i. According to 1H NMR chemical shifts, the exo
X
5
6
wŽ
. Ž
.
.
xq
Ž
.
isomer is formed in the majority exo:endo ca. 75:25 during electrosynthesis of compounds 4a–i. We could explain these unexpected
results by an epimerization in the electrolysis media. The amines 4a,b were re-oxidized by oxygen into the starting imine 3a,b under very
Ž
.
mild Al2O3-catalysis conditions 77–80% yield . q 1998 Elsevier Science S.A.
Keywords: Iron; Cyclopentadienyl; Arene; Electrochemical reduction; Secondary amine; O2-oxidation
w x
In a precedent paper 63 , we described the condensa-
1. Introduction
Ž
tion reaction of various nitrosoarenes with Cp Fe
5
6
q
q
w
Ž
. Ž
.
xq
.
Ž
.
h -Cp h -arene Fe cations have widely con-
diphenylmethane and Cp Fe fluorene complexes.
tributed to the transition metal activated aromatic chem-
This reaction afforded a very useful synthesis route to
q
w
x
Ž
Ž
.
.
istry 1–4 . In the last decade, numerous publications
have appeared describing the use of such complexes in
mixtures of Cp Fe benzophenone-N- aryl nitrone and
q
Ž
.
Ž
Cp Fe benzophenone anil
or to various Cp Fe
q
w
x w
x
.
the field of macromolecular chemistry 5–15 16–21
and organic synthesis 22–32 33–43 44,45 . How-
ever, owing to the reductible character of the
fluorenone anil cations. In this work, polarographic
investigations revealed the two successive reduction
steps of nitrones into amines functions, via the imine
compounds 64 Scheme 1 . Following our research on
benzylic C–H activation applied to the formation of
Carbon–Nitrogen bonds, we report herein a highly effi-
w
x w
x w
x
w
x
w
x
Ž
.
organometallic moiety 46–51 and the sensitivity of the
w
x
arene ligand towards hydride addition 52–55 , their use
in processes involving a reduction step may be poten-
tially restricted. In this perspective, electrochemistry can
be a powerful technique for selective reducing of the
w
x
functions borne by the ligands 56–61 . Control of the
electrode potential has shown to be very efficient to
w
x
attain a good selectivity in many redox reactions 62 .
)
Corresponding author. Tel.: q33-2-99-28-62-90; fax: q33-2-99-
28-16-60; e-mail: didier.floner@univ-rennesl.fr.
Scheme 1.
0022-328Xr98r$19.00 q 1998 Elsevier Science S.A. All rights reserved.

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)
254
F. Pierre et al.rJournal of Organometallic Chemistry 553 1998 253–267
Table 1
cient electrochemical reduction of these nitrone and
imines cations and discuss some particular features of
the resulting amines.
X
Electrochemical data of nitrone–imine mixtures 1a–dq1 a–d
Compound
a
Ž
.
E1r2 V vs. SCE
Coulometric datab
nitrone imine FeII ™ FeI "0.1 F moly1
X
Ž
.
1aq1 a 90:10 y0.72 y0.95 y1.42
3.8
3.4
3.5
3.6
X
2. Results and discussion
Ž
.
1bq1 b 70:30 y0.84 y0.97 y1.39
X
Ž
Ž
.
.
1cq1 c 80:20 y0.79 y1.07 y1.44
5
6
X
[(
h -Cp
) (
h -a-
2.1. Electrosynthesis of some
1dq1 d 85:15 y0.77 y0.97 y1.42
q
(
)
)
]
arylamino diphenylmethane Fe cations
a
Ammonium buffer NH4 2 SO4 0.25 mol ly1 qNH3,H2O 0.5 mol
ŽŽ
.
.
ly1 -acetone 1:1, v:v .
.
Ž
The controlled potential reduction of nitrone–imine
bEsy1.2 V vs. SCE.
X
mixtures 1a–dq1 a–d at a mercury cathode, in ammo-
nium buffer NH4 2 SO4 0.25 mol ly1 qNH3, H2O 0.5
ŽŽ
.
mol ly1 -acetone 1:1, v:v led to the corresponding
.
Ž
.
coupling experiments and comparison between the four
Ž
.
Ž
.
amine complexes 2a–d with good yields Scheme 2 .
The nitrone functions were reduced by a four-electron
process and the imines by a two electron process. We
measured coulometric data between two and four Fara-
days per mole of substrate, depending on the composi-
products of the series variation of the methyl position .
The structural data are reported in Section 4, but some
of them have to be highlighted here. All the amines are
identified in 1H NMR by an AB system with a 3J
coupling constant of ca. 9.5 Hz, corresponding to the
two protons H-7 and NH. 13C spectra exhibits six
metal-bonded carbon signals, showing that C-2, C-3 and
C-6, C-5 respectively are diastereotopic. This feature,
resulting from the presence of the chiral carbon C-7 and
the non equivalence of both sides of the complexed
ring, is in agreement with the proposed structures.
The electroreduction is thus highly selective and
allows the simultaneous reduction of both nitrone and
imine functions with preservation of the organometallic
moiety.
Ž
Ž
.
tion of the starting mixtures Table 1 . For each com-
.
pound, the reduction wave ca. y1.40 V vs. SCE
which may be attributed to the reduction of the iron unit
remained unchanged after the electrochemical process.
After work-up, the new compounds 2a–d were fully
characterized by high resolution Liquid Secondary Ions
Ž
.
Mass Spectrometry LSIMS , I.R. spectroscopy, ele-
1
mental analyses, H and 13C NMR spectroscopy. NMR
signals assignments were determined on the grounds of
shielding effects of the metal complexation, gated de-
Scheme 2.

(
)
F. Pierre et al.rJournal of Organometallic Chemistry 553 1998 253–267
255
Table 2
Electrochemical data of imines complexes 3a–h and imine–nitrone
mixture 3iH3X i
Compound Mediuma E1r2 V vs. SCE
imine
FeII ™ FeI "0.1 F moly1
Coulometric datab
Ž
.
3a
3b
3c
3d
3e
3f
3g
A
B
A
A
B
C
B
A
A
y0.47 y1.33
y0.44 y1.31
y0.46 y1.32
y0.42 y1.30
y0.41 y1.29
y0.65 y1.30
y0.45 y1.32
y0.39 y1.33
y0.43c y1.30
2.0
2.0
2.0
2.0
1.9
2.0
2.1
2.1
2.9
3h
3iq3X i
aA: acetic buffer CH3CO2 Na 1.5 mol ly1 qCH3CO2 H 0.5 mol
Ž
ly1 -acetone 1:1,v:v ; B: acetic buffer CH3CO2 Na 0.5 mol ly1 q
.
Ž
.
Ž
CH3CO2 H 0.5 mol ly1 -acetone 1:1,v:v ; C: ammonium buffer
ŽŽ
.
Ž
.
NH4 2 SO4 0.25 mol ly1 qNH3,H2O 0.5 mol ly1 -acetone
.
.
Ž
.
1:1,v:v .
bEsy1.0 V vs. SCE.
c The imine and the nitrone are reduced at the same potential in this
medium.
tion waves of the iron units at ca. y1.30 V vs. SCE
were not affected by the electroreduction. The air-sensi-
tive complexes 4a–i were isolated in satisfactory purity
under argon atmosphere and fully characterized by I.R.
Scheme 3.
Ž
.
spectroscopy, mass spectrometry LSIMS , elemental
1
analyses, H and 13C NMR spectroscopy.
5
6
[(
h -Cp
) (
h -9-
2.2. Electrosynthesis of some
Two diastereomers exo and endo are formed during
the electrolysis, as is evident from the NMR spectra
which displays two signal sets of unequal intensity
q
(
)
)
]
arylamino fluorene Fe cations
q
Ž
.
Ž
.
Table 3 . Complete signal attributions were conducted
Cp Fe fluorenone anil derivatives 3a–h and the
imine–nitrone mixture 3iq3X i were electrochemically
reduced in acidic hydro-organic media, leading to the
corresponding amine complexes 4a–i with good yields
on complexes 4a and 4i by using 2D-1
H,13 C correlation
1
and H,1H COSY experiments, and by taking into
w
x
account the well-known 65 metal-bonding effects on
chemical shifts and coupling constants. 1H and 13C
assignments of the other fluorene derivatives 4b–h were
done by reference to 4a and 4i, using
Ž
.
Schemes 3 and 4 . The coulometric data reported in
Table 2 are in agreement with a two electron process for
the reduction of the imines 3a–i and four electron
process for the reduction of the nitrone 3X i. The reduc-
1H coupling 13C
spectra and gated decoupling experiments. Some se-
Scheme 4.

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)
256
F. Pierre et al.rJournal of Organometallic Chemistry 553 1998 253–267
Table 3
Table 4
Diastereomer ratios of amino complexes 4a–i based on 1H NMR
1
Selected 13C and H NMR data of amine derivatives 4a–i d ppm
Ž
Ž
Ž
.
.
Ž
.
.
integrals in CD3CN
from TMS , J Hz , solvent: CD3CN
1JC-9,H-9
dH-9
3JH-9,NH
Compound
R
exo:endo
Complex dC-9
4a
4b
4c
4d
4e
4f
4g
4h
4i
H
75:25
85:15
75:25
75:25
80:20
80:20
80:20
70:30
exo
endo exo endo exo endo exo endo
2X-Me
4a
4b
4c
4d
4e
4f
4g
4h
4i
61.07 59.65 142 137
60.99 59.64 141 136
6.12 5.87 9.2 7.9
3X-Me
6.19 5.94 9.3 7.3
6.11 5.86 9.9 8.0
6.07 5.82 8.9 7.9
6.21 6.01 9.5 8.4
6.09 5.84 9.7 7.9
6.18 5.93 9.2 7.8
6.22 5.97 9.2 7.8
6.30 6.09 8.8 8.7
4X-Me
61.02 59.64 142 136
61.49 60.00 142 136
60.74 58.93 141 135
61.05 59.63 142 138
61.06 59.81 142 136
60.20 58.95 142 138
60.06 58.12 142 139
2X-Cl
4X-Cl
2X-CH2CO2 Me
4X-COMe
2X-CO2 Me
a
Ž
.
45:55 60:40
a
in DMSO-d6.
lected data listed in Table 4 emphasize typical differ-
ences which permitted the assignments of both isomers
signals in each mixture.
q
Ž
.
over, in Cp Fe fluorene series these effects has been
unambiguously demonstrated in 1977 by Johnson and
w
x
Ž
.
According to previous works on electrochemical re-
Treichel 69 Scheme 5 . A transposition of these ob-
servations to our phenylamino complexes seems to be
reasonably thinkable.
q
Ž
.
duction of Cp Fe arene complexes in hydro-organic
w
x
media 58–61 , one might attempt that upon electroly-
sis, the C-9 protonation step takes place in trans to the
metal, leading preferentially to the endo isomer. Sur-
prisingly, it can be taken as evidence that, except for 4i,
the exo amino complex is present in the majority. This
is based on an analysis of protons chemical shifts of the
R-C6 H4-NH– fragment and H-9. The data resumed in
Table 5 point out that H-9 in the major isomer under-
goes a downfield shift of 0.25 ppm compared with the
minor isomer. In regard to a series of contributions of
In order to explain these unexpected results, the
Ž
.
amine 4b exo:endo-85:15 was submitted to recrystal-
lization in CH2Cl2 at y258C, leading to a mixture
Ž
.
enriched with the endo isomer exo:endo-55:45 . By
stirring it in acetic buffer-acetone at room temperature
for one night, after work-up we could recover in 80%
Ž
. Ž
yield the initial mixture ratio exo:endo-85:15 Fig. 2A
and B . This result clearly demonstrate that in the acidic
electrolysis media, the endo isomer is epimerized into
the more stable exo isomer. According to precedent
reports on highly stereoselective electrolyses of Cp Fe
arene cations 58–61 , we may assume that our reduc-
tion process is also stereoselective. However the experi-
ments described above show that the reaction can be
followed by a rearrangement which leads to the thermo-
.
w
x
w x
Moriarty et al. 66 , McGlinchey et al. 67 and Top et
w
x
Ž
al. 68 , this clearly indicates its localization on the
complexed side of the fluorene plane, whereas the
opposite effect is being observed for the protons of the
q
.
w
x
Ž
.
arylamino fragment Fig. 1 . McGlinchey et al. ana-
lyzed the diamagnetic anisotropy of various
organometallic moieties. Their studies suggested that a
downfield shift is observed for the protons located on
the side of the metal moiety and an upfield shift for
protons located on the other side of the plane. More-
Ž
.
dynamic equilibrium Scheme 6 . The isomer ratio re-
Ž
.
sulting from the electrosynthesis of 4i exo:endo-45:55
may be explained by a slower epimerization rate. This
rate could be enhanced in DMSO, as is evident from an
Table 5
1
Ž
.
variation of H chemical shifts between exo and endo isomers of 4a–i. R-C6 H4-NH– group and H-9 solvent CD3CN
Ž .
