Synthesis and stereochemical studies of di and tetra 9,9′- spirobifluorene porphyrins: New building blocks for catalytic material

Article abstract of DOI:10.1016/j.tet.2003.10.080

We report the synthesis and stereochemical properties of a new class of molecules containing a covalently-linked porphyrin and spiro-9,9′- bifluorene derivatives. The large spiro substituents hinder rotation about the meso position to give atropisomers which can be detected by ¹H NMR after phosphine or isocyanide complexation to the ruthenium spiroporphyrins.

Full text of DOI:10.1016/j.tet.2003.10.080

Tetrahedron 60 (2004) 145–158
Synthesis and stereochemical studies of di and tetra
0
9
,9 -spirobifluorene porphyrins: new building blocks for
catalytic material
Cyril Poriel, Yann Ferrand, Sandrine Juillard, Paul Le Maux and G e´ rard Simonneaux
*
Laboratoire de Chimie Organom e´ tallique et Biologique, UMR CNRS 6509 Universit e´ de Rennes 1, 35042 Rennes cedex, France
Received 29 July 2003; revised 13 October 2003; accepted 28 October 2003
Abstract—We report the synthesis and stereochemical properties of a new class of molecules containing a covalently-linked porphyrin and
0
spiro-9,9 -bifluorene derivatives. The large spiro substituents hinder rotation about the meso position to give atropisomers which can be
1
detected by H NMR after phosphine or isocyanide complexation to the ruthenium spiroporphyrins.
q 2003 Elsevier Ltd. All rights reserved.
1. Introduction
2. Results and discussion
0
Since the
0
A series of spiro-bridge polymers based on 9,9 -spiro-
1
bifluorene have been recently synthesized.
2.1. Synthesis of 9,9 -spirobifluorene-2-carbaldehyde
–4
0
bifluorene rings are orthogonally arranged through a
tetracoordinated carbon, it is expected to enhance the
We decided to explore a method for preparing 9,9 -
spirobifluorene-2-carbaldehyde that can be scaled-up to
2
,3
0
spirobifluorene and then its monoformylated compound is
outlined in Scheme 1. 9,9 -Spirobifluorene was prepared
rigidity of the polymer and the thermal stability.
5
In
addition to model receptors for chiral recognition, spiro
multigram quantities. The synthetic approach to 9,9 -
6
0
derivatives provide a potentially useful stereochemistry
that makes the molecules suitable for interconnection in
from two different ways of synthesis, both of them used
2-iodobiphenyl synthesized from commercially available
2-amino-biphenyl and 9-fluorenone.
which was described by Tour et al. used a strong base
7
,8
future molecular devices. Three dimensional polymers
can also be prepared by anodic oxidation of spiro-
1
3,14
The first way (A),
9
,10
13
bifluorenes.
Giving the importance of these polymers,
incorporation of metalloporphyrins to spirobifluorene
polymers is an attractive approach to obtain materials for
heterogeneous catalysis. The major synthetic challenge is to
prepare a pool of monomers containing a covalently-linked
porphyrin and a spirobifluorene. Recently, we reported a
preliminary communication on a new class of manganese-
t-butyllithium in very drastic conditions has been first tested
(Scheme 1). The intermediate 9-(1,1 -biphenyl-2-yl)-9H-
0
fluoren-9-ol 2, obtained before cyclization and dehydrata-
tion has been isolated. Thus condensation of 2-iodo-1,1 -
0
biphenyl to 9-fluorenone in t-BuLi/pentane solution
afforded 9-(1,1 -biphenyl-2-yl)-9-H-fluoren-9-ol as an inter-
0
1
1
porphyrin-polymers as heterogeneous oxidation catalysts.
In complement to this work, here we report the synthesis of
mediate in 60% yield. Refluxing this intermediate in acetic
acid in presence of a few drops of HCl (13N) gave the
0
groups have been attached at the meso positions. Two
generations of porphyrins, di and tetra 9,9 -spirobifluorene
0
9
,9 -spirobifluorene porphyrins in which spirobifluorene
1
expected 9,9 -spirobifluorene with 90% yield. However, the
2
second pathway (B) has been preferred giving better yield,
in a one pot and mild reaction. This procedure is modified
0
1
4
porphyrins, were employed to determine the effect of the
bulky spirobifluorene groups on the periphery of the
porphyrin ring. Thus, the presence of spirobifluorene groups
gives substantial steric hindrance and atropisomers can be
from the one reported by Winter-Werner in 1996.
A general synthesis of monosubstituted derivative of
0
leading to mixture of di and mono substituted compounds.
9,9 spirobifluorene via electrophilic substitution is difficult
15
1
detected by H NMR.
0
spirobi[fluorene]-2-carbaldehyde 4 was however realized
Monoformylation of the spiro compound to prepare 9,9 -
Keywords: Spirobifluorene; Porphyrins; Ruthenium; Atropisomer;
Phosphine.
using TiCl /Cl CHOCH reagent with 65% yield. A related
4
2
3
0
route to 9,9 -spirobifluorene-2-carbaldehyde has been
1
recently described with a lower yield (30%).
*
Corresponding author. Tel.: þ33-2-23236285; fax: þ33-2-23235637;
6
e-mail address: gerard.simonneaux@univ-rennes1.fr
0040–4020/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2003.10.080

146
C. Poriel et al. / Tetrahedron 60 (2004) 145–158
Scheme 1.
Scheme 2.
Scheme 3.

C. Poriel et al. / Tetrahedron 60 (2004) 145–158
147
1
Figure 1. High field portion of the H NMR spectrum for compounds 8, 11 and 12 (CDCl
3
). (a) Mixture of atropisomers (DSP)Ru(II)(PMePh
2 2 2 2
atropisomers of D(o-OMeP)PRu(II)(PMePh ) 11. (c) D(m-OMeP)PRu(II)(PMePh ) 12.
2
)
2
8. (b) Separated
2.2. Syntheses of dispiroporphyrins
Due to possible difficulties with the synthesis of tetra-
0
spiroporphyrins bearing bulky substituents such as 9,9 -
spirobifluorene, we decided first to target porphyrins
bearing only two spirobifluorene groups. Such 5,15-
disubstituted porphyrins are typically synthesized from a
1
7,18
dipyrromethane derivative and an aldehyde.
This would
be expected to yield a mixture of just two porphyrins if there
0
porphyrin 6 (called DSP for simplication) was synthesized
by condensation of 9,9 -spirobifluorene-2-carbaldehyde 4
are atropisomers. The bis-5,15-(9,9 -spirobifluoren-2-yl)
0
1
9
and dipyrromethane 5 in dichloromethane with trifluoro-
acetic acid catalysis. A mixture of porphyrins was isolated
and separated by column chromatography and found to
contain a small amount of monospiroporphyrin along with
another porphyrin that we expected to be the dispiro-
porphyrin. However, identification of this major product
was not straightforward. Mass spectrometry gave a
1
molecular ion consistent with 6 but H NMR spectroscopy
did not give the simple spectra that we have expected.
Furthermore this meso free porphyrin is insoluble in a
variety of common organic solvents such as dichloro-
methane, chloroform, acetone and dimethylformamide. Due
1
to this strong insolubility, the H NMR spectrum was
recorded by adding deuterated trifluoroacetic acid steam in
1
the NMR tube. The H NMR (500 MHz) spectrum showed
an unusual slight splitting of the meso and b pyrrole
hydrogen according possibly to two rotational isomers (aa
and ab (Scheme 2).
In the aa atropisomer, the substituents attached to the meso-
aryl groups lie on the same side of the porphyrin plane, in
the a,b atropisomer on opposite sides. Although
Scheme 4.