Dd ppm sdexo–dendo
Complex
H-9
R-C6 H4-NH–
ortho
meta
para
R
H-2X
H-6X
H-3X
H-5X
H-4X
4a
4b
4c
4d
4e
4f
4g
4h
4i
q0.25
q0.25
q0.25
q0.25
q0.20
q0.25
q0.25
q0.25
q0.21
y0.37
y
y
y0.17
y0.2
y
y0.11
y0.1
y0.10
y
y
X
Ž
.
.
.
y0.5
y0.37
y
y0.2
y0.17
y
y0.22 2 -Me
X
Ž
y0.32
y0.38
y
y
y0.11 3 -Me
X
Ž
y0.18
y0.17
y0.18
y0.16
y0.18
y0.14
y0.10 4 -Me
y0.67
y
y0.30
y
y0.17
y
y
y
y0.37
y
y0.37
y
X
Ž
.
y0.5
y
y0.2
y
y0.1
y
y0.16
y0.25 2 -CH2–
X
Ž .
y0.08 4 -COMe
X
Ž .
y0.05 2 -CO2 Me
y0.69
y0.30

(
)
F. Pierre et al.rJournal of Organometallic Chemistry 553 1998 253–267
257
Fig. 1. Variations of 1H NMR chemical shifts between exo and endo
X
Ž
isomers of para-substituted amines 4a, 4d, 4f and 4h RsH, 4 -Me,
X
X
.
4 -COMe, 4 -Cl .
NMR spectrum in this solvent which displayed an
exo:endo isomer ratio of 60:40 respectively.
Scheme 6.
To support the hypothesis of a stereoselective reac-
tion leading to the endo complex, the imine 3b was
reduced into 4b by sodium borohydride in
This observation prompt us to further investigate the
reactivity of the amines 4a,b toward oxygen. When
bubbling O2 in a solution of amines 4a or 4b in basic
Ž
.
dichloromethane. Despite a low yield 40% and an
Ž
.
incomplete reduction 20% of 3b was detected , the
endo isomer was clearly formed in a large majority
Ž
ŽŽ
.
hydro-organic media ammonium buffer NH4 2 SO4
Ž
.Ž
.
0.25 mol ly1 qNH3, H2O 0.5 mol ly1 -acetone
exo:endo-10:90 Fig. 2C .
.
An attempt to characterize the exo epimer by X-ray
diffraction study failed. From slow crystallization of the
Ž
..
1:1,v:v the reduction wave of imine functions were
rapidly recovered whereas in acidic media, no oxidation
was detected. At a preparative scale, O2-oxidation of
Ž
.
isomer mixture 4b exo:endo-85:15 in CH2Cl2rpen-
tane, a monocrystal revealed an endo-type molecular
Ž
.
amines 4a and 4b in the presence of alumina Al2O3
was the more efficient technique and led to the imine
Ž
.
structure Fig. 3 . This conflicting observation may be
easily explained by the lower solubility of the endo
complex in CH2Cl2 as shown above, and by a better
ability of this epimer to crystallize.
Ž
.
complexes 3a and 3b with good yields Scheme 7 .
The reaction proceeded selectively under very mild
conditions. Oxidation of amines into imines has been
w
x
thoroughly investigated 70–72 and is generally diffi-
cult to control or require harsh oxidant conditions. In a
first assumption, the high selectivity observed in our
reaction and its base catalysis may be explained by a
high stability of the anil cations and by an increased
acidity of the proton H-9.
5
6
[(
)
(
h -9 -
2 .3 . O 2 -o xid a tio n o f
h -C p
q
(
)
)
]
arylamino fluorene Fe cations
Upon isolation of the amine 4a,b under air atmo-
sphere, we noticed in the isolated products the presence
of appreciable amounts 10–15% of the starting imine
3a,b, despite a complete disappearance of their polaro-
graphic reduction wave at the end of the electrolysis.
Ž
.
3. Conclusion
This work further demonstrates the efficiency of
electrochemical processes. We have shown that highly
q
Ž
.
chemio-selective reduction occurs on Cp Fe arene
Ž
Ž
complexes, providing various Cp Fe a- aryl
amino arene derivatives with good yield. In connec-
tion with the nitrosoarene condensation 63 , this
methodology constitutes an efficient two-step introduc-
tion of a secondary arylamino group onto a benzylic
q
.
.
w
x
Ž
.
chain Scheme 8 .
Otherwise, these amino complexes still possess a
benzylic carbon liable to be deprotonated and to react
Scheme 5.

1
Ž
. Ž .
Ž .
Fig. 2. H NMR spectra of varied exo– endo isomer mixtures of 4b ppm from TMS, CD3CN . A after recrystallization in CH2Cl2 at y258C, exo:endo-55:45; B after epimerization of the
precedent mixture in acetic buffer CH3CO2 Na 0.5 mol ly1 qCH3CO2 H 0.5 mol ly1 -acetone 1:1,v:v , exo:endo-85:15; C after partial NaBH4 reduction of imine 3b, exo:endo-10:90.
Ž .
Ž
.
Ž
.

(
)
F. Pierre et al.rJournal of Organometallic Chemistry 553 1998 253–267
259
˚
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Fig. 3. ORTEP drawing of the endo isomer of 4b. Selected interatomic distances A : Fe–C 1 2.023 9 , Fe–C 2 2.03 1 , Fe–C 3 2.04 1 ,
Ž .
Ž .
Ž
Ž .
Ž .
Ž .
Ž
Ž .
Ž .
Ž .
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž
.
Ž .
Ž
.
Fe–C 4 2.03 1 , Fe–C 5 2.04 1 , Fe–C 6 2.10 1 , Fe–C 7 2.08 1 , Fe–C 8 2.059 9 , Fe–C 9 2.071 8 , Fe–C 10 2.078 8 , Fe–C 11
Ž .
.
.
.
2.096 9 , N–C 18 1.41 1 , N–C 19 1.38 1 , N–H 26 0.972 8 .
with electrophiles. Additional studies are underway to
use such complexes in further syntheses.
IR spectra were recorded on a Nicolet 205 FT-IR
Ž
.
instrument in KBr . Elemental analyses were done at
the Service Central d’Analyse, Departement Analyse
´
Ž
.
Elementaire Vernaison .
´
4. Experimental section
Mass spectra were obtained on a VG Analytical ZAB
Spec TOF high resolution mass spectrometer EBE TOF
.
Geometry at the Centre Regional de Mesures Physiques
´
de l’Ouest C.R.M.P.O. . Ionization type was LSIMS
Liquid Secondary Ions Mass Spectrometry with Cs
ions, the matrix was 3-nitro-benzylique alcohol m-
NBA and the acceleration potential was 8 kV.
Ž
4.1. General methods
Ž
.
q
Ž
.
Conventional electrochemical equipment was used
Ž
Ž
for polarography and electrolyses EG&G Princeton
.
Applied Research model 362-scanning potentiostat with
.
an XY recorder . Controlled potential electrolyses were
NMR spectra were recorded on a Brucker AM 300
Ž1
.
H
performed at a mercury pool cathode, under nitrogen
atmosphere, in a cell previously described by Moinet
FT spectrometer at the C.R.M.P.O. at 300 MHz
Ž13
.
and 75.5 MHz C . Chemical shifts were expressed in
Ž .
ppm downfield from TMS and coupling constants J
w
x
and Peltier 73,74 . Electrolyses were monitored by
y1
Ž
.
Ž) .
in hertz. Values with an asterisk could be inverted.
polarography Scan-rate: 5 mV s ; drop-time t : 2 s .
The coulometric measurements were determined with a
current integrator Tacussel model IG 5 N.
13C NMR broad band and gated decoupling spectra
were recorded. 2D-1H,13 C correlation and 1H,1H-COSY
Scheme 7.

(
)
260
F. Pierre et al.rJournal of Organometallic Chemistry 553 1998 253–267
1
Ž
..
H2 SO4-acetone 1:1,v:v : y0.23 V vs. SCE. H NMR
3
Ž
.
Ž
.
Ž
.
Ž
CD3CN : anti 75% : ds4.89 s, Cp , 7.02 d, Js
3
3
.
Ž
.
Ž
.
6.3, H-1 , 6.50 t, Js6.2, H-2 , 6.55 t, Js6.1, H-3 ,
3
3
Ž
.
Ž
.
Ž
7.09 d, Js6.4, H-4 , 7.99 d, Js7.7, H-5 , 7.64 t,
3
3
3
.
Ž
.
Ž
Js7.7, H-6 , 7.31 t, Js7.7, H-7 , 6.74 d, Js7.9,
3
X
3
X)
.
Ž
.
Ž
.
H-8 , 7.63 d, Js7.8, H-3 , 7.33 t, Js7.8, H-4 ,
3
X)
3
X
Ž
.
Ž
.
7.47 t, Js7.7, H-5 , 7.12 d, Js7.9, H-6 , for
attribution of H-5, H-6, H-7 and H-8 irradiation at 6.74
Ž
.
Ž
.
Ž
and 7.99 ppm; syn 25% : ds4.79 s, Cp , 5.56 d,
3
3
3
.
Ž
.
Ž
Js6.5, H-1 , 6.10 t, Js6.4, H-2 , 6.46 t, Js6.3,
3
3
.
Ž
.
Ž
.
H-3 , 7.03 d, Js6.4, H-4 , 8.06 d, Js7.5, H-5 ,
3
3
Ž
.
Ž
.
Ž
7.76 t, Js7.5, H-6 , 7.68 t, Js7.5, H-7 , 7.99 d,
3
3
X
3
.
Ž
Ž
.
Ž
Js7.7, H-8 , 7.68 d, Js8.0, H-3 , 7.37 t, Js7.8,
3
X)
3
H-4X) , 7.49 t, Jf8, H-5 , 7.13 d broad, Jf8,
.
.
Ž
X
.
H-6 , for attribution of H-1, H-2, H-3 and H-4 irrad. at
13
Ž
.
Ž
.
.
6.46 ppm. C NMR CD3CN : anti : ds80.41 Cp ,
Ž
.
Ž
.
Ž
.
Ž
Ž
84.70 C-1 , 88.11 C-2 , 89.20 C-3 , 83.01 C-4 ,
Ž
.
Ž
.
.
.
103.57 C-4a , 95.51 C-9a , 140.81 C-4b , 124.48
Ž
Ž
.
Ž
.
Ž
.
Ž
Ž
C-5 , 135.09 C-6 , 132.50 C-7 , 127.57 C-8 , 132.62
X
X
.
Ž
.
.
Ž
.
C-8a , 164.07 C-9 , 148.25 C-1 , 122.29 C-2 ,
X
X
X
)
)
Scheme 8.
Ž
.
Ž
.
Ž
.
131.39 C-3 , 127.48 C-4 , 129.59 C-5 , 120.31
X
X
Ž
.
C-6 , for attribution of C-3 , irradiation at 7.62 ppm;
Ž
.
Ž
.
Ž
.
syn: ds80.65 Cp , 86.89 C-1 , 87.87 C-2 , 89.63
Ž
Ž
Ž
.
Ž
.
Ž
.
Ž
.
spectra were recorded in some particular cases. The
solvent was CD3COCD3 or CD3CN. Samples were
C-3 , 84.06 C-4 , 104.31 C-4a , 88.29 C-9a , 139.44
.
Ž
.
Ž
.
Ž
.
C-4b , 123.70 C-5 , 135.00 C-6 , 132.74 C-7 , 124.91
X
X
Ž
.
Ž
.
Ž
.
Ž
.
.
filtered through a small column of celite 477 5=10
mm prior to being poured into the NMR tubes.
C-8 , 138.19 C-8a , 163.69 C-9 , 148.09 C-1 , C-2
non detected, 131.74 C-3 , 127.76 C-4 , 129.79
X
X
)
)
.
Ž
.
Ž
X
X
Ž
.
Ž
.
C-5 , 120.16 C-6 .
4.2. Reagents
X
5
6
(
) [
(
4.2.2. h -Cyclopentadienyl
1-9a-h -fluorenone- 4 -
q
Ž
.