148
C. Poriel et al. / Tetrahedron 60 (2004) 145–158
1
Figure 2. Low field portion of the H NMR spectrum: (a) for compound D(o-OMeP)PH
D(o-OMeP)PRu(II)(PMePh ).
11 (aaþab) (CDCl
2
(aaþab); (b) for D(o-OMeP)PRu(II)(CO) 10 (aaþab); (c) for
2
)
2
3
atropisomers are not expected when the meso-aryl groups
atoms of the phenyl rings of the phosphine ligands for
complex 8.
2
0
0
are substituted in meta position, the large size of the 9,9 -
spirobifluorene group may hinder rotation around the
Cmeso–Caryl bond.
1
Since the H NMR spectrum showed multiple resonances
for the phosphine ligand consistent with atropisomers,
1
2.3. Ruthenium complexation to dispiroporphyrins and
stereochemistry
variable temperature H NMR studies were undertaken to
determine the activation energy for aryl rotation in
compound 8. At the coalescence temperature (361 K), free
energy of 20.26 kcal/mol was calculated. As recently
To confirm atropisomerism, the ruthenium complex
(DSP)RuII(CO) 7 was first prepared by treatment of 6
with Ru (CO) in highly degassed o-dichlorobenzene at
2
2
reported for a porphyrin–carborane system, and a
3
2
porphyrin–fullerene system,
the large size of
3
12
0
1
60 8C during 2 h. Then it was decided to study a possible
9,9 spirobifluorene substituent in meta position increases
the energy barrier for aryl rotation; no attempts were made
to separate the two atropisomers of compound 8 given the
short lifetimes calculated from the activation energy.
atropisomerism through the complexation of two identical
axial ligands. Indeed, complexation of methyldiphenyl-
phosphine or t-butylisocyanide offered the greater
simplicity because these bis-ligated complexes provided a
ruthenium molecule with two topologically identical faces
2
4
To confirm that aryl-porphyrin rotation was the dynamic
process being observed, we synthesized the diaryl-
18
porphyrins bearing methoxy groups in ortho position
for the a,b isomer and two different faces for the a,a isomer
1
(
Scheme 3). The H NMR spectrum of the bis(methyl-
diphenylphosphine) adduct (DSP)Ru(II)(PMePh ) 8 dis-
(Scheme 4) and their ruthenium derivatives D(o-OMeP)-
PRu(II)(CO) 10. In this case, we were able to separate the
mixture of the two atropisomers by silica gel chromato-
graphy. As already shown for 6, the mixture of atropisomers
2
2
played two singlets for the meso hydrogens as expected for
the presence of two isomers. Moreover the spectrum showed
one triplet for the methyl resonance of the axial ligands with
the a,b isomer and two triplets of the same intensity for the
1
of the free base presented a quite identical H NMR
(Fig. 2(a)) spectra but the lost of symmetry in the ab isomer
methyl resonance of PMePh for the a,a isomer (Fig. 1(a)).
2
1
The triplets are due to virtual coupling as reported for
after ruthenium complexation induces a difference in the H
21
similar complexes. These data suggest the presence of a
mixture of two conformers, an anti (C2h symmetry) and a
syn isomer (C2v symmetry). It should be underlined that the
atropisomerism can also be observed for the ortho proton
NMR spectrum (Fig. 2(b)). Indeed the aa isomer
exhibits two doublets for b pyrrole protons and four
separated doublets can be detected for the ab isomer in
the spectrum.

C. Poriel et al. / Tetrahedron 60 (2004) 145–158
149
each atropisomer. Indeed, for the (DSP)Ru(II)(PMePh ) 8
2
2
complex, only two signals of the same intensity were
detected at 2.66 and 2.55 ppm (free ligand: 226.6 ppm),
one for ab isomer and one for the aa isomer. In the later
3
1
case, the two different faces were not detected by P NMR.
Such a situation has been already observed for ruthenium
2
5
picket fence porphyrin.
In order to precise the influence of the steric hindrance
caused by the two bulky phenyl groups of the phosphine
above the porphyrin ring, t-butylisocyanide complexes were
also prepared for all compounds previously described.
(DSP)Ru(II)(t-BuCN) 9 was prepared by addition of excess
of ligand to the precursor (DSP)Ru(II)(CO) 7 (85%). As
2
1
expected, the H NMR spectrum showed three resonances
for the t-butyl groups due to the presence of the two
conformers (Fig. 4(b)). This complex displayed one singlet
for the a,b isomer (20.70 ppm) and two singlets (20.57,
2
0.94 ppm) of the same intensity for the a,a isomer due to
inequivalent faces. These results were also compared with
the pure ab and aa D(o-OMeP)PRu(II)(t-BuCN)2 13
isomers which exhibit respectively, one and two singlets.
As expected, the meta D(m-OMeP)PRu(II)(t-BuCN)2
complex 14 showed only one singlet for the t-butyl groups
(
Fig. 4(a)).
In order to extend the synthesis and the study of
dispiroporphyrins, an other dipyrromethane was syn-
0
0
,2 dipyrromethane 15 as starting material was not arbitrary.
thesized. The choice of 4,4 diethyl-3,3 dimethyl-
2
0
As previously reported by Young and Chang for other meso-
2
4
diphenylporphyrins, the ethyl side chains on b pyrrole
1
Figure 3. Low field portion of the H NMR spectrum: (a) for (DSP)H
2
6;
2 2
(b) for (DSP)RuII(CO) 7; (c) for (DSP)Ru(II)(PMePh ) 8.
1
H NMR spectrum of the bis(methyldiphenylphosphine)
adduct, D(o-OMeP)PRu(II) (PMePh ) 11, was obtained
2
2
from addition of an excess of ligand to each atropisomer of
the D(o-OMeP)PRu(II)(CO) precursor 10. This lead us, in
analogy, to assign the two triplets for a,a isomer and the
single triplet to the other isomer (Fig. 1(b)). Thermal
atropisomerization of each pure isomer in dimethyl-
formamide at 140 8C lead to the statistical mixture 1:1.
The synthesis of ruthenium(II) diarylporphyrin complex
bearing
D(m-OMeP)PRu(II)(PMePh ) 12 was also performed. As
methoxy
groups
in
meta
position
2
2
expected, the spectrum did not show the presence of
isomers, displaying only one signal for the methyl group
(
Fig. 1(c)).
Conformational effect was also established by examining
1
the H NMR splitting pattern of the meso and pyrrole
protons in the low-field part of the spectrum of 8 and 11
which showed two different meso protons due to the
phosphine complexation (Fig. (3c)). In contrast, only one
meso proton is detected in 6 and 7 (Fig. (3a,b)).
Observation of phosphorus NMR may be a second
possibility to see two different topological faces in theses
3
1
complexes. The P NMR spectra were performed for all the
bis phosphine ligated compounds but the sensitivity of this
nucleus did not permit to distinguish the different faces of
1
Figure 4. High field portion of the H NMR spectrum a for D(m-
OMeP)PRu(II)(t-BuCN) 13 and b for (DSP)Ru(II)(t-BuCN) 9 (mixture of
2
2
3
isomers) (CDCl ).