)
]
( )
(
All Cp Fe arene
complexes were handled with
chloro -anil iron II hexafluorophosphate syn–anti
(
)) ( (
)y)
mixture 30:70 3f PF6
minimal exposure to visible light. Amine complexes
4a–i were isolated and manipulated in solution under
argon atmosphere by using conventional Schlenck tech-
niques. Solvents reagent grade were used without
further purification, with the exception of THF which
was distilled from sodium benzophenone under nitro-
gen.
y
Ž
.qŽ
.
Ž
Obtained by reacting Cp Fe fluorene PF6
1.08
.
Ž
.
g, 2.5 mmol , 4-chloronitrosobenzene 0.55 g, 3.5 mmol
and t-BuOK 15 mg, 0.13 mmol for 10 min. Recrystal-
Ž
.
Ž
.
Ž
lized in CH2Cl2rEther for eliminating of ca. 5% of Cp
y
.qŽ
.
Ž
Fe fluorenone PF6
detected as by-product 61%
.
w
xw
x
Ž
.
yield C24 H17 NFeCl PF6 found calc. : C, 51.67
X
X
Ž
.
Ž
.
Ž
.
Ž
.
.
Ž
.
Ž
.
Nitrone–imine mixtures 1a–dq1 a–d , 3iq3 i
51.87 ; H, 3.10 3.09 ; N, 2.47 2.52 ; Cl, 6.14 6.38% .
Ž
w
xq
and imines 3a–h were synthesized by t-BuOK-cata-
HRMS LSIMS : calc. for C24 H17 NFeCl 410.0399,
5
y1
w
Ž
Ž
.
Ž
.
Ž
lysed condensation of various nitrosoarenes with h -
found 410.0403. IR n cm : CsN 1655 . E1r2 0.1
N H2 SO4-acetone 1:1,v:v : y0.23 V vs. SCE. 1H
6
5
6
. Ž
.
xq
wŽ
. Ž
Ž
..
Cp h -diphenylmethane Fe
and h -Cp h -
.
xq
w x
X
Ž
.
Ž
.
Ž
.
Ž
fluorene Fe according to our precedent paper 63 .
NMR CD3CN : anti 70% : ds4.86 s, Cp , 7.00 d,
3
3
3
Jf6, H-1) , 6.47 t, Js6.3, H-2 , 6.52 t, Js6.2,
Ž
.
.
Ž
.
Ž
Characterization data of complexes 3e–g and 3iq3 i
3
3
)
.
Ž
.
Ž
Ž
.
have not been described in this report.
H-3 , 7.02 d, Jf6, H-4 , 7.98 d, Js7.5, H-5 ,
3
3
Ž
.
.
Ž
7.62 t, Js7.6, H-6 , 7.31 t, Js7.7, H-7 , 6.88 d,
X
3
3
X
3
5
6
(
) [
(
.
Ž
.
Ž
Ž
4.2.1. h -Cyclopentadienyl
1-9a-h -fluorenone- 2 -
Js7.8, H-8 , 7.09 d, Js8.8, H-2 , 7.53 d, Js8.8,
X
3
)
]
( )
(
.
Ž
Ž
.
Ž
.
.
chloro -anil iron II hexafluorophosphate syn–anti
H-3 ; syn 30% : ds4.77 s, Cp , 5.61 d, Js6.5,
3
3
(
)) (
)y)
mixture 25:75 3e PF6
(
.
Ž
.
H-1 , 6.09 t, Js6.3, H-2 , 6.44 t, Js6.3, H-3 ,
y
Ž
.qŽ
.
Ž
Ž
.
Obtained by reacting Cp Fe fluorene PF6
1.08
H-4 overlapped with H-1 and H-4 anti 7.0 ppm , 8.00
3
3
.
Ž
.
Ž
.
Ž
.
Ž
g, 2.5 mmol , 2-chloronitrosobenzene 0.55 g, 3.5 mmol
d, Js7.3, H-5 , 7.66 t, Js7.5, H-6 , 7.74 t,
3
3
3
Ž
.
Ž
.
.
Ž
.
Ž
and t-BuOK 15 mg, 0.13 mmol for 5 min 90% yield .
xw
Js7.4, H-7 , 7.97 d, Js7.4, H-8 , 7.11 d, Js8.6,
X
3
X
13
w
x
Ž
.
.
Ž
.
.
Ž
.
Ž
.
C24 H17 NFeCl PF6 found calc. : C, 51.95 51.87 ; H,
H-2 , 7.57 d, Js8.8, H-3 . C NMR CD3CN :
Ž
.
Ž
Ž
.
Ž
.
Ž
.
Ž
.
3.11 3.09 ; N, 2.47 2.52 ; Cl, 6.50 6.38% . HRMS
anti : ds80.35 Cp , 84.45 C-1 , 88.06 C-2 , 89.14
Ž
.
w
xq
Ž
Ž
.
Ž
.
Ž
.
.
Ž
.
.
LSIMS : calc. for C24 H17 NFeCl 410.0399, found
C-3 , 82.80 C-4 , 103.30 C-4a , 95.75 C-9a , 140.97
y1
Ž
.
Ž
.
Ž
.
Ž
.
Ž
Ž
410.0400. IR n cm : C5N 1658 . E1r2 0.1 N
C-4b , 124.41 C-5 , 134.73 C-6 , 132.06 C-7 , 128.18

(
)
F. Pierre et al.rJournal of Organometallic Chemistry 553 1998 253–267
261
X
Ž
.
Ž
.
Ž
.
Ž
.
w
x
Ž
Ž
..
C-8 , 132.19 C-8a , 162.69 C-9 , 150.20 C-1 ,
63 , E1r2 1 N H2 SO4-acetone 1:1,v:v : nitrone y0.09
X
X
X
y1
Ž
.
Ž
.
Ž
.
Ž
.
:
120.60 C-2 , 130.79 C-3 , 131.14 C-4 ; syn: ds
V vs. SCE, imine y0.18 V vs. SCE. IR n cm
1
Ž
.
.
Ž
.
Ž
.
Ž
.
Ž
.
Ž
.
Ž
.
80.50 Cp , 87.35 C-1 , 87.71 C-2 , 89.42 C-3 ,
C5N 1657 , CsO 1722 , N™O 1288 . H NMR
Ž
Ž
.
Ž
.
Ž
.
Ž
.
83.84 C-4 , 104.45 C-4a , 88.11 C-9a , 139.19 C-4b ,
123.57 C-5 , 134.73 C-6 , 132.65 C-7 , 124.77 C-8 ,
138.47 C-8a , 162.43 C-9 , 149.99 C-1 , 120.38
CD3COCD3 : The spectrum indicate the presence of
several isomers for the imine 3i and the nitrone 3X i.
Ž
.
Ž
.
Ž
.
Ž
.
X
X
Ž
.
Ž
.
Ž
Ž
.
Ž
Owing to broad signals slow rotation around the C1 –N
bond and complexity of the spectrum, we could not
X
X
X
Ž
.
Ž
.
.
.
C-2 , 131.18 C-3 , 131.34 C-4 .
achieve the complete interpretation of the data.; ds
Ž
.
5.7–8.9 m, 12H, aromatic , 5.17, 5.10, 5.03, 5.00
X
5
6
(
) [
)
(
4.2.3. h -Cyclopentadienyl
1-9a-h -fluorenone- 2 -
Ž
.
Ž
.
broad , 4.91 five singlets, 5H, Cp , 3.99, 3.91, 3.81,
]
( )
)) (
methoxycarbonylmethylene -anil iron II hexafluo-
Ž
.
3.70, 3.62 five singlets, 3H, CO2 Me . The reduction of
the mixture into the amine 4i 84% yield and the
coulometric data 2.9 F mol
the composition of the mixture.
(
(
(
)y)
Ž
rophosphate syn–anti mixture 20:80 3g PF6y
Ž
.
Ž
.qŽ
.
Ž
Obtained by reacting Cp Fe fluorene PF6
1.08
y1
Ž
.
are in agreement with
.
Ž
.
g, 2.5 mmol , methyl- 2-nitroso phenylacetate 0.63 g,
.
Ž
.
3.5 mmol and t-BuOK 15 mg, 0.13 mmol for 10 min
xw
Ž
.
w
x
Ž
.
95% yield . C27 H22 NO2 Fe PF6 found calc. : C,
Ž
.
Ž
.
Ž
.
4.3. General synthesis procedure of amine complexes
2a–d
54.59 54.66 ; H, 3.74 3.75 ; N, 2.66 2.36% . HRMS
Ž
.
w
xq
LSIMS : calc. for C27 H22 NO2 Fe 448.1000, found
y1
Ž
.
Ž
.
Ž
.
448.0991. IR n cm : C5N 1660 , C5O 1737 .
..
X
y
Ž
Ž
.
E1r2 0.1 N H2 SO4-acetone 1:1,v:v : y0.28 V vs.
Ž
.Ž
.
The nitrone–imine mixture 1a0.9 q1 a0.1 PF6
1
Ž
SCE. H NMR CD3COCD3 : Owing to very broad
signals, aromatic protons were not attributed. This is
Ž
.
Ž
0.50 g, 0.93 mmol was dissolved in a mixture 150
ml of ammonium buffer NH4 2 SO4 0.25 mol ly1
ŽŽ
q
.
.
X
NH3,H2O 0.5 mol ly1 and acetone 1:1,v:v . The
solution was electrolyzed at a mercury pool cathode at
y1.20 V vs. SCE until consumption of 3.8 Faradays
per mole of substrate. The electrolysis was stopped and
the hydro-organic mixture was separated from mercury.
After elimination of acetone by rotary evaporation and
addition of 1 g of NH4 PF6, the amine complex 2a was
probably due to slow rotation around the C1 –N bond.
.
Ž
.
Attempts to simplify the spectrum at lower or higher
Ž
.
temperature failed; ds6.0–8.2 m, 12H, aromatic ,
Ž
.
Ž
. Ž
5.13 anti, 80% and 5.08 syn, 20% two singlets, 5H,
.
Ž
Cp , 3.79 AB, dA s3.83, dB s3.75, JAB s15.3, 2H,
13
.
Ž
.
Ž
.
CH2 , 3.42 s, 3H, Me . C NMR CD3COCD3 : anti :
Ž
.
.
Ž
.
Ž
.
Ž
.
ds80.25 Cp , 84.50 C-1 , 87.99 C-2 , 89.19 C-3 ,
Ž
Ž
.
Ž
.
Ž
.
83.00 C-4 , 103.34 C-4a , 95.72 C-9a , 140.94 C-4b ,
Ž
.
extracted with CH2Cl2 2=75 ml . The organic layer
was dried over MgSO4 and concentrated by rotary
evaporation. Addition into 300 ml of cold ether induced
Ž
.
Ž
.
Ž
.
Ž
.
124.16 C-5 , 134.49 C-6 , 131.77 C-7 , 127.97 C-8 ,
X
Ž
.
Ž
.
Ž
.
132.41 C-8a , 162.45 C-9 , 150.03 C-1 , 125.42
X
X
X
X
Ž
.
Ž
.
Ž
Ž
.
Ž
.
C-2 , 132.47 C-3 , 126.57 C-4 , 129.24 C-5 ,
formation of a precipitate which was filtered and washed
X
y
Ž
.
.
Ž
.
Ž
.
.
118.54 C-6 , 38.27 CH2 , 172.12 CO , 52.16 CH3 ;
Ž
.
Ž
with ether. After drying under vacuum, 2a PF6
0.44
)
)
Ž
.
Ž
.
Ž
syn: ds80.60 Cp , 87.21 C-1 , 87.39 C-2 , 89.64
.
g, 0.84 mmol was isolated as a fine pale yellow powder
Ž
Ž
Ž
.
Ž
.
Ž
.
Ž
.
.
C-3 , 83.92 C-4 , 103.92 C-4a , 88.83 C-9a , 139.25
Ž
.
90% yield .
.
Ž
.
.
Ž
.
Ž
C-4b , 123.41 C-5 , 134.42 C-6 , 132.28 C-7 , 124.53
C-8 , 138.76 C-8a , 161.91 C-9 , 149.50 C-1 , C-2
non detected, 132.70 C-3 , 126.91 C-4 , 129.41 C-
5 , 118.73 C-6 , 37.85 CH2 , 172.42 CO , 52.16
X
X
.
Ž
Ž
.
Ž
.
5
6
(
)
[
4 .3 .1 .
h -C yclop en tad ienyl
1-6-h -a -
( )
X
X
Ž
.
Ž
Ž
.
Ž
(
)
]
phenylamino diphenylmethane iron II hexafluo-
X
X
.
Ž
.
.
Ž
.
(
(
)y)
rophosphate 2a PF6
xw
Ž
.
CH3 .
w
x
Ž
.
.
Ž
.