150
C. Poriel et al. / Tetrahedron 60 (2004) 145–158
1
3
Figure 5. H NMR spectrum for compound 16 (CDCl ).
positions rendered dispiroporphyrin more soluble than the
non-substituted derivative 6. Furthermore the methyl group
methyl porphyrin 16 with 40% yield. The increase of
solubility compared to porphyrin 6 allowed us to record the
H NMR spectra of free base 16 in neutral conditions
(Fig. 5). The internal NH protons of the porphyrin core were
detected as two singlets at 22.33 and 22.35 ppm for the
two atropisomers aa and ab. As expected, signals due to
equivalent methyl groups of b pyrrole positions (3, 7, 13 and
17) were separated for each atropisomer (2.16 and
2.17 ppm) and gave a ratio of 1:1 (Scheme 5).
1
1
in position 3 constituted a very interesting H NMR probe to
detect possible atropisomers. Finally, in contrast to previous
2
6
synthesis of tetramethyldipyrrylmethane, the yields herein
2
were better than 70% in each step.
4
0
,3 dimethyl-2,2 dipyrromethane 15 with 9,9 -spirobi-
[
bis(spirobifluoren-2-yl)-2,8,18-tetraethyl-3,7,13,17-tetra-
Mac Donald ‘2þ2’ condensation of 4,4 diethyl-
0
0
fluorene]-2-carbaldehyde 4 lead to the expected 5,15
0
3
After ruthenium insertion (complex 17) followed by
Scheme 5.

C. Poriel et al. / Tetrahedron 60 (2004) 145–158
151
Scheme 6.
p
phosphine (complex 18) or isocyanide (complex 19)
complexation, the presence of two different conformers
was also detected by H NMR. The complex 18
exhibited three resonances at 22.7, 22.54 and 22.30 ppm
corresponding to the phosphine methyl groups, and the
complex 19 exhibited three resonances at 20.94, 20.70 and
the activation free energy DG for 18 to that for the
unsubstituted complex 8. The activation free energy for
rotation in the compound 18 is similar to that for 8
(20.26 kcal/mol) giving rise to a similar energy of rotation
around the single bond between porphyrin and spiro-
bifluorene moieties. Intuitively, the addition of flanking
alkyl groups should bring more hindrance than the b-pyrrole
protons in preventing rotation. However, the absence of an
1
2
0.58 ppm, corresponding to the isocyanide methyl groups.
1
Variable temperature H NMR spectroscopy was applied to
quantify the spirobifluorene interaction with the methyl
group in b pyrrole position. By monitoring the coalescence
p
increase in DG for 18 suggests that this is not true.
Therefore the added steric constraints may be not enough to
compensate the remote spiro groups in meta position.
Similar results were previously observed with ortho
of the free meso hydrogen in toluene d between 298 and
8
p
78 K, DG at the coalescence temperature (370 K) was
3
estimated as 20.35 kcal mol . This allows us to compare
2
1
24
substituents.
1
Figure 6. High field portion of the H NMR spectrum for compound 23 (CDCl
3
) with relative intensity of each atropisomer.

152
C. Poriel et al. / Tetrahedron 60 (2004) 145–158
high-field position due to the ring current shift and with a
relative intensity corresponding to the isocyanide methyl
groups of the complex 23. As presented Figure 6, the
statistical mixture of four atropisomers was observed. The
aaaa isomer has two different faces and exhibit two
resonances at 21.18 and 20.50 ppm with relative intensity
according with its statistical weight. The two topological
faces of this isomer are the more different of all the mixture;
one bearing the four spirobifluorene groups and the other
completely free. This cause a difference of 0.68 ppm
between the two resonances; the interpretation and the
assignation of all the signals have been made using this
argument. The two resonances at 20.96 and 20.62 have
been assigned to the aaab isomer. The aabb and abab
isomer exhibit both two identical faces according to
resonances at respectively, 20.74 and 20.86 ppm.
8
Figure 7. Variable temperature study in toluene d for compound 23
(lowfield part of the spectrum).
2.4. Syntheses and stereochemistry of tetraspiro-
porphyrin
Due to weakness of the meso free position toward oxidation
process, more resistant tetraspirobifluorene porphyrin
ruthenium complexes have also been synthesized for further
1
Variable temperature H NMR spectroscopy was applied to
detect the spirobifluorene interaction with the proton in b
pyrrole position for compound 23, by monitoring the
coalescence of the pyrrole hydrogens in toluene d between
2
7
19
catalytic studies. Following the Lindsey procedure,
condensation of 9,9 -spirobifluorene-2-carbaldehyde 4 and
0
pyrrole led to a satisfactory yield (40%) of meso-tetra-
8
298 and 378 K, (Fig. 7). A coalescence temperature was
detected near 350 K. The coalescence temperature was
361 K for 8, suggesting a similar energy of rotation around
the single bond between porphyrin and spirobifluorene
moieties for the di and tetraspiro derivatives. As already
reported for di-meso-substituted compounds, comparison
with ruthenium tetraphenylporphyrine derivatives bearing
on aryl group meta substituents was undertaken. Thus, first
T(m-MeP)PRu(II)(PPh Me) 26 and then T(m-MeP)-
0
Indeed, the H NMR spectrum of compound 20 displayed
several peaks for the pyrrole resonances between 8.74 and
(
m-9,9 -spirobifluoren-2yl)porphyrin 20 (Scheme 6).
1
8
(
.68 ppm, and four resonances at high-field position
22.43, 22.52, 22.54 and 22.56 ppm) assigned to internal
NH. Attempts to isolate these free-base atropisomers by
classical chromatography techniques were however
unsuccessful, due probably to the meta position of the
bulky spirobifluorene.
2
2
PRu(II)(t-BuCN)2 27 were synthesized from the corre-
1
sponding Ru(II)(CO) derivatives. As expected, the H NMR
After ruthenium insertion (complex 21) followed by
isocyanide complexation (Scheme 6), the presence of four
different conformers was also detected by H NMR (Fig. 6).
1
The identification of the various isomers in the H NMR
spectrum exhibits only one resonance at high field for the
methyl group of the phosphine for 26 and for the methyl of
the isocyanide for 27, respectively (Scheme 7).
1
spectrum of the tetraspirobifluorene porphyrins was based
on a combination of two arguments. First the quantities of
each isomer present in the equilibrium mixture should
correspond to the statistical composition: 1:2:4:1 respect-
3. Conclusion
The phenomenon of atropisomerism in porphyrins with
meso aryl substituents in ortho position is well known. It
2
5
28
ively for aaaa, aabb, aaab, abab, as we and others
2
9
have frequently observed. Secondly, two conformers show
identical faces whereas the others show different faces. As
expected, the spectrum exhibited six resonances found at
was first described in 1969 by Gottwald and Ullman with
tetraphenylporphyrins. This concept has been nicely
2
8
30,31
extended first by Collman and then by others
with
Scheme 7.

C. Poriel et al. / Tetrahedron 60 (2004) 145–158
153
3
7
meso-tetraaminophenylporphyrins. Since then atropisomer-
ism has also been reported for ortho di-meso substituted
singlets. Although the use of this equation can be
criticized, it has been shown that the free energies of
activation are in good agreement with the results of
complete shape analysis based on equally populated two-
2
4,32,33
aryl-porphyrins.
In contrast, meta-substitution rarely
shows restricted aryl rotation in tetra and di-arylporphyrins.
Thus there are only few examples such as porphyrin
3
7
site system. High-resolution mass spectra were recorded
on a ZabSpec TOF Micromass spectrometer for FAB mode
or ESI positif mode and on a Varian MAT 311 for EI mode.
The spectra were recorded by the CRMPO at the University
of Rennes 1. Infrared spectra were recorded on a Bruker IFS
28. Solid samples were prepared in KBr pellets. Liquid
samples were prepared in dichloromethane. Melting points
were recorded on WME HEIZBANK KOFLER apparatus.
UV-visible spectra were recorded on a UVIKON XL from
Biotech.
2
2
23,34
carborane system, meta aryl fullerene porphyrins
3
and
multimetallic porphyrin monomers. Therefore the large
5
0
size of the 9,9 -spirobifluorene group also hinders rotation
around the Cmeso–Caryl bond. Unfortunately, energy barrier
was too low to get each atropisomer as a pure compounds. In
summary, we have developed new efficient syntheses for
preparing in mild conditions and with high yield spiro-
bifluorenylporphyrins. These compounds exhibit atrop-
1
isomers forms which can be easily detected by H NMR
though the aryl substituents are in meta position. Oxidative
electropolymerization of tetraspirobifluorenylporphyrin
ruthenium (II) carbonyl complexes 21 can be used to coat
Pt electrodes with polymeric films as we already reported
All electrochemical experiments were performed using a Pt
disk electrode (diameter 1 mm), the counter electrode was a
vitreous carbon rod and the reference electrode was a silver
1
1
for manganese-porphyrin-polymers. When unsticked
from the electrode, these polymeric ruthenium materials
are able to catalyze the heterogeneous cyclopropanations
and 2.3 sigmatropic rearrangements with ethyl diazo-
wire in 0.1 M AgNO3 solution in CH CN. Ferrocene was
3
added to the electrolyte solution at the end of a series of
experiments. The ferrocene/ferricinium (Fc/Fcþ) couple
served as internal standard and all reported potentials are
referenced to its reversible formal potential. The three
electrodes cell was connected to a PAR Model 179 signal
coulometer. The cyclic voltammetry traces (CVs) were
recorded on a XY SEFRAM-type TGM 164. Acetonitrile
with less than 5% of water and dichloromethane with less
than 100 ppm of water were used without purification.
Tetrabutyl ammonium hexafluorophosphate from FLUKA
was used without any purification.
3
6
acetate.
4
. Experimental
.1. General experiments
All reactions were performed under argon and were
4
magnetically stirred. Solvents were distilled from appro-
priate drying agent prior to use: Et O and THF from sodium
and benzophenone, toluene from sodium, CH Cl2 from
2
4.2. Preparation of spirobifluorene derivatives
2
0
38
2-amino-1,1 -biphenyl (27 g, 160 mmol) in concentrated
4.2.1. 2-Idodo-1,1 -biphenyl 1. To a suspension of
0
CaH , CHCl from P O and all other solvents were HPLC
2
3
2 5
grade. Commercially available reagents were used without
further purification unless otherwise stated. All reactions
were monitored by TLC with Merck pre-coated aluminium
foil sheets (Silica gel 60 with fluorescent indicator UV254).
Compounds were visualized with UV light at 254 and
hydrochloric acid (32.2 mL) and water (160 mL) cooled at
0 8C was added carefully an aqueous solutionof sodium nitrite
(13.3 g, 193 mmol) in 10 min. The brown mixture was then
stirred at 0 8C for 45 min and added carefully to an aqueous
solution of potassium iodide (53.1 g, 320 mmol) in 5 min. The
finalsolutionwasstirredatroomtemperature for 12 h and then
extractedfourtimeswithdiethylether. Theorganiclayerswere
then washed with a solution 3 N of hydrochloric acid, a
saturated solution of sodium bicarbonate, sodium chloride,
water and dried on magnesium sulphate. The solvents were
removed under vacuum to give the 2-idodobiphenyl 1 as
purple oil. This compound was used without any other
3
silica gel from Merck (0.063–0.200 mm). H NMR and
65 nm. Column chromatography was carried out using
1
13
C
NMR in CDCl and toluene d were recorded using Bruker
3
8
(
Advance 500dpx, 300dpx and 200dpx) spectrometers. The
assignments have been performed by 2D NMR experiments:
COSY (Correlation Spectroscopy), HMBC (Heteronuclear
Multiple Bond Correlation), HMQC (Heteronuclear
Multiple Quantum Coherence) and NOESY (Nuclear
Overhauser Effect Spectroscopy). The rates of confor-
1
purification (yield: 98%). H NMR (CDCl , ppm): d 7.1 (H ,
3
bI
1
3
m, 1H); 7.3–7.6 (m, 7H); 8.03 (H , m, 1H). C NMR
aI
mational interchange (k ) and the activation free energies
c
(CDCl , ppm): d 99.3; 128.2; 128.3; 128.6; 128.8; 129.4;
3
p
DG at the coalescence temperatures were calculated using
129.9; 130.7; 131.5; 140.1; 144.7; 147.2. MS (EI) (m/z): calcd
zþ
1
/2
approximate equation: k ¼pDn/(2) for the coalescence of
for C H I (M ): 279.97490. Found: 279.9748.
12 9
c