C24 H22 NFe PF6 found calc. : C, 54.81 54.88 ; H,
Ž
.
Ž
Ž
.
4.28 4.22 ; N, 2.71 2.67% . HRMS LSIMS : calc. for
5
6
(
) [
w
xq
380.1102, found 380.1108. IR
4.2.4. Mixture of h -cyclopentadienyl 1-9a-h -fluo-
renone- 2 -methoxycarbonyl -anil iron II hexafluo-
C24yH1 22 NFe
n
X
1
(
)
]
( )
Ž
Ž
.
Ž
.
Ž
.
.
cm : N-H 3416 . H NMR CD3COCD3 : ds5.10
3
5
6
(
) [
)
.
Ž
Ž
.
rophosphate and h -Cyclopentadienyl 1-9a-h -fluo-
s, 5H, Cp , 6.46–6.52 m, 3H 6.57 t, Js6.0, 1H
X
3
(
]
( )
Ž
. Ž
.
renone-n- 2 -methoxycarbonyl phenyl nitrone iron II
6.87 d, Js6.5, 1H H-2, H-3, H-4, H-5 and H-6 ,
hexafluorophosphate 3i0.6 q3X i0.4 PF6
3
3
(( )(
)y)
Ž
.
.
Ž
.
.
7.65 d, Js7.1, 2H, H-9 , 7.42 t, Jf7, 2H, H-10 ,
3
y
Ž
.qŽ
.
Ž
Ž
Ž
Ž
Obtained by reacting Cp Fe fluorene PF6
1.08
7.32 t, Js7.3, 1H, H-11 , 6.13 AB, dA s6.09 H-7 ,
3
3
.
Ž
.
Ž
Ž
.
.
Ž
g, 2.5 mmol , methyl- 2-nitroso benzoate 1.24 g, 7.5
mmol and t-BuOK 15 mg, 0.13 mmol for 1 h 77%
yield . C26 H20 NO2.4 Fe PF6 found calc. : C, 53.17
53.33 ; H, 3.36 3.44 ; N, 2.36 2.39% . HRMS
dB s6.18 broad,NH , JA3B s9.5, 2H , 6.95 d, Js
X
X
.
Ž
.
Ž
.
Ž
.
Ž
7.7, 2H, H-2 , 7.15 t, Jf7, 2H, H-3 , 6.68 t,
3
X
13
.
w
xw
x
Ž
.
.
Ž
.
Js7.3, 1H, H-4 . C NMR CD3COCD3 : ds78.04
Ž
Ž
.
Ž
.
Ž
.
Ž
.
Ž
Cp ,.86.97, 88.19, 88.27, 88.33 and 88.52 C-2, C-3,
.
w
xq
.
Ž
.
Ž
.
LSIMS : calc. for C26 H20 NO3Fe 450.0793, found
C-4, C-5 and C-6 , 111.21 C-1 , 60.48 C-7 , 142.49
w
xq
)
Ž
.
Ž
.
Ž
.
Ž
.
450.0807, calc. for C26 H20 NO2 Fe 434.0843, found
434.0844. The ratio of each compound could be esti-
mated by polarography according to our precedent work
C-8 , 128.21 C-9 , 129.92
C-10 , 129.08 C-11 ,
X
X
X
)
Ž
.
Ž
.
Ž
.
147.91 C-1 , 114.97 C-2 , 130.07
C-3 , 119.05
X
Ž
.
C-4 .

(
)
262
F. Pierre et al.rJournal of Organometallic Chemistry 553 1998 253–267
X
5
6
y
(
)
]
[
(
Ž
.
Ž
.
w
xw
x
Ž
.
4.3.2. h -Cyclopentadienyl
1-6-h -a- 2 -methyl
2d PF6
C, 55.67 55.68 ; H, 4.63 4.49 ; N, 2.54 2.60% .
xq
85% yield . C25H24 NFe PF6 found calc. :
)
( )
Ž
.
Ž
.
Ž
.
phenylamino diphenylmethane iron II hexafluorophos-
(
(
)y)
Ž
.
w
phate 2b PF6
Electrolysis of the nitrone–imine mixture 1b0.7
HRMS LSIMS : calc. for C25 H24 NFe
394.1258,
1
y1
Ž
Ž
.
Ž
.
q
found 394.1253. IR n cm : N-H 3405 . H NMR
X
y
.Ž
1 b0.3 PF6
.
Ž
.
Ž
.
Ž
Ž
.
Ž
.
0.55 g, 1.00 mmol consumed 3.4 Fara-
days per mole of substrate and lead to 0.48 g of
CD3COCD3 : ds5.12 s, 5H, Cp , 6.43–6.55 m, 3H
3
3
Ž
.
. Ž
6.59 t, Jf6, 1H 6.87 d, Jf6, 1H H-2, H-3, H-4,
3
y
Ž
.
Ž
Ž
.
w
xw
x
Ž
.
.
.
Ž
.
Ž
2b PF6
C, 55.01 55.68 ; H, 4.53 4.49 ; N, 2.48 2.60% .
xq
89% yield . C25H24 NFe PF6 found calc. :
H-5 and H-6 , 7.63 d, Js7.8, 2H, H-9 , 7.41 t,
3
3
.
Ž
.
Ž
.
Ž
.
Jf7, 2H, H-10 , 7.32 t, Js7.3, 1H, H-11 , 6.02
3
Ž
.
w
Ž
Ž
.
Ž
.
HRMS LSIMS : calc. for C25 H24 NFe
394.1258,
AB, dA s5.98 broad, NH , dB s6.07 H-7 , JAB
s
1
3
y1
Ž
.
Ž
.
.
Ž
found 394.1252. IR n cm : N-H 3413 . H NMR
9.7, 2H , 6.91 AB, dA s6.86, dB s6.97, JAB s8.4,
4H, H-2X and H-3 , 2.17 s, 3H, Me . 13C NMR
X
Ž
.
Ž
.
Ž
.
.
Ž
.
CD3COCD3 : ds5.10 s, 5H, Cp , 6.40–6.52 m, 3H
3
3
Ž
.
Ž
. Ž
Ž
.
Ž
.
6.58 t, Jf6, 1H 6.96 d, Js6.5, 1H H-2, H-3,
CD3COCD3 : ds78.03 Cp , 86.86, 88.19, 88.24,
3
.
Ž
Ž
.
Ž
Ž
Ž
.
.
H-4, H-5 and H-6 , 7.72 d, Js7.1, 2H, H-9 , 7.45 t,
88.27 and 88.47 C-2, C-3, C-4, C-5 and C-6 , 111.36
3
3
3
.
.
Ž
Ž
.
Ž
.
Ž
.
Ž
Jf7, 2H, H-10 , 7.35 t, Jf7, 1H, H-11 , 6.16 d,
C-1 , 60.84 C-7 , 142.68 C-8 , 128.18 C-9 , 129.87
3
X
X
.
Ž
.
.
Ž
.
Ž
Ž
.
Ž
.
Js8.9, 1H, H-7 , 5.30 d broad, Js9.0, 1H, NH ,
C-10 , 129.00 C-11 , 145.60 C-1 , 115.28 C-2 ,
3
X
7.07 d, Js7.6, 1H, H-3 , 6.64 t, 3Js7.3, 1H,
X
X
Ž
.
Ž
Ž
.
.
Ž
.
130.54 C-3 , 128.04 C-4 , 20.43 Me .
X
3
X
3
.
Ž
.
Ž
H-4 , 7.02 t, Js7.5, 1H, H-5 , 6.91 d, Jf8, 1H,
X
13
4.4. General synthesis procedure of amine complexes
.
Ž
.
Ž
.
H-6 , 2.29 s, 3H, Me . C NMR CD3COCD3 : ds
4a–i
Ž
.
Ž
78.00 Cp , 87.68, 88.15, 88.24, 88.40 and 88.58 C-2,
.
Ž
.
Ž
.
C-3, C-4, C-5 and C-6 , 111.03 C-1 , 60.55 C-7 ,
142.22 C-8 , 128.34 C-9 , 129.97 C-10 , 129.18 C-
y
Ž
.
Ž
.
0.98 g, 1.88 mmol
The imine complex 3a PF6
Ž
.
Ž
Ž
.
Ž
Ž
.
Ž
Ž
.
was dissolved in a mixture 150 ml of acetic buffer
X
X
X
.
.
.
Ž
.
11 , 145.43 C-1 , 124.45 C-2 , 131.30 C-3 , 119.17
y1
CH3CO2 Na 1.5 mol l qCH3CO2 H 0.5 mol ly1
Ž
.
X
X
X
Ž
.
Ž
.
Ž
.
Ž
.
C-4 , 127.63 C-5 , 112.89 C-6 , 18.08 Me .
Ž
.
and acetone 1:1,v:v . The solution was electrolyzed at a
mercury pool cathode at y1.00 V vs. SCE until con-
sumption of 2.0 Faradays per mole of substrate. The
electrolysis was stopped and the hydro-organic mixture
was poured into a schlenk tube under argon atmosphere.
After elimination of acetone by evaporation under vac-
uum and addition of 1 g of NH4 PF6 , the amine complex
X
5
6
(
)
]
[
(
1-6-h -a- 3 -methyl
4.3.3. h -Cyclopentadienyl
)
( )
phenylamino diphenylmethane iron II hexafluorophos-
(
(
)y)
phate 2c PF6
Electrolysis of the nitrone–imine mixture 1c0.8
Ž
q
X
y
.Ž
1 c0.2 PF6
.
Ž
.
1.10 g, 2.00 mmol consumed 3.5 Fara-
days per mole of substrate and lead to 0.92 g of
y
Ž
.
4a was extracted with CH2Cl2 2=25 ml . The organic
layer was dried over MgSO4 and concentrated. Addition
into 200 ml of cold ether induced formation of a
precipitate which was filtered and washed with ether.
After drying under vacuum, 4a PF6
Ž
.
Ž
.
w
xw
x
Ž
.
.
2c PF6
C, 55.80 55.68 ; H, 4.71 4.49 ; N, 2.59 2.60% .
xq
85% yield . C25H24 NFe PF6 found calc. :
Ž
.
Ž
.
Ž
Ž
.
w
HRMS LSIMS : calc. for C25 H24 NFe
394.1258,
1
y1
Ž
.
Ž
.
found 394.1259. IR n cm : N-H 3406 . H NMR
y
Ž
.
Ž
0.87 g, 1.66
Ž
.
Ž
.
Ž
.
CD3COCD3 : ds5.10 s, 5H, Cp , 6.41–6.61 m, 4H
3
.
Ž
mmol was isolated as a fine pale yellow powder 88%
Ž
Ž
. Ž
.
6.87 d, Js6.5, 1H H-2, H-3, H-4, H-5 and H-6 ,
3
3
.
yield .
.
Ž
.
7.63 d, Js7.1, 2H, H-9 , 7.41 t, Jf7, 2H, H-10 ,
3
Ž
.
Ž
7.32 t, Js7.3, 1H, H-11 , 6.09 AB, dA s6.06
5
6
(
)
[
1-9a -h -9-
4.4.1.
h -C yclopentadienyl
( )
3
Ž
.
Ž
.
.
Ž
Ž
broad,NH , dB s6.12 H-7 , JAB s9.6, 2H , 6.82 s
(
(
)
]
phenylamino fluorene iron II hexafluorophosphate
X
3
X
.
Ž
.
.
broad, 1H, H-2 , 6.76 d, Js8.0, 1H, H-4 , 7.03 t,
(
)) (
(
)y)
exo–endo mixture 75:25 4a PF6
xw
3
X
3
X
.
Ž
Ž
Js7.8, 1H, H-5 , 6.52 d, Jf8, 1H, H-6 , 2.22 s,
w
x
Ž
.
Ž
.
C24 H20 NFe PF6 found calc. : C, 54.79 55.09 ; H,
X
X
.
3H, Me , for attribution of H-4 and H-6 irradiation at
Ž
.
Ž
.
Ž
.
3.97 3.86 ; N, 2.66 2.68% . HRMS LSIMS : calc. for
13
Ž
.
Ž
.
7.03 ppm. C NMR CD3COCD3 : ds78.04 Cp ,
y1
w
xq
Ž
.
:
C24 H20 NFe 378.0945, found 378.0946. IR n cm
Ž
86.79, 88.21, 88.25, 88.29 and 88.48 C-2, C-3, C-4,
N-H 3416 broad . NMR: H, 13C-correlation experi-
1
Ž
.
.
Ž
.
Ž
.
Ž
.
C-5 and C-6 , 111.37 C-1 , 60.43 C-7 , 142.65 C-8 ,
128.17 C-9 , 129.89 C-10 , 129.02 C-11 , 147.91
C-1 , 115.75 C-2 , 139.59 C-3 , 120.00 C-4 ,
1
Ž
.