154
C. Poriel et al. / Tetrahedron 60 (2004) 145–158
0
previously described by Tour et al. is not described here.
However the spectroscopic data of the intermediate 9-(1,1 -
biphenyl-2-yl)-9H-fluoren-9-ol 2 are reported.
The synthesis of 9,9 -spirobifluorene 3 which was
1
NMR (500 MHz, CDCl ): d 6.74 (H , ddd, 2H), 6.82 (H8,
0
3 1
3
ddd, 1H), 7.14 (H2
1H), 7.43 (H3 , td, 2H), 7.47 (H , td, 1H), 7.91 (H
2H), 7.94 (H , dd, 1H), 7.96 (H , ddd, 1H), 8.04 (H , dd,
0
, td, 2H), 7.22 (H , td, 1H), 7.30 (H , sdd,
7 1
0
0
0
, ddd,
4
6
3
5
4
1
3
1H), 9.84 (CHO, s, 1H). C NMR (75 MHz, CDCl ): d 65.6
(C ); 120.2; 120.3; 121.1; 123.8; 124.3; 124.5; 125.2; 127.9;
3
0
CDCl , ppm): d 2.28 (OH, s, 1H); 6.01 (dd, 4H); 6.62 (td,
1
4
(
.2.2. 9-(1,1 -Biphenyl-2-yl)-9H-fluoren-9-ol 2. H NMR
9
128; 129.5; 130.2; 135.9; 140.1; 141.8; 147.4; 147.8;
149.7; 150 (C aromatic); 191.6 (CvO). UV–VIS
3
4
H); 6.92 (m, 4H); 7.34 (td 1H); 7.6 (td, 2H); 8.1 (dd, 2H).
C NMR (CDCl , ppm): d 82.88; 120.51; 124.79; 125.55;
1
3
(CH Cl ): l
2
(log 1): 225 (4.59), 282 (4.31), 292
max/nm
3
2
1
1
26.55; 126.71; 127.32; 127.54; 128.35; 129.10; 129.32;
31.7; 140.14; 140.65; 140.79; 151.02. MS (EI) (m/z): calcd
(4.32), 303 (4.38), 328 (4.08). MS (FAB) (m/z): calcd for
C H O (M ): 344.1201. Found: 344.1199. Mp: 209 8C.
zþ
CV (CH Cl 0.2 M/Bu NPF , Fc/Fc ): 1.34 V, 1.66 V.
2
6 16
zþ
þ
for C H O (M ): 334.13577. Found: 334.1368. Mp:
2
5
18
2
2
4
6
1
80 8C.
0 0
.2.5. 2,2 Dipyrromethane 5. The 2,2 -dipyrromethane 5
was prepared according to the literature procedure and use
4
0
0
4
2
.2.3. 9,9 -Spirobifluorene 3. Under argon atmosphere
-iodo-1,1 -biphenyl 1 (44.3 g, 158 mmol) was added
19 1
without other purification (yield: 35%). H NMR (CDCl3,
ppm): d 4.01 (CH C , s, 2H); 6.14 (CH m, 2H); 6.24 (CH,
dropwise in 30 mn to magnesium turning (5 g, 205 mmol)
in 100 mL of diethylether freshly distilled. The addition was
controlled to maintained a gentle reflux of diethylether. The
mixture was heated to reflux for 90 min and then diluted
with 100 mL of diethylether. The mixture was then filtered
under argon atmosphere and a solution of 9-fluorenone
2
2
,
m, 2H); 6.65 (CH, m, 2H); 7.90 (NH, s br, 2H). MS (EI)
zþ
(m/z): calcd for C H N (M ):146.0844. Found: 146.0849.
10 2
9
0
0
0
4.2.6. 4,4 -Diethyl-3,3 -dimethyl-2,2 -dipyrromethane 15.
0
0
0
0
5,5 -Bis(ethoxycarbonyl)-4,4 -diethyl-3,3 -dimethyl-2,2 -di-
pyrromethane (5.3 mmol) which was obtained from pentan-
(
37 g, 205 mmol) dissolved in 300 mL of toluene was added
3
9
dropwise. The mixture was heated to reflux for 24 h. After
cooling, the solution was added to 250 g of crushed ice,
diluted with 200 mL of toluene and finally 300 mL of
concentrated hydrochloric acid was carefully added in
2,4-dione as previously reported by Lash was dissolved at
100 8C in ethylene glycol (20 mL). The orange solution was
degassed for 15 min before adding sodium hydroxide
(53 mmol) and heated at 180 8C under an argon atmosphere
for 1 h. The mixture was diluted with water and extracted
several times with hexane. The organic layers were
concentrated, dried over magnesium sulphate and evapor-
5
min. The solution was stirred for 3 h at room temperature.
The two layers were separated and the aqueous layer
extracted with dichloromethane. The organic layers were
then washed with a saturated solution of sodium bicarbon-
ate, sodium chloride, and water and dried on magnesium
sulphate. The solvents were removed under vacuum and the
crude product was purified by chromatography on silica gel
0
0
0
ated under reduce pressure. 4,4 -diethyl-3,3 -dimethyl-2,2 -
dipyrromethane 15 was stored and protected from light,
under an argon atmosphere at 210 8C and used without
1
other purification (yield: 70%). H NMR (CDCl , ppm): d
3
(first: pentane, second: pentane with a gradient of
dichloromethane (from 1 to 30%). Finally the 9,9 -
1.33 (CH C , t, 6H); 2.27 (CH C , s, 6H); 2.67 (CH C , q,
4
4H); 3.95 (CH C , s, 2H); 6.43 (CHC , s, 2H); 7.31 (NH, s,
2 2 5
zþ
2H). MS (EI) (m/z): calcd for C H N (M ): 230.1783.
15 22 2
3
3
3
2 3
0
spirobifluorene 3 was washed with a few amount of cold
1
ethanol to afford a white powder (yield: 90%). H NMR
(
Found: 230.1763.
CDCl , ppm): d 6.79 (H , dd, 4H); 7.16 (H , td, 4H); 7.42
3 1 2
1
3
0
solution of 2,2 -dipyrromethane 5 (225 mg, 1.54 mmol) and
(
H , td, 4H); 7.91 (H , dd, 4H). C NMR (CDCl , ppm): d
3
4.2.7. 5,15-Bis(9,9 -spirobifluoren-2-yl) porphyrin 6. A
0
9,9 -spirobifluorene-2-carbaldehyde 4 (530 mg, 1.54 mmol)
4
3
6
C). MS (FAB) (m/z): calcd for C H (M ): 316.1252.
6 (C ); 119.87; 123.9; 127.6; 127.7; 141.6; 148.6 (aromatic
zþ
9
0
2
5 16
Found: 316.1249. UV–VIS (CH Cl ): l (log 1): 225
max/nm
in freshly distilled dichloromethane was degassed 10 min.
Trifluoroacetic acid (95 mL, 1.22 mmol) was added and the
reaction mixture was stirred and protected from light under
an argon atmosphere for 15 h. 2.1 mmol (520 mg) of
tetrachlorobenzoquinone was added to irreversibly oxidize
the di-spiroporphyrinogene and the solution was stirred at
air for 60 min and 30 min to reflux. After addition of several
drops of triethylamine and the ordinary work-up, concen-
tration, washing, drying, the crude reaction mixture was
purified by chromatography on silica gel respectively, with
diethyl ether, dichloromethane, mixture of dichloro-
methane/methanol (8:2) and dichloromethane saturated
with concentrated hydrochloric acid. These two last
fractions were evaporated and washed with a saturated
solution of sodium bicarbonate, sodium chloride, and water
and dried on magnesium sulphate. The crude product was
dissolved in dichloromethane saturated with concentrated
hydrochloric acid and a second chromatography was
performed using the same solvents. The last green fraction
2
2
(
2
1
4.79); 236 (4.59); 261 (4.51); 294 (4.11); 305 (4;34). Mp:
þ
028C. CV (CH Cl 0.2 M/Bu NPF , Fc/Fc ): 1.3 V;
2
2
4
6
.42 V.
0
4
.2.4. 9,9 -Spirobifluorene-2-carbaldehyde 4. To a sol-
0
ution of 9,9 -spirobifluorene (12.7 mmol) in 100 mL of
distilled and degassed dichloromethane, cooled at 0 8C, was
added a,a-dichloro-methyl-methylether (31.6 mmol) in one
portion. After 5 min titanium tetrachloride (31.6 mmol in
5
0 mL dichloromethane) was added drop wise over a period
of 45 min. The dark green solution was then stirred at room
temperature for 75 min and 250 g of ice was then added and
let under vigorous stirring for 30 min. The two layers were
then separated and the aqueous layer was extracted two
times with 100 mL of dichloromethane. The organic layers
were then washed with a saturated solution of sodium
bicarbonate, sodium chloride, and water and dried on
magnesium sulphate. The solvents were removed under
0
vacuum and the crude product was purified by chromato-
1
afforded pure protonated 5,15-bis(9,9 -spirobifluoren-2-yl)
porphyrin 6. The previous work up was performed, the
graphy on silica gel (CHCl /Pentane: 6/4) (yield: 65%). H
3

C. Poriel et al. / Tetrahedron 60 (2004) 145–158
155
solvent was removed under vacuum and 6 was crystallized
1
by chromatography twice on silica gel: first with dichloro-
methane and then with cyclohexane/dichloromethane: 1/3.
Crystallization in distilled toluene for one night at room
temperature afforded a purple powder of meso-tetrakis
in pentane (yield: 30%). H NMR (CDCl /TFA, ppm) (aa
3
and ab): d 7.01 (H , dd, 2H); 7.12 (H , dd, 4H); 7.32 (H2 ,
0 0
8
1
td, 4H); 7.36 (H , td, 2H); 7.5 (H , td, 4H); 7.6 (H , td, 2H);
0
7
3 6
1
7
.91 (H , sd, 2H); 7.94 (H
1
0
, dd, 4H); 8.2 (H , dd, 2H); 8.41
5
5,10,15,20-(spirobifluoren-2-yl) porphyrin (yield: 40%). H
NMR (CDCl , ppm) (4a, 3ab, 2a2b, abab): d-3.13 (s, 2H,
4
(
H , dd, 2H); 8.43 (H , dd, 2H); 8.73 (HIII,VII,XIII,XVII, b
3
4
3
3
pyrrole, d, J¼4.83 Hz, 4H); 9.25 (HII,VIII,XII,XVIII, b
NH); 6.88 (H , d, 4H); 7.07 (H , m, 8H); 7.21 (H2 /H , m,
0 0
8 1 7
3
pyrrole, d, J¼4.82 Hz, 4H); 10.66 (H
meso, s, 2H).
12H), 7.32 (H3
8H); 8.07–8.15 (H /H /H , m, 12H); 8.55 (H b pyrrole,
0
, m, 8H); 7.50 (H þH , m, 8H); 7.71 (H
0
, m,
4
X,XX
6
1
1
3
C NMR (CDCl /TFA, ppm): d 66.3 (C ); 106.6 (C
9
3
X,XX
5
4
3
1
3
meso); 119.8; 120.5 (C ); 121.1 (C
4
0
); 121.8 (C5);
0
m, 4H); 8.57 (H b pyrrole, m, 4H). C NMR (CDCl , ppm):
3
4
1
24.3 (C1
0
); 125 (C ); 128.5 (C
0
); 128.6 (C2
); 128.7
C ); 129.2 (CII,VIII,XII,XVIII, b pyrrole); 129.6 (C7);
d 66.1 (C ); 118; 119.8; 120.1; 120.3; 123.9; 124.2; 127.7;
9
8
3
(
127.9; 128.1; 128.2; 129; 131(C b pyrrole); 134.9; 141.2;
141.5; 141.7; 141.8; 147.4; 147.6; 148.7; 149.6. MS (FAB)
6
1
29.8 (CIII,VII,XIII,XVII, b pyrrole); 133.8 (C ); 139.7; 140
1
þ
(
(
C ); 142; 142.5; 142.7 (CI,IX,XI,XIX); 143.7; 146.5
3
CIV,VI,XIV,XVI); 148; 149.8; 150 (NMR experiments have
(m/z): calcd for C120H N (MþH) : 1567.5634. Found:
71 4
1567.5600. UV–VIS (CH Cl ): l (log 1): 228 (5.08);
max/nm
2
2
been performed by adding TFA in the NMR tube due to the
insolubility of free base 6). MS (FAB) (m/z): calculated for
297 (4.58); 309 (4.67); 427 (5.32); 520 (4.17); 556 (4.09);
594 (3.74); 652 (3.76). CV (CH Cl 0.2 M/Bu NPF , Fc/
Fc ): 0.585; 0.915; 1.395 (sh); 1.505.
2
2
4
6
þ
CH Cl ): l (log 1): 227 (4.62); 297 (4.13); 307
þ
C H N (MþH) : 939.3488. Found: 939.3477. UV–VIS
7
0 43 4
(
(
(
2
2
max/nm
4.16); 412 (5.11); 505 (3.92); 541 (3.85); 575 (3.51); 632
3.38).
4.3. Typical procedure for ruthenium insertion
Free base porphyrin (313 mmol) was dissolved in distilled
1,2-dichlorobenzene and degassed for 15 min. The reaction
mixture was heated at 160 8C and dodecacarbonyl tri-
ruthenium was added (830 mmol) over a period of 2 h under
an argon atmosphere. The ruthenium insertion was followed
by TLC and UV–Vis spectroscopy. The solvents were
removed under vacuum, the residue was dissolved in
dichloromethane and purified by chromatography on silica
gel. The dodecacarbonyl triruthenium was eluted first with
pentane and the desired ruthenium complex was eluted with a
mixture dichloromethane/diethylether (9:1). Ru(II)(CO) com-
plex was further crystallized from pentane–dichloromethane.
0
ethyl-3,7,13,17-tetramethylporphyrin 16. A solution of
4
.2.8. 5,15-Bis(9,9 -spirobifluoren-2-yl)-2,8,12,18-tetra-
0
.54 mmol) and 9,9 -spirobifluorene-2-carbaldehyde
0
0
4
1
,4 -diethyl-3,3 -dimethyl-2,2 -dipyrromethane15(354.2 mg,
4
0
(
530 mg, 1.54 mmol) in freshly distilled dichloromethane
was degassed 10 min. Trifluoroacetic acid (95 mL,
.22 mmol) was added and the reaction mixture was stirred
protected from light under an argon atmosphere for 15 h,
.1 mmol (520 mg) of tetrachlorobenzoquinone was added to
1
2
irreversibly oxidize the di-spiroporphyrinogene and the
solution was stirred in air at room temperature for 60 min
and then 30 min in refluxing solvent. After addition of several
drops of triethylamine and the ordinary work-up, concen-
tration, washing, drying, the crude reaction mixture was
0
ruthenium carbonyl 7. Yield: 76%. H NMR (CDCl ,
4.3.1. 5,15-Bis(9,9 -spirobifluoren-2-yl) porphyrinato
1
3
1
purified by chromatography on silica gel (yield: 40%). H
NMR (CDCl /TFA, ppm) (aa and ab): d 22.35 (NH, s, 1H);
ppm) (aa and ab): d 6.88 (H spirobifluorene, dd, 2H); 7.1–
7.26 (H spirobifluorene, m, 8H); 7.29–7.38 (H spiro-
bifluorene, m, 6H); 7.54 (H spirobifluorene, m, 4H); 7.73 (H
spirobifluorene, m, 4H); 8.11–8.29 (H spirobifluorene,
m, 6H); 8.72 (H b pyrrole, d, 2H); 8.75 (H b pyrrole, m,
3
22.33 (NH, s, 1H); 1.30 (CH ethyl, t, 12H); 2.16 (CH
methyl, s, 6H); 2.17 (CH methyl, s, 6H); 3.62 (CH ethyl, q,
3 3
3
2
8
H); 6.99 (H spirobifluorene, m, 6H); 7.2–7.45 (H spiro-
bifluorene, m, 10H); 7.59 (H spirobifluorene, m, 4H); 7.85 (H
spirobifluorene, dd, 4H); 8.14(H spirobifluorene, m, 4H); 8.35
2H); 9.04 (H b pyrrole, d, 4H); 9.93 (H
1
meso, s,
þ
X,XX
02
2H). MS (FAB) (m/z): calcd for C H N O Ru (MþH) :
7
1 41 4
(
(
(
(
(
(
H spirobifluorene, dd, 2H); 10.07 (HX,XX meso, s, 2H). MS
ESI: CH Cl /MeOH: 9/1) (m/z): calcd for C H N
1067.2344. Found: 1067.2349. UV–VIS (CH Cl ): l
2
2
max/nm
(log 1): 228 (4.80); 296 (4.40); 308 (4.50); 404 (5.11); 521
21
2
2
82 67 4
þ
CH Cl ): l (log 1): 227 (4.60); 297 (4.10); 307
MþH) : 1107, 5366. Found: 1107, 5375. UV–VIS
(4.02); 552 (3.58). IR (KBr, cm ): nCO 1943.
2
2
max/nm
4.13); 410 (5.13); 508 (3.90); 543 (3.81); 577 (3.44); 634
3.30).
4.3.2. 5,15-Bis(2-methoxyphenyl) porphyrinato ruthe-
nium carbonyl 10. Yield: 70%. The free base compound
has been synthesized according the procedure described by
0
18
4
.2.9. meso-5,10,15,20-Tetrakis (9,9 -spirobifluoren-2-yl)
Manka and Lawrence.
0
porphyrin 20. Pyrrole (524 mL, 7.5 mmol) and 9,9 -
spirobifluorene-2-carbaldehyde 4 (2.5 g, 7.5 mmol) were
allowed to react at room temperature in dry and degassed
dichloromethane (750 mL) under an argon atmosphere and
protected from light with trace acid catalysis (BF (OEt)
1
H NMR (CDCl , ppm) (ab isomer): d 3.45 (s, 6H, methyl
3
group); 7.25–8 (m, 8H, H phenyl ring); 8.54 (Hb pyrrole, d,
3
3
J¼4.5 Hz, 2H); 8.87 (Hb pyrrole, d, J¼4.6 Hz, 2H); 9.02
3
(Hb pyrrole, d, J¼4.6 Hz, 2H); 9.25 (Hb pyrrole, d,
3
2
3
4
8%: 0.75 mmol). Under these conditions, the reaction
J¼4.8 Hz, 2H); 10.02 (H meso, s, 2H). (aa isomer): d 3.6
reaches equilibrium in about 3 h. 6.25 mmol (1.54 g) of
p-chloranil was added to irreversibly oxidize the tetra-
spiroporphyrinogene and the solution was stirred at air for
(s, 6H, methyl group); 7.25–8 (m, 8H, H porphyrin phenyl
ring); 8.76 (Hb pyrrole, d, J¼4.6 Hz, 4H); 9.15 (Hb
3
3
pyrrole, d, J¼4.6 Hz, 4H); 9.92 (H meso, s, 2H). MS (FAB)
1
02
þ
(m/z): calcd for C H N O Ru (M ): 650.0898. Found:
35 24 4 3
6
0 and 30 min to reflux. After addition of several drops of
triethylamine and the ordinary work-up, concentration,
washing, drying, the crude reaction mixture was purified
650.0902. UV–VIS (CH Cl ): l
2
517 (4.19). nCO 1936
(log 1): 398 (5.28);
2
max/nm