Ž
.
Ž
.
Ž
ment. H NMR CD3CN : exo 75% : ds4.80 s, Cp ,
Ž
.
Ž
.
Ž
.
3
3
Ž
.
Ž
.
6.71 d, Js6.2, H-1 , 6.17 t, Js6.2, H-2 , 6.31 t,
X
X
X
X
Ž
.
Ž
.
Ž
.
Ž
.
3
3
3
.
Ž
.
Ž
Js6.2, H-3 , 6.91 d, Js6.2, H-4 , 7.98 d, Jf7,
X
X
Ž
.
Ž
.
Ž
.
129.99 C-5 , 112.14 C-6 , 21.67 Me , for attribution
3
3
.
Ž
.
Ž
.
H-5 , 7.58 t, Jf7, H-6 , 7.56 t, Jf7, H-7 , 7.66
of C-8 and C-9 irrad. at 6.12 ppm, for C-1, C-2X, C-3X
X
3
3
Ž
.
Ž
.
Ž
d, Jf7, H-8 , 6.12 d, Js9.2, H-9 , 5.10 d broad,
and C-4X irrad. at 2.22 ppm.
3
3
X
3
.
Ž
.
Ž
Js9.4, NH ,6.75 d, Jf8, H-2 , 7.16 t, Jf8,
X
X
3
X
5
6
(
)
]
[
(
.
Ž
.
4.3.4. h -Cyclopentadienyl
1-6-h -a- 4 -methyl
H-3 , 6.74 t, Jf8, H-4 , for attribution of H-9 irrad.
at 5.10 ppm, for H-1, H-2, H-3 and H-4 irrad. at 6.17
and 6.31 ppm and gated decoupling 13C experiment
)
( )
phenylamino diphenylmethane iron II hexafluorophos-
phate 2d PF6
Electrolysis of the nitrone–imine mixture 1d0.85
0.90 g, 1.63 mmol consumed 3.6 Fara-
days per mole of substrate and lead to 0.75 g of
(
(
)y)
Ž
Ž
.
q
6.12 ppm showing by off-resonance the long range
X
y
.Ž
1 d0.15 PF6
.
Ž
.
coupling of H-2 with C-9a, for attribution of H-5, H-6,
H-7 and H-8 gated dec. 13C at 7.99 ppm showing long

(
)
F. Pierre et al.rJournal of Organometallic Chemistry 553 1998 253–267
263
range coupling of H-5 with C-4a, C-7 and C-8a; endo
quaternary carbons C-9a, C-4a, C-4b, C-8a irrad. at
3
Ž
.
Ž
.
Ž
.
Ž
Ž
.
25% : ds4.75 s, Cp , 6.55 d, Js6.4, H-1 , 6.13 t,
8.01, 7.57 and 7.60 ppm; endo: ds78.37 Cp , 85.02
3
3
3
.
Ž
.
Ž
Ž
Ž
.
Ž
.
Ž
.
Ž
.
Js6.2, H-2 , 6.32 t, Js6.1, H-3 , 6.94 d, Jf6,
C-1 , 85.85 C-2 , 87.71 C-3 , 81.40 C-4 , 103.57
3
3
.
Ž
.
Ž
.
Ž
.
Ž
.
Ž
.
H-4 , 7.98 d, Jf7, H-5 , 7.68 t, Jf7, H-6 and
C-4a , 112.28 C-9a , 137.26 C-4b , 123.57 C-5 ,
3
3
)
.
Ž
.
Ž
.
Ž
.
Ž
. Ž .
C-7 , 126.78 C-8 , 147.50
X X
H-7 , 7.68 d, Jf7, H-8 , 5.87 d, Js7.9, H-9 , 5.23
130.60 C-6 , 131.64
3
3
X
Ž
.
Ž
.
Ž
Ž
.
Ž
.
Ž
.
Ž
.
d broad, Js7.7, NH , 7.12 d, Jf8, H-2 , 7.33 t,
C-8a , 59.64 C-9 , 146.39 C-1 , 124.18 C-2 ,
3
X
3
X
X
X
X
131.92) C-3 , 119.65 C-4 , 128.52 C-5 , 111.64
.
Ž
.
Ž
.
Ž
.
Ž
.
Jf8, H-3 , 6.85 t, Js7.3, H-4 , for attribution of
H-2X, H-3X and H-4X irrad. at 7.13 and 7.33 ppm. 13C
X
Ž
.
Ž
.
C-6 , 18.48 Me .
Ž
.
Ž
.
Ž
.
NMR CD3CN : exo : ds79.11 Cp , 86.61 C-1 ,
X
5
6
(
)
[
(
1-9a-h -9- 3 -methyl
4.4.3. h -Cyclopentadienyl
Ž
.
Ž
.
Ž
Ž
.
Ž
.
86.74 C-2 , 87.57 C-3 , 80.99 C-4 , 104.96 C-4a ,
)
]
( )
phenylamino fluorene iron II hexafluorophosphate
Ž
.
Ž
.
Ž
.
110.07 C-9a , 136.86 C-4b , 123.35 C-5 , 130.75
(
(
)) (
(
)y)
exo–endo mixture 75:25 4c PF6
Electrolysis of the imine 3c PF6
Ž
Ž
.
.
.
Ž
.
Ž
Ž
.
C-6 , 132.06 C-7 , 126.80 C-8 , 145.71 C-8a , 61.07
y
Ž
.
Ž
0.92 g, 1.71
X
X
X
Ž
.
.
Ž
.
C-9 , 147.79 C-1 , 115.20 C-2 , 130.51 C-3 ,
y1
.
Ž
mmol in acetic buffer CH3CO2 Na 1.5 mol l
q
X
Ž
.
119.67 C-4 , for attribution of C-7, quaternary carbons
C-9a, C-4a, C-4b, C-8a and C-1 irrad. at 6.12 and 7.99
CH3CO2 H 0.5 mol ly1 -acetone 1:1,v:v consumed 2.0
.
Ž
.
X
Faradays per mole of substrate and lead to 0.75 g of
Ž
.
.
Ž
.
Ž
.
ppm; endo: ds78.43 Cp , 85.12 C-1 , 85.76 C-2 ,
y
Ž
.
Ž
.
w
xw
x
Ž
.
4c PF6
81% yield . C25H22 NFe PF6 found calc. :
Ž
.
Ž
Ž
.
Ž
.
87.57 C-3 , 81.30 C-4 , 103.50 C-4a , 112.85 C-9a ,
Ž
.
Ž
.
Ž
.
C, 55.80 55.89 ; H, 4.11 4.14 ; N, 2.62 2.61% .
Ž
.
Ž
.
Ž
Ž
.
Ž
Ž
.
.
137.29 C-4b , 123.57 C-5 , 130.63 C-6 , 131.61 C-7 ,
126.63 C-8 , 147.07 C-8a , 59.65 C-9 , 148.89 C-1 ,
Ž
.
w
xq
HRMS LSIMS : calc. for C25 H22 NFe
392.1102,
X
Ž
.
Ž
.
.
1
y1
Ž
.
Ž
.
found 392.1124. IR n cm : N-H 3419 broad . H
X
X
X
Ž
.
Ž
.
Ž
.
114.15 C-2 , 130.85 C-3 , 119.54 C-4 for attribu-
tion of C-7, C-9a, C-4a, C-4b and C-8a irrad. at 7.99
ppm.
Ž
.
Ž
.
Ž
.
Ž
NMR CD3CN : exo 75% : ds4.80 s, Cp , 6.71 d,
3
3
3
.
Ž
Ž
.
Ž
Js6.1, H-1 , 6.17 t, Js6.2, H-2 , 6.31 t, Js6.2,
3
.
.
Ž
.
H-3 , 6.91 d, Js6.6, H-4 , 7.95–8.03 m, H-5 ,
Ž
.
Ž
.
7.52-7.64 m, H-6 and H-7 , 7.64–7.75 m, H-8 , 6.11
X
5
6
(
)
[
(
1-9a-h -9- 2 -methyl
4.4.2. h -Cyclopentadienyl
( )
3
3
Ž
.
Ž
.
Ž
d, Js9.9, H-9 , 4.74 d broad, Js9.7, NH , 6.64 s
)
]
phenylamino fluorene iron II hexafluorophosphate
X
3
X
3
.
Ž
Ž
.
Ž
Ž
broad, H-2 , 6.59 d, Jf8, H-4 , 7.04 t, Js7.7,
(
(
)) (
(
)y)
exo–endo mixture 85:15 4b PF6
Electrolysis of the imine 3b PF6
X
3
X
.
.
.
H-5 , 6.55 d, Jf8, H-6 , 2.24 s, Me , for attribu-
y
Ž
.
Ž
0.70 g, 1.31
tion of H-4X, H-5X and H-6X irrad. at 7.04 ppm; endo
y1
.
Ž
mmol in acetic buffer CH3CO2 Na 0.5 mol l
q
X
Ž
.
Ž
.
25% : ds4.75 s, Cp , H-1 overlapped with H-4 and
CH3CO2 H 0.5 mol ly1 -acetone 1:1,v:v consumed 2.0
.
Ž
.
X
3
Ž
.
Ž
.
H-6 exo 6.55–6.59 ppm , 6.13 t, Js6.2, H-2 , 6.32
Faradays per mole of substrate and lead to 0.59 g of
3
3
Ž
.
Ž
.
Ž
t, Js6.1, H-3 , 6.93 d, Js6.5, H-4 , 7.95-8.03 m,
y
Ž
.
Ž
.
w
xw
x
Ž
.
4b PF6
84% yield . C25H22 NFe PF6 found calc. :
.
Ž
.
Ž
.
.
Ž
H-5 , 7.52-7.64 m, H-6 and H-7 , 7.64–7.75 m, H-8 ,
Ž
.
Ž
.
Ž
.
C, 55.64 55.89 ; H, 4.15 4.14 ; N, 2.67 2.61% .
3
3
Ž
.
Ž
5.86 d, Js8.0, H-9 , 5.13 d broad, Js8.2, NH ,
Ž
.
w
xq
HRMS LSIMS : calc. for C25 H22 NFe
392.1102,
X
3
X
Ž
.
Ž
Ž
.
6.96 s broad, H-2 , 6.69 d, Jf8, H-4 , 7.21 t,
1
y1
Ž
.
Ž
.
found 392.1104. IR n cm : N-H 3411 . H NMR
3
X
3
X
Js7.7, H-5 , 6.92 d, Jf8, H-6 , 2.35 s, Me . 13C
.
.
Ž
Ž
.
3
Ž
.
Ž
.
Ž
.
Ž
CD3CN : exo 85% : ds4.81 s, Cp , 6.73 d, Js
Ž
.
.
Ž
.
.
NMR CD3CN : exo : ds79.11 Cp , 86.59 C-1 ,
3
3
.
Ž
.
Ž
.
6.5, H-1 , 6.18 t, Js6.2, H-2 , 6.32 t, Js6.2, H-3 ,
Ž
.
Ž
.
Ž
Ž
.
Ž
86.71 C-2 , 87.57 C-3 , 80.99 C-4 , 104.91 C-4a ,
3
Ž
.
Ž
.
Ž
6.92 d, Js6.3, H-4 , 7.97–8.04 m, H-5 , 7.53–7.64
Ž
.
Ž
.
Ž
.
110.09 C-9a , 136.86 C-4b , 123.32 C-5 , 130.75
3
Ž
.
Ž
.
m, H-6 and H-7 , 7.64–7.80 m, H-8 , 6.19 d, Js9.3,
Ž
Ž
.
.
.
Ž
.
Ž
Ž
.
C-6 , 132.04 C-7 , 126.80 C-8 , 145.81 C-8a , 61.02
3
.
Ž
.
Ž
Ž
H-9 , 4.74 d broad, Js9.5, NH , 7.07 d broad,
X
X
X
Ž
.
.
Ž
.
.
C-9 , 147.83 C-1 , 116.06 C-2 , 140.38 C-3 ,
3
3
X
3
X
.
Ž
Ž
.
Jf8, H-3 , 6.68 t, Js7.4, H-4 , 7.02 t broad,
X
X
X
Ž
.
Ž
.
Ž
.
Ž
120.59 C-4 , 130.41 C-5 , 112.21 C-6 , 21.76 Me ;
X
3
X
.
.
Ž
.
Js7.4, H-5 , 6.76 d, Js7.5, H-6 , 2.08 s, Me ,for
Ž
.
.
Ž
.
Ž
.
endo: ds78.41 Cp , 85.16 C-1 , 85.74 C-2 , 87.57
attribution of H-9 irrad. at 4.74 ppm and gated dec. 13C
Ž
Ž
Ž
Ž
.
Ž
Ž
.
Ž
.
C-3 , 81.28 C-4 , 103.48 C-4a , 112.91 C-9a , 137.28
at 6.19 ppm, for H-3X, H-4X, H-5X and H-6Xgated dec. 13
C
.
Ž
.
.
Ž
.
Ž
.
.
C-4b , 123.57 C-5 , 130.62 C-6 , 131.61 C-7 , 126.63
C-8 , 147.11 C-8a , 59.64 C-9 , 148.90 C-1 , 114.85
Ž
.
at 7.02, 7.07, 6.68 and 6.76 ppm; endo 15% : ds4.79
X
.
.
Ž
Ž
.
Ž
3
3
Ž
.
Ž
Ž
Ž
.
Ž
.
s, Cp , 6.61 d, Js6.2, H-1 , 6.17 t, Js6.2, H-2 ,
X
X
X
X
Ž
.
Ž
Ž
.
Ž
.
C-2 , 140.71 C-3 , 120.43 C-4 , 130.75 C-5 ,
3
3
.
Ž
.
6.34 t, Js6.2, H-3 , 6.96 d, Js6.2, H-4 , 7.97–
X
Ž
.
.
111.32 C-6 , 21.91 Me .
.
Ž
.
8.04 m, H-5 , 7.53–7.64 m, H-6 and H-7 , 7.64–7.80
3
3
X
5
6
Ž
.
Ž
.
Ž
(
)
[
(
1-9a-h -9- 4 -methyl
m, H-8 , 5.94 d, Js7.4, H-9 , 4.52 d broad, Js7.3,
4.4.4. h -Cyclopentadienyl
X
X
X
.
Ž
Ž
.
)
]
( )
)) ( (
NH , 7.21–7.29 m, H-3 , H-5 and H-6 , 6.80–6.85
phenylamino fluorene iron II hexafluorophosphate
X
13
(
(
)y)
Ž
.
.
Ž
.
m, H-4 , 2.30 s, Me . C NMR CD3CN : exo :
exo–endo mixture 75:25 4d PF6
Electrolysis of the imine 3d PF6
y
Ž
.
.
Ž
.
Ž
Ž
.
Ž
.
Ž
.
Ž
0.56 g, 1.04
ds79.09 Cp , 86.74 C-1 , 86.74 C-2 , 87.53 C-3 ,
y1
Ž
Ž
.
.
Ž
.
Ž
80.85 C-4 , 105.14 C-4a , 110.39 C-9a , 136.85 C-
mmol in acetic buffer CH3CO2 Na 1.5 mol l
q
CH3CO2 H 0.5 mol ly1 -acetone 1:1,v:v consumed 2.0
.
Ž
.
Ž
Ž
.
.
Ž
.
.
Ž
.
4b , 123.36 C-5 , 130.69 C-6 , 132.11 C-7 , 126.69
C-8 , 146.09 C-8a , 60.99 C-9 , 145.47 C-1 , 124.62
X
Ž
Ž
.
Ž
.
Ž
.
Faradays per mole of substrate and lead to 0.49 g of
X
X
X
X
y
.
Ž
.
Ž
.
Ž
.
Ž
.
Ž
Ž
.
w
xw
x
Ž
.
C-2 , 131.73 C-3 , 119.39 C-4 , 128.00 C-5 ,
4d PF6
87% yield . C25H22 NFe PF6 found calc. :
X
Ž
.
Ž
.
.
Ž
.
Ž
.
112.54 C-6 , 18.01 Me , for attribution of C-7 and
C, 55.54 55.89 ; H, 4.04 4.14 ; N, 2.68 2.61% .

(
)
264
F. Pierre et al.rJournal of Organometallic Chemistry 553 1998 253–267
Ž
.
w
xq
HRMS LSIMS : calc. for C25 H22 NFe
Ž
.
Ž
.
Ž
.
Ž
.
392.1102,
132.22 C-7 , 126.57 C-8 , 145.22 C-8a , 60.74 C-9 ,
1
X
X
X
y1
Ž
.
Ž
.
Ž
.
Ž
.
Ž
.
found 392.1091. IR n cm : N-H 3419 broad . H
143.31 C-1 , 120.74 C-2 , 130.74 C-3 , 120.10
C-4 , 129.12 C-5 , 114.22 C-6 for attribution of
X
X
X
Ž
.
Ž
.
Ž
.
Ž
Ž
.
Ž
.
Ž
.
NMR CD3CN : exo 75% : ds4.79 s, Cp , 6.68 d,
3
3
3
X
.
Ž
.
Ž
Ž
.
Js6.2, H-1 , 6.16 t, Js6.2, H-2 , 6.30 t, Js6.2,
C-1 irrad. at 7.08 ppm; endo: ds78.43 Cp , 85.00
3
.
Ž
.
Ž
.
Ž
Ž
.
Ž
.
Ž
.
Ž
.
H-3 , 6.90 d, Js6.4, H-4 , 7.90–8.05 m, H-5 ,
C-1 , 85.91 C-2 , 87.84 C-3 , 81.56 C-4 , 103.82
Ž
.
Ž
.
.
Ž
.
Ž
.
Ž
.
7.50–7.63 m, H-6 and H-7 , 7.63–7.75 m, H-8 , 6.07
C-4a , 111.15 C-9a , 137.23 C-4b , 123.72 C-5 , C-6
non detected, 131.87 C-7 , 126.64 C-8 , 146.98 C-8a ,
3
3
Ž
Ž
Ž
.
Ž
.
Ž
.
Ž
Ž
.
Ž
.
.
d, Js8.9, H-9 , 4.90 d broad, Js9.0, NH , 6.65
3
X
3
X
X
X
X
.
Ž
.
Ž
.
Ž
.
.
Ž
d, Js8.3, H-2 , 6.97 d broad, Js8.1, H-3 , 2.20
58.93 C-9 , 144.05 C-1 , 120.46 C-2 , 130.86 C-3 ,
s, Me , for attribution of H-2 gated dec. 13C at 6.65
X
X
X
X
.
Ž
.
Ž
.
Ž
.
120.46 C-4 , 129.75 C-5 , 113.60 C-6 .
3
Ž
.
Ž
.
Ž
ppm; endo 25% : ds4.75 s, Cp , 6.54 d, Js6.2,
X
5
6
(
)
[
(
1-9a-h -9- 4 -chloro
4.4.6. h -Cyclopentadienyl
( )
3
3
.
Ž
.
Ž
.
H-1 , 6.13 t, Js6.2, H-2 , 6.32 t, Jf6, H-3 , 6.92
)
]
phenylamino fluorene iron II hexafluorophosphate
3
Ž
.
Ž
.
Ž
d, Jf6, H-4 , 7.90–8.05 m, H-5 , 7.50–7.63 m,
(
(
)) ( (
)y)
exo–endo mixture 80:20 4f PF6
3
.
Ž
.
Ž
H-6 and H-7 , 7.63–7.75 m, H-8 , 5.82 d, Js7.9,
y
Ž
.
Ž
0.70 g, 1.26
Electrolysis of the imine 3f PF6
3
.
Ž
.
Ž
H-9 , 5.01 d broad, Js8.0, NH , 7.09 AB, dA s7.03,
mmol in ammonium buffer NH4 2 SO4 0.25 mol ly1
.
ŽŽ
.
Ž
dB s7.15, 3JAB s8.4, H-2 and H-3 , 2.30 s, Me . 13C
X
X
.
Ž
Ž
.
Ž
qNH4,H2O 0.5 mol ly1 -acetone 1:1,v:v consumed
.
.
Ž
Ž
.
.
.
.
NMR CD3CN : exo : ds79.08 Cp , 86.57 C-1 ,
2.0 Faradays per mole of substrate and lead to 0.55 g of
.
Ž
.
Ž
Ž
.
Ž
86.70 C-2 , 87.53 C-3 , 80.96 C-4 , 104.95 C-4a ,
y
Ž
.
Ž
.
w
xw
x
4f PF6
79% yield . C24 H19 NClFe PF6 found
Ž
.
.
Ž
.
110.19 C-9a , 136.84 C-4b , 123.31 C-5 , 130.69
Ž
.
Ž
.
Ž
.
Ž
.
calc. : C, 51.84 51.68 ; H, 3.54 3.44 ; N, 2.32 2.51 ;
Cl, 6.26 6.36% . HRMS LSIMS : calc. for
C24 H19 NClFe
cm : N-H 3444 . H NMR CD3CN : exo 80% :
Ž
Ž
.
.
Ž
.
Ž
.
Ž
Ž
.
C-6 , 132.01 C-7 , 126.80 C-8 , 145.86 C-8a , 61.49
C-9 , 145.39 C-1 , 115.55 C-2 , 130.92 C-3 ,
Ž
.
Ž
.
X
X
X
Ž
.
Ž
.
Ž
.
w
xq
412.0556, found 412.0575. IR n
X
Ž
.
.
Ž
.
128.98 C-4 , 20.53 Me ; endo: ds78.40 Cp , 85.11
1
y1
Ž
.
Ž
.
Ž
.
Ž
.
Ž
Ž
.
Ž
.
Ž
.
Ž
Ž
.
C-1 , 85.73 C-2 , 87.53 C-3 , 81.28 C-4 , 103.47
3
3
Ž
.
Ž
.
Ž
ds4.80 s, Cp , 6.70 d, Js6.5, H-1 , 6.18 t, Js
.
Ž
.
.
Ž
.
C-4a , 113.00 C-9a , 137.25 C-4b , 123.55 C-5 ,
130.58 C-6 , 131.59 C-7 , 126.58 C-8 , 147.31 C-8a ,
60.00 C-9 , 146.55 C-1 , 114.36 C-2 , 131.25 C-3 ,
128.72 C-4 , 20.59 Me .
6.2, H-2 , 6.32 t, Js6.1, H-3 , 6.91 d, 3Js6.2,
3
.
Ž
.
Ž
Ž
.
Ž
.
Ž
.
Ž
.
.
Ž
.
Ž
.
Ž
H-4 , 7.96-8.01 m, H-5 , 7.51–7.63 m, H-6 and H-7 ,
X
X
X
Ž
.
Ž
.
Ž
.
Ž
.
3
Ž
.
.
Ž
.
7.64–7.70 m, H-8 , 6.09 d, Js9.7, H-9 , 5.19 d
X
Ž
.
Ž
.
3
3
X
Ž
.
Ž
Ž
broad, Js9.7, NH , 6.73 d, Js8.9, H-2 , 7.14 d,
3
3
X
.
Ž
.
Ž
.
Js8.9, H-3 ; endo 20% : ds4.75 s, Cp , 6.54 d,
X
5
6
(
)
[
(
1-9a-h -9- 2 -chloro
4.4.5. h -Cyclopentadienyl
3
3
.
Ž
.
Ž
Js6.3, H-1 , 6.13 t, Js6.5, H-2 , 6.33 t, Js6.2,
)
]
( )
phenylamino fluorene iron II hexafluorophosphate
exo–endo mixture 80:20 4e PF6
3
.
Ž
.
Ž
.
H-3 , 6.93 d, Jf6, H-4 , 7.96–8.01 m, H-5 , 7.51–
(
(
)) (
(
)y)
Ž
.
Ž
.
.
Ž
Ž
7.63 m, H-6 and H-7 , 7.64–7.70 m, H-8 , 5.84 d,
y
Ž
.
Ž
0.70 g, 1.26
Electrolysis of the imine 3e PF6
3
3
3
.
Ž
Js7.9, H-9 , 5.33 d broad, Js8.0, NH , 7.10 d,
y1
.
Ž
mmol in acetic buffer CH3CO2 Na 0.5 mol l
q
X
3
X
Js9.0, H-2 , 7.32 d, Js8.8, H-3 . 13C NMR
.
Ž
.
Ž
CH3CO2 H 0.5 mol ly1 -acetone 1:1,v:v consumed 1.9
.
Ž
.
Ž
Ž
Ž
.
Ž
.
.
CD3CN : exo : ds79.14 Cp , 86.67 C-1 , 86.78
Faradays per mole of substrate and lead to 0.62 g of
.
Ž
.
Ž
.
Ž
.
C-2 , 87.62 C-3 , 81.03 C-4 , 104.93 C-4a , 109.67
y
Ž
.
Ž
.
w
xw
x
4e PF6
88% yield . C24 H19 NClFe PF6 found
.
Ž
.
Ž
.
Ž
Ž
.
.
C-9a , 136.85 C-4b , 123.39 C-5 , 130.84 C-6 ,
Ž
.