156
C. Poriel et al. / Tetrahedron 60 (2004) 145–158
0
ethyl-3,7,13,17-tetramethylporphyrinato ruthenium car-
3
3
4
.3.3. 5,15-Bis(9,9 -spirobifluoren-2-yl)-2,8,12,18-tetra-
pyrrole, d J¼4 Hz, 4H); 8.48 (H b pyrrole, d J¼4 Hz, 4H);
8.70 (Hmeso, s, 2H). ab isomer: d 22.24 (CH phosphine, t,
3
6H); 3.68 (CH methoxy group, s, 6H); 4.25 (H phosphine
3
1
bonyl 17. Yield: 75%. H NMR (CDCl , ppm) (aa and ab):
3
d 1.73 (CH ethyl, t, 12H); 2.35 (CH methyl, s, 12H); 3.84
3
o-phenyl ring, m, 8H); 6.43 (H phosphine m-phenyl ring, t,
8H); 6.77 (H phosphine p-phenyl ring, t, 4H); 7.38–7.67 (H
porphyrin phenyl ring, m, 8H); 8.27 (H b pyrrole, d
3
(
CH ethyl, q, 8H); 6.69–6.91 (H spirobifluorene, m, 6H);
2
7
.12 (H spirobifluorene, m, 4H); 7.36–7.58 (H spiro-
3
3
bifluorene, m, 6H); 7.71 (H spirobifluorene, m, 4H); 7.94 (H
spirobifluorene, m, 6H); 8.16 (H spirobifluorene, m, 4H);
J¼4.1 Hz, 4H); 8.45 (H b pyrrole, d J¼4.1 Hz, d, 4H);
8.68 (Hmeso, s, 2H). MS FAB (m/z): calcd for C H N -
4
7 37 4
1
02
zþ
9
.84 (HX,XX meso, s, 2H). MS (ESI: CH Cl /MeOH: 9/1)
2
O2P Ru (M2P(Ph) CH ¼822.1721. Found: 822.1711.
UV–VIS (CH Cl ): l (log 1): 423 (5.13), 507 (3.86).
2 2 max/nm
2
2
3)
1
02
zþ
(
m/z): calcd for C H N O Ru (M ):1234.4124. Found:
8
3
64
4
1
2
234.4170. UV–VIS (CH Cl ): l
(log 1): 228 (4.84);
96 (4.47); 308 (4.50); 401 (5.01); 521 (3.99); 552 (3.90).
2
2
max/nm
4.3.7. 5,15-Bis(3-methoxyphenyl)porphyrinato ruthe-
nium bis(methyl-diphenyl phosphine) 12. Yield: 84%.
2
1
IR (KBr, cm ): nCO 1938.
1
H NMR (CDCl ): d 22.35 (CH phosphine, t, 6H); 4.05
3
3
0
yl)porphyrinato ruthenium carbonyl 21. Yield: 82%. H
4
.3.4. meso-5,10,15,20-Tetrakis(9,9 -spirobifluoren-2-
1
(CH methoxy group, s, 6H); 4.15 (H phosphine o-phenyl
3
ring, m, 8H); 6.50 (H phosphine m-phenyl ring, t, 8H); 6.81
(H phosphine p-phenyl ring, t, 4H); 7.32–7.85 (H porphyrin
NMR(toluene d , ppm) (4a, 3ab,2a2b, abab): 6.90 (H
8
3
spirobifluorene, dd, 4H); 7.11–7.20 (H spirobifluorene, m,
12H), 7.22–7.30 (H spirobifluorene, m, 12H); 7.50–7.83 (H
spirobifluorene, m, 16H); 7.9–8.33 (H spirobifluorene, m,
phenyl ring, m, 8H); 8.34 (H b pyrrole, d, J¼4.2 Hz, 4H);
3
8.65 (H b pyrrole, d, J¼4.2 Hz, 4H); 9.13 (Hmeso, s, 2H).
1
02
MS FAB (m/z): calcd for C H N O P Ru (M2P(Ph) -
2
4
7
37
4
2
zþ
1
9
1
6H); 8.87 (H b pyrrole, m, 8H). MS (ESI: CH Cl /MeOH:
2
/1) (m/z): calcd for C121H N ONa Ru (MþNa ):
CH ¼822.1721. Found: 822.1711.
2
3)
1
02
þ
717.4334. Found: 1717.4330. UV–VIS (CH Cl ):
68
4
0
ethyl-3,7,13,17-tetramethyl porphyrinato ruthenium
4.3.8. 5,15-Bis(9,9 -spirobifluoren-2-yl)-2,8,12,18-tetra-
2
2
lmax/nm (log 1): 228 (5.1); 298 (4.66); 309 (4.74); 420
2
1
1
(
CV (CH Cl 0.2 M/Bu NPF , Fc/Fc ): 0.46 V; 0.89 V;
5.31); 533 (4.28); 569 (3.84). IR (KBr, cm ): nCO 1938.
þ
bis(methyl-diphenyl phosphine) 18. Yield: 85%.
H
NMR (CDCl , ppm): (aa and ab): d 22.70 (CH
3 3
2
2
4
6
1
.37 V.
phosphine, t, 1, 5H); 22.54 (CH3 phosphine, t, 3H);
2.30 (CH phosphine, t, 1, 5H); 1.53 (CH ethyl, m,
2
3
3
4.3.5. Typical procedure for phsophine ligation: 5,15-
bis(9,9 -spirobifluoren-2-yl)porphyrinato ruthenium bis
(
carbonyl complex (50 mmol) dissolved in distilled and
degassed chloroform or dichloromethane was added
methyldiphenylphosphine (300 mmol) under an argon
atmosphere. The solution was stirred at room temperature
until the reaction was completed (5 min). The bis-ligation
was checked by monitoring the UV–VIS spectrum. After
removal of the solvent, the crude product was crystallized in
12H); 2.13 (CH methyl, s, 12H); 3.60 (CH ethyl, m, 8H);
3 2
0
methyl-diphenyl phosphine) 8. To a solution of ruthenium
3.80 (H phosphine o-phenyl ring, m, 2H); 4.02 (H phosphine
o-phenyl ring, m, 4H); 4.12 (H phosphine, o-phenyl ring, m,
2H); 5.75 (H phosphine m-phenyl ring, m, 4H); 6.01–6.10
(H phosphine, m-phenyl ring, m, 4H); 6.26 (H phosphine
p-phenyl ring, m, 2H); 6.39 (H phosphine, p-phenyl ring, m,
2H); 6.87–7.93 (Hspirobifluorene, m, 30H); 9 (H
1
meso,
s, 1H); 9.1 (HX,XX meso, s, 1H). P NMR (CDCl , ppm)
X,XX
3
3
(aa and ab): 3.14 (P phosphine, 1P); 3.16 (P phosphine,
1P). MS (ESI: CHCl /MeOH: 95/5) (m/z): calcd for
3
zþ
1
02
hexane or pentane to give the Ru(II)bis(methyldiphenyl-
1
C108H N P
4 2
Ru (M ):1606.5715. Found: 1606.5707.
90
phosphine) complex (yield: 85%). H NMR (toluene d ,
8
UV–VIS (CH Cl ): l (log 1): 426 (5.10); 507 (4.2).
max/nm
2
2
ppm) (aa and ab): d 22.64 (CH phosphine, t, 1.5H);
3
0
yl)porphyrinato ruthenium bis(methyl-diphenyl phos-
phine) 22. Yield: 88%. H NMR (toluene d , ppm) (4a,
8
3ab, 2a2b, abab): d 22.90 (CH phosphine, t, 0.37H);
3
2
2.36 (CH phosphine, t, 3H); 22.14 (CH phosphine, t,
3
4.3.9. meso-5,10,15,20-Tetrakis(9,9 -spirobifluoren-2-
3
1
.5H); 4.19 (H phosphine o-phenyl ring, m, 2H); 4.25 (H
1
phosphine o-phenyl ring, m, 4H); 4.41 (H phosphine
o-phenyl ring, m, 2H); 5.96–6.31 (H phosphine m-phenyl
ring, m, 8H); 6.45–6.61 (H phosphine p-phenyl ring, m,
22.64 (CH phosphine, t, 1.5H); 22.36 (CH phosphine, t,
3
3
4
H); 6.96 (H spirobifluorene, m, 3H); 7.46–8.25 (H
spirobifluorene, m, 27H); 8.51 (H b pyrrole, m, 4H); 8.69
H bpyrrole, m, 4H); 9.17 (H meso, s, 1H); 9.21 (HX,XX
1.5H); 22.31 (CH3 phosphine, t, 0.75H); 22.04 (CH3
phosphine, t, 1.5H); 21.82 (CH phosphine, t, 0.37H); 4.09
3
(
(H phosphine, o-phenyl ring, m, 2H); 4.39 (H phosphine,
o-phenyl ring, m, 4H); 4.50 (H phosphine, o-phenyl ring, m,
2H); 5.84 (H phosphine, m-phenyl ring, m, 2H); 6.12 (H
phosphine m-phenyl ring, m, 6H); 6.52 (H phosphine,
p-phenyl ring, m, 4H); 6.97–8.32 (H spirobifluoreneþH b
X,XX
3
1
meso, s, 1H). P NMR (toluene d , ppm) (aa et ab): 2.6 (P
8
phosphine, 1P); 2.7 (P phosphine, 1P). MS (ESI: CH Cl /
2
2
1
02
MeOH: 9/1) (m/z): calcd for C H N P Ru
9
6 66 4 2
zþ
M ):1438.3806. Found: 1438.3847. UV–VIS (CH Cl ):
2 2
(
3
1
lmax/nm (log 1): 426 (5.3); 510 (4).
pyrrole, m, 68H). P NMR (toluene d , ppm): 2.42 (s, br,
8
1P); 2.45 (s, br, 0.75P); 2.56 (s, 0.25P). UV–VIS (CH Cl ):
lmax/nm (log 1): 437 (5.43); 522 (3.47).
2 2
4
.3.6. 5,15-Bis(2-methoxyphenyl) porphyrinato ruthe-
1
nium bis(methyl-diphenyl phosphine) 11. Yield: 85%. H
NMR (CDCl ): aa isomer: d 2 2.37 (CH phosphine, t,
4.3.10. meso-5,10,15,20-Tetrakis(3-methylphenyl)-
porphyrinato-rutheniumbis(methyl-diphenyl phos-
3
3
3
H); 22.15 (CH phosphine, t, 3H); 3.74 (CH methoxy
3
3
1
group, s, 6H); 4.16 (H phosphine o-phenyl ring, m, 4H);
.35 (H phosphine o-phenyl ring, m, 4H); 6.45 (H phosphine
m-phenyl ring, m, 8H); 6.76 (H phosphine p-phenyl ring, m,
H); 7.41–7.7 H porphyrin phenyl ring, m, 8H); 8.25 (H b
phine) 26. Yield: 85%. H NMR (CDCl , ppm): d 22.12
3
4
(CH3 phosphine, t, 6H); 2.61 (CH , s, 12H); 4.34 (H
3
phosphine o-phenyl ring, m, 8H); 6.51 (H phosphine
m-phenyl ring, t, 8H); 6.80 (H phosphine p-phenyl ring, t,
4