Ž
.
Ž
.
Ž
.
calc. : C, 52.10 51.68 ; H, 3.56 3.44 ; N, 2.44 2.51 ;
Cl, 6.43 6.36% . HRMS LSIMS : calc. for
C24 H19 NClFe
cm : N-H 3402 . H NMR CD3CN : exo 80% :
Ž
Ž
.
Ž
.
Ž
.
132.11 C-7 , 126.80 C-8 , 145.34 C-8a , 61.05 C-9 ,
Ž
.
Ž
.
X
X
X
.
Ž
.
Ž
.
146.70 C-1 , 116.54 C-2 , 130.19 C-3 , 123.60
w
xq
412.0556, found 412.0575. IR n
X
Ž
.
Ž
.
Ž
.
Ž
.
C-4 ; endo: ds78.46 Cp , 85.13 C-1 , 85.76 C-2 ,
1
y1
Ž
.
Ž
.
Ž
.
Ž
3
.
Ž
.
Ž
.
Ž
.
Ž
.
87.62 C-3 , 81.33 C-4 , 103.60 C-4a , 112.48 C-9a ,
3
Ž
.
Ž
.
Ž
ds4.82 s, Cp , 6.75 d, Jf6, H-1 , 6.21 t, Js6.2,
Ž
.
Ž
.
Ž
.
Ž
.
137.29 C-4b , 123.60 C-5 , 130.71 C-6 , 131.63 C-7 ,
3
3
.
Ž
.
Ž
.
.
H-2 , 6.33 t, Js6.2, H-3 , 6.93 d, Js6.4, H-4 ,
)
Ž
.
Ž
) Ž
126.65 C-8 , 146.70 C-8a , 59.63 C-9 , 147.79 C-
.
Ž
.
Ž
Ž
Ž
.
Ž
8.00–8.03 m, H-5 , 7.54–7.72 m, H-6, H-7 and H-8 ,
X
X
X
X
.
.
Ž
.
.
1 , 115.47 C-2 , 130.50 C-3 , 123.39 C-4 .
3
3
Ž
.
Ž
.
Ž
6.21 d, Js9.5, H-9 , 5.42 d broad, Js9.5, NH ,
3
X
3
X
X
5
6
Ž
.
Ž
.
(
) [
(
7.30 d, Js7.9, H-3 , 6.72 t, Js7.6, H-4 , 7.08 t,
4.4.7. h -Cyclopentadienyl 1-9a-h -9- 2 -methoxy-
3
X
3
X
.
Ž
.
)
]
( )
Js7.8, H-5 , 6.76 d, Jf8, H-6 , for attribution of
carbonylmethylene phenylamino fluorene iron II hex-
H-3X, H-4X, H-5X and H-6X irrad. at 7.30 ppm and gated
(
(
))
afluorophosphate exo–endo mixture 80:20
13
Ž
.
(
(
)y)
dec. C at 6.72, 7.08 and 7.30 ppm; endo 20% :
4g PF6
Electrolysis of the imine 3g PF6
3
3
y
Ž
.
Ž
.
Ž
Ž
.
Ž
0.50 g, 0.84
ds4.82 s, Cp , 6.55 d, Js6.2, H-1 , 6.17 t, Js
6.2, H-2 , 6.36 t, Js6.3, H-3 , 6.97 d, 3Js6.4,
3
y1
.
Ž
.
Ž
.
Ž
mmol in acetic buffer CH3CO2 Na 0.5 mol l
q
CH3CO2 H 0.5 mol ly1 -acetone 1:1,v:v consumed 2.1
.
Ž
.
Ž
.
Ž
.
H-4 , 8.00–8.03 m, H-5 , 7.54–7.72 m, H-6, H-7 and
3
3
.
Ž
Ž
.
.
Ž
Ž
H-8 , 6.01 d, Js8.4, H-9 , 5.04 d broad, Js8.6,
Faradays per mole of substrate and lead to 0.35 g of
3
X
3
X
y
.
.
Ž
.
Ž
.
.
w
xw
x
NH , 7.47 d, Js8.1, H-3 , 6.89 t, Js7.5, H-4 ,
4g PF6
70% yield . C27 H24 NO2 Fe PF6 found
3
X
3
X
7.38 t, Jf8, H-5 , 7.43 d, Jf8, H-6 . 13C NMR
Ž
.
Ž
.
Ž
.
Ž
Ž
Ž
.
Ž
.
calc. : C, 54.59 54.47 ; H, 4.20 4.07 ; N, 2.23 2.35 ;
P, 5.19 5.20% . HRMS LSIMS : calc. for
Ž
Ž
Ž
.
Ž
.
Ž
.
Ž
.
.
CD3CN : exo : ds79.20 Cp , 86.85 C-1 , 86.85
w
xq
.
Ž
.
Ž
.
Ž
.
C-2 , 87.67 C-3 , 80.98 C-4 , 105.07 C-4a , 109.53
C27 H24 NO2 Fe
450.1157, found 450.1138. IR n
cm : N-H 3423 broad , C5O 1733 . 1H NMR
y1
.
Ž
.
Ž
.
Ž
.
Ž
.
Ž
.
Ž
.
C-9a , 136.93 C-4b , 123.53 C-5 , 130.90 C-6 ,

(
)
F. Pierre et al.rJournal of Organometallic Chemistry 553 1998 253–267
265
3
)
)
Ž
.
Ž
.
Ž
.
Ž
Ž
Ž
Ž
.
Ž
.
Ž
.
CD3CN : exo 80% : ds4.81 s, Cp , 6.71 d, Js
CD3CN : exo : ds79.25 Cp , 86.79 C-1 , 86.86
3
3
.
Ž
.
Ž
.
.
Ž
.
Ž
.
Ž
.
6.2, H-1 , 6.19 t, Js6.2, H-2 , 6.32 t, Js6.2, H-3 ,
C-2 , 87.72 C-3 , 81.13 C-4 , 104.89 C-4a , 109.30
C-9a , 136.90 C-4b , 123.50 C-5 , 130.98 C-6 ,
132.20 C-7 , 126.79 C-8 , 144.96 C-8a , 60.20 C-9 ,
151.97 C-1 , 113.72 C-2 , 131.66 C-3 , 128.83
3
Ž
.
Ž
.
.
Ž
.
Ž
.
Ž
.
.
6.92 d, Js6.3, H-4 , 7.99–8.03 m, H-5 , 7.54–7.64
3
Ž
.
Ž
.
Ž
Ž
.
Ž
.
Ž
.
Ž
m, H-6 and H-7 , 7.65–7.72 m, H-8 , 6.18 d, Js9.3,
3
3
X
X
X
.
Ž
Ž
.
Ž
Ž
.
Ž
.
Ž
.
H-9 , 5.01 d broad, Js9.2, NH , 7.10 d, Js7.5,
X
3
X
3
X
X
.
.
Ž
.
.
Ž
.
Ž
.
Ž
.
Ž
.
.
H-3 , 6.76 t, Js7.4, H-4 , 7.13 t, Js7.8, H-5 ,
C-4 , 197.08 CO , 26.52 Me ; endo: ds78.53 Cp ,
3
X
Ž
.
Ž
.
Ž
Ž
.
Ž
.
Ž
.
Ž
6.86 d, Js7.5, H-6 , 3.52 s, CH2 , 3.53 s, CH3 ,
85.07 C-1 , 85.85 C-2 , 87.72 C-3 , 81.39 C-4 ,
for attribution of H-3X, H-4X and H-5X irrad. at 6.86 ppm;
Ž
.
Ž
.
Ž
.
103.55 C-4a , 111.97 C-9a , 137.39 C-4b , 123.68
3
Ž
.
Ž
.
Ž
.
Ž
Ž
Ž
.
Ž
.
Ž
Ž
.
Ž
Ž
.
endo 20% : ds4.82 s, Cp , 6.63 d, Js6.3, H-1 ,
C-5 , 130.87 C-6 , 131.66 C-7 , 126.79 C-8 , 146.00
C-8a , 58.95 C-9 , 153.06 C-1 , 113.01 C-2 , 132.05
C-3 , 128.97 C-4 , 197.15 CO , 26.61 Me for
attribution of C-3 and C-7 overlapped with C-3 exo
irrad. at 7.97 ppm.
3
3
X
X
Ž
.
Ž
.
Ž
.
.
Ž
.
.
.
6.21 t, Js6.2, H-2 , 6.36 t, Js6.2, H-3 , 6.98 d,
3
X
X
.
Ž
.
Ž
Ž
.
Ž
.
Ž
.
Js6.3, H-4 , 7.99–8.03 m, H-5 , 7.54–7.64 m, H-6
3
X
X
.
Ž
.
Ž
.
Ž
.
and H-7 , 7.65–7.72 m, H-8 , 5.93 d, Js7.8, H-9 ,
3
3
X
Ž
.
Ž
.
5.26 d broad, Js7.8, NH , 7.26 d, Js7.0, H-3 ,
X
X
Ž
.
H-4 overlapped with H-6 and H-4 exo f6.9 ppm ,
X
X
X
5
6
Ž
.
Ž
.
Ž
(
) [
(
7.32–7.39 m, H-5 and H-6 , 3.77 s, CH2 , 3.62 s,
4.4.9. h -Cyclopentadienyl
1-9a-h -9- 2 -methoxy-
13
)
.
.
Ž
.
Ž
.
)
]
( )
CH3 . C NMR CD3CN : exo : ds79.12 Cp , 86.74
carbonyl phenylamino fluorene iron II hexafluo-
)
(
(
)) ( (
)y)
Ž
Ž
Ž
.
Ž
.
Ž
Ž
.
C-1 , 86.81 C-2 , 87.57 C-3 , 80.95 C-4 , 105.01
rophosphate exo–endo mixture 45:55 4i PF6
.
Ž
.
.
.
.
Ž
.
Ž
C-4a , 110.14 C-9a , 136.83 C-4b , 123.41 C-5 ,
130.76 C-6 , 132.12 C-7 , 126.76 C-8 , 145.91 C-8a ,
61.06 C-9 , 145.82 C-1 , 122.04 C-2 , 132.71 C-3 ,
119.86 C-4 , 129.59 C-5 , 113.99 C-6 , 38.20
Electrolysis of the imine–nitrone mixture 3i0.6
q
3X i0.4 PF6
Ž
0.86 g, 1.47 mmol in acetic buffer
y
Ž
.
Ž
.
.
Ž
Ž
Ž
Ž
.
.Ž
.
Ž
.
X
X
X
CH3CO2 Na 1.5 mol l qCH3CO2 H 0.5 mol ly1
-
y1
Ž
.
Ž
Ž
.
.
X
X
X
Ž
.
.
Ž
.
Ž
.
acetone 1:1,v:v consumed 2.9 Faradays per mole of
y
Ž
.
Ž
.
Ž
.
Ž
.
Ž
.
CH2 , 172.80 CO , 52.63 CH3 , for attribution of
substrate and lead to 0.72 g of 4i PF6
xw
84% yield .
X
Ž
.
.
w
x
Ž
.
Ž
.
C-1 irrad. at 6.18 and 3.52 ppm; endo: ds78.53 Cp ,
C26 H22 NO2 Fe PF6 found calc. : C, 52.55 53.72 ;
Ž
.
Ž
.
Ž
.
Ž
Ž
.
.
Ž
.
Ž
.
84.75 C-1 , 85.78 C-2 , 87.80 C-3 , 81.66 C-4 ,
H, 3.64 3.82 ; N, 2.44 2.41 ; P, 5.28 5.33% . HRMS
Ž
w
xq
Ž
.
Ž
.
Ž
.
103.22 C-4a , 111.60 C-9a , 137.28 C-4b , 123.63
C-5 , 130.60 C-6 , 131.63 C-7 , 126.44 C-8 , 148.00
C-8a , 59.81 C-9 , 147.17 C-1 , 121.71 C-2 , 132.91
C-3 , 120.18 C-4 , 130.18 C-5 , 113.21 C-6 ,
LSIMS : calc. for C26 H22 NO2 Fe 436.1000, found
y1
Ž
Ž
Ž
.
Ž
.
Ž
Ž
.
Ž
Ž
.
.
Ž
.
Ž
.
436.0995. IR n cm : N-H 3420 broad, 3328 broad ,
X
X
1
1
C5O 1682 . NMR: H,13C-correlation and H,1H-
.
Ž
.
.
Ž
.
X
X
X
X
1
.
Ž
.
Ž
Ž
.
Ž
.
Ž
.
Ž
.
COSY experiments. H NMR CD3CN : exo 45% :
3
3
Ž
.
.
Ž
.
Ž
.
Ž
.
Ž
39.15 CH2 , 173.80 CO , 53.05 CH3 .
ds4.83 s, Cp , 6.78 d, Js6.1, H-1 , 6.21 t, Js
6.2, H-2 , 6.33 t, Js6.2, H-3 , 6.95 d, 3Js6.3,
3
.
Ž
.
Ž
X
3
5
6
(
)
[
(
1-9a-h -9- 4 -acetyl
phenylamino fluorene iron II hexafluorophosphate
.
Ž
.
Ž
4.4.8. h -Cyclopentadienyl
H-4 , 8.03 d, Js7.4, H-5 , 7.54–7.70 m, H-6, H-7
3
3
)
]
( )
.
.
Ž
.
Ž
and H-8 , 6.30 d, Js8.8, H-9 , 8.42 d broad, Js
3
X
3
(
(
)) (
(
)y)
Ž
.
Ž
exo–endo mixture 70:30 4h PF6
Electrolysis of the imine 3h PF6
8.5, NH , 7.92 d, Js8.1, H-3 , 6.72 t, Js8.1,
X
3
X
3
X
y
Ž
.
Ž
0.63 g, 1.12
.
Ž
Ž
.
Ž
.
H-4 , 7.32 t, Js8.4, H-5 , 6.77 d, Js8.5, H-6 ,
y1
.
Ž
.
.
Ž
.
Ž
.
Ž
mmol in acetic buffer CH3CO2 Na 1.5 mol l
q
3.79 s, CH3 ,; endo 55% : ds4.81 s, Cp , 6.58 d,
3
3
3
CH3CO2 H 0.5 mol ly1 -acetone 1:1,v:v consumed 2.1
Faradays per mole of substrate and lead to 0.51 g of
81% yield . C26 H22 NOFe PF6 found
calc. : C, 54.75 55.24 ; H, 3.85 3.93 ; N, 2.51
2.48% . HRMS LSIMS : calc. for C26 H22 NOFe
420.1051, found 420.1058. IR n cm : N-H 3412
.
Ž
.
Ž
.
Ž
Ž
Js6.3, H-1 , 6.19 t, Js6.2, H-2 , 6.38 t, Js6.2,
3
3
.
Ž
.
.
H-3 , 6.99 d, Js6.3, H-4 , 8.03 d, Js7.4, H-5 ,
3
y
Ž
.
Ž
.
w
xw
x
Ž
.
Ž
Ž
4h PF6
Ž
Ž
7.54–7.70 m, H-6, H-7 and H-8 , 6.09 d, Js8.7,
3
3
.
Ž
.
.
Ž
.
.
Ž
.
H-9 , 8.42 d broad, Js8.5, NH , 8.06 d, Js8.1,
X
3
X
3
X
.
Ž
w
xq
.
Ž
.
Ž
.
H-3 , 6.88 t, Js8.1, H-4 , 7.62 t, Js8.5, H-5 ,
3
X
7.46 d, Js8.5, H-6 , 3.84 s, CH3 . 13C NMR
y1
Ž
.
Ž
Ž
.
Ž
.
1
.
Ž
.
Ž
.
Ž
Ž
Ž
.
Ž
.
Ž
.
broad, 3360 broad , CsO 1661 . H NMR CD3CN :
CD3CN : exo : ds79.24 Cp , 86.78 C-1 , 86.86
3
Ž
Ž
.
Ž
.
Ž
Ž
.
.
Ž
.
Ž
.
Ž
.
exo 70% : ds4.82 s, Cp , 6.75 d, Js6.5, H-1 ,
C-2 , 87.66 C-3 , 81.14 C-4 , 104.88 C-4a , 109.75
3
3
.
Ž
.
Ž
.
Ž
.
Ž
.
Ž
.
.
6.20 t, Js6.2, H-2 , 6.34 t, Js6.2, H-3 , 6.94 d,
C-9a , 136.83 C-4b , 123.66 C-5 , 130.98 C-6 ,
132.28 C-7 , 126.53 C-8 , 145.20 C-8a , 60.06 C-9 ,
150.26 C-1 , 112.82 C-2 , 132.90 C-3 , 117.78
C-4 , 135.81 C-5 , 113.85 C-6 , 169.70 CO , 52.52
3
3
.
.
Ž
Ž
.
Ž
.
Ž
.
Ž
Js6.2, H-4 , 8.00 d, Js7.1, H-5 , 7.50–7.75 m,
3
X
X
X
.
Ž
Ž
.
.
Ž
Ž
Ž
.
Ž
.
Ž
.
H-6, H-7 and H-8 , 6.22 d, Js9.2, H-9 , 5.76 d
3
3
X
X
X
X
.
Ž
Ž
.
.
Ž
.
Ž
.
Ž
.
broad, Js9.2, NH , 6.78 d, Js8.8, H-2 , 7.79 d,
3
X
.
Ž
.
Ž
.
Ž
.
Ž
.
Js8.8, H-3 , 2.44 s, Me , for attribution of H-9
CH3 ; endo: ds78.64 Cp , 84.69 C-1 , 85.84 C-2 ,
irrad. at 5.76 ppm, for H-1, H-2X and H-3X irrad. at 7.79
Ž
.
Ž
.
Ž
.
Ž
.
87.91 C-3 , 81.87 C-4 , 103.64 C-4a , 110.63 C-9a ,
3
Ž
.
Ž
.
Ž
Ž
Ž
.
Ž
.
.
Ž
.
.
Ž
.
ppm; endo 30% : ds4.79 s, Cp , 6.55 d, Js6.3,
137.29 C-4b , 123.80 C-5 , 130.83 C-6 , 131.93 C-7 ,
3
3
X
.
Ž
.
Ž
.
.
Ž
Ž
Ž
.
H-1 , 6.15 t, Js6.2, H-2 , 6.34 t, Jf6, H-3 , 6.95
126.08 C-8 , 147.88 C-8a , 58.12 C-9 , 151.41 C-1 ,
3
3
X
X
X
Ž
Ž
.
Ž
.
Ž
.
Ž
.
Ž
.
d, Js6.1, H-4 , 8.00 d, Js7.1, H-5 , 7.50–7.75
112.31 C-2 , 133.05 C-3 , 117.92 C-4 , 136.53
C-5 , 113.06 C-6 , 170.39 CO , 52.73 CH3 . For
attribution of quaternary carbons of both isomers, irrad.
at 3.84 and 3.79 ppm CO , irrad. at 6.98 and 6.94 ppm
C-9a , irrad. at 6.08 ppm C-1, C-8a, C-9a and C-4a ,
X
X
.
Ž
Ž
Ž
.
Ž
.
Ž
.
Ž
.
m, H-6, H-7 and H-8 , 5.94 AB, dA s5.91 broad,
3
3
.
Ž
.
.
Ž
.
NH , dB s5.97 H-9 , JAB s7.8 , 7.15 d, Js8.8,
X
3
X
.
Ž
.
Ž
Ž
.
Ž
H-2 , 7.97 d, Js8.8, H-3 , 2.52 s, Me , for attribu-
tion of H-2X and H-3X irrad. at 7.14 ppm. 13C NMR
X
Ž
.
.

(
)
266
F. Pierre et al.rJournal of Organometallic Chemistry 553 1998 253–267
X
1
y1
˚
Ž
.
Ž
.
Ž
.
irrad. at 7.45 ppm C-2 . H NMR DMSO-d6 : exo
A, ms7.862 cm , F 000 s546, Ts294 K, final
Ž
.
Ž
.
Ž
.
Ž
60% : ds4.98 s, 5H, Cp , 3.76 s, 3H, Me , 6.58 d,
Rs0.074 for 2222 observations.
3
)
)
.
Ž
.
Ž
.
Ž
Ž
.
Jf9, H-9 ; endo 40% : ds4.88 s, 5H, Cp , 3.83 s,
The sample 0.20 0.30 0.35 mm was studied on an
automatic diffractometer CAD4 ENRAF-NONIUS with
graphite monochromatized MoK a radiation. The cell
parameters were obtained by fitting a set of 25 high-theta
3
.
Ž
.
.
3H, Me , 6.40 d, Js9.8, H-9 , the other signals were
Ž
not attributed: 6.3-8.6 m, 13H .
Ž
4.5. Epimerization of the endo isomer of 4b
50 mg of the amine 4b enriched with the endo
reflections. The data collection 2umax s508, scan
vr2us1, tmax s60 s, range HKL: H 0,12 K y12,12
L y13,13, intensity controls without appreciable decay
Ž
.
Ž
.
Ž
Ž
.
isomer exo:endo-55:45 was dissolved in a mixture 10
0.4% gave 4263 reflections from which 2222 indepen-
y1
.
Ž
.
Ž .
ml of acetic buffer CH3CO2 Na 0.5 mol l
q
dent Rs0.011 with I)3s I .
CH3CO2 H 0.5 mol ly1 and acetone 1:1,v:v . After
stirring at room temperature overnight and work-up as
Ž
.
After Lorenz and polarization corrections the struc-
ture was solved by direct method with the program
Ž
.
Ž
.
described in Section 4.4, 40 mg 80% yield of the
amine 4b was isolated exo:endo-85:15 .
SHELX-86 Sheldrick, 1985 which revealed all the non
hydrogen atoms of the compound in particular disor-
Ž
.
Ž
.
Ž
Ž
.
dered anion . After isotropic Rs0.11 , then anisotropic
.
4.6. NaBH4 reduction of the imine complex 3b
refinement Rs0.086 , some hydrogen atoms were
found with a Fourier Difference. The whole structure
was refined by the full-matrix least square techniques
Ž
.
In a Schlenck tube the imine 3b 0.50 g, 0.93 mmol
was dissolved in 30 ml of CH2Cl2 and 1 ml of water.
Ž
use of F magnitude; x, y, z, bij for Fe, P, N and C
Ž
.
NaBH4 70 mg, 1.86 mmol was added and the solution
was stirred at room temperature for 3 h. After hydroly-
sis with 20 ml of 1N HCl, the organic layer was
decanted and washed with 20 ml of a saturated aqueous
solution of NH4 PF6. The solution was dried over MgSO4
and the solvent evaporated under vacuum. Precipitation
of the resulting dark brown residue in acetonerether,
atoms, x, y, z, B for F atoms and x, y, z fixed for H
atoms; 294 variables and 2222 observations: ws
2
2 2
Ž
.
w
2Ž .
Ž
.
xy1r2
.
1rs Fo s s I q 0.04 Fo
with the re-
Ž
sulting Rs0.077, Rw s0.074 and Sw s1.88 residual
y3
˚
.
DrF1.26 e A
.
Atomic scattering factors from International Tables
Ž
.
for X-ray Crystallography 1974 . The calculations were
performed on a Hewlett Packard 9000-710 for structure
determination and on a Digital Micro VAX 3100 com-
puter with the MOLEN package Enraf-Nonius, 1990
for refinement and Ortep calculations 75–78 .
Ž
.
filtration and washing with ether gave 0.2 g 40% yield
of a mixture containing 80% of the amine 4b
exo:endo-10:90 and 20% of the starting imine 3b.
Ž
.
Ž
.
w
x
4.7. O2-oxidation of amines 4a and 4b
5. Supplementary material
In a conical flask equipped with an oxygen inlet the
amine 4a 0.35 g, 0.67 mmol was dissolved in 15 ml of
Ž
.
Complete crystallographic data of complex 4b are
available from the authors.
Ž
.
Ž
acetone. 1 g 10 mmol of Alumina activated neutral,
.
aldrich type 507 C, brockman 1 standard, 150 mesh
was added and the solution was stirred under bubbling
of O2 for two hours. The solution was filtered to
remove Al2O3 and added dropwise in 100 ml of ether.
Filtration and drying under vacuum of the resulting
Acknowledgements
The authors gratefully thank Dr. T. Weyland for
technical assistance and Dr. P. Guenot CRMPO for
HRMS.
Ž
precipitate led to 0.28 g of pure imine 3a syn:anti-
Ž
.
.
Ž
.
30:70 as a fine yellow powder 80% yield .
Under the same experimental conditions, the amine
4b was oxidized within one hour into imine 3b
Ž
.
syn:anti-20:80 in 77% yield.
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Ž
.
1
w x
2
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Ž
.
302 1986 307.
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Ž
. Ž
.
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D. Astruc, Tetrahedron 39 24 1983 4027.
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.
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7
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.
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.
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.
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Ž
.
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.
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.
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.
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.
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Ž
. Ž
.
x
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Ž
.
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x
36 J.R. Hamon, P. Hamon, S. Sinbandhit, P. Guenot, D. Astruc, J.
Ž
.
w
w
w
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