C. Poriel et al. / Tetrahedron 60 (2004) 145–158
157
1
4H); 7.32–7.8 (H porphyrin phenyl ring, m, 16H); 8.1 (H b
pyrrole, s, 8H).
Yield: 90%. H NMR (CDCl , ppm) (4a, 3ab, 2a2b,
3
abab): d-1.18 (CH3 t-BuCN, s, 1.1H); 20.96 (CH3
t-BuCN, s, 4.5H); 20.86 (CH t-BuCN, s, 2.25H); 20.74
3
4
.4. Typical procedure for isocyanide ligation
(CH t-BuCN, s, 4.5H); 20.62 (CH t-BuCN, s, 4.5H);
3
3
2
0.50 (CH t-BuCN, s, 1.1H); 6.88 (H spirobifluorene, d,
3
To a solution of ruthenium carbonyl complex (50 mmol) in
distilled chloroform or dichloromethane was added
t-butylisocyanide (300 mmol) under an argon atmosphere.
The solution was stirred at room temperature until the
reaction was completed. The bis-ligation was checked by
monitoring the UV–VIS spectrum. After filtration, the
solvents were removed under vacuum and the residue was
dissolved in dichloromethane. Pentane was then added and
the solution was set aside for one day for crystallization at
4H); 7.02 (H spirobifluorene, m, 8H), 7.18 (H spirobi-
fluorene, m, 12H); 7.30–7.51 (H spirobifluorene, m, 16H);
7.70 (H spirobifluorene, t, 8H); 8.02 (H spirobifluorene, m,
12H); 8.12 (H b pyrrole, m, 8H). MS (ESI: CH Cl /MeOH:
2
2
1
02
zþ
9/1) (m/z): calcd for C130H N
Ru (M ): 1832.5957.
Found: 1832.6014. UV–VIS (CH Cl ): l (log 1): 227
86
6
2
2
max/nm
(5.21); 297 (4.68); 307 (4.7); 425 (5.52); 532 (3.55). IR
(KBr, cm2 ): nCN 2107.
1
0 8C. Purple crystals of Ru(II) bis(t-butylisocyanide) com-
plex were collected by filtration and washed with hexane.
4.4.6. meso-5,10,15,20-Tetrakis(3-methylphenyl)por-
phyrinato-ruthenium bis(t-butylisocyanide) 27. Yield:
1
90%. H NMR (CDCl , ppm) 20.41 (CH t-BuNC, s,
18H); 2.65 (CH , s, 12H); 7.6 (H porphyrin phenyl ring, m,
3
3
0
ruthenium bis(t-butylisocyanide) 9. Yield: 85%.
4
.4.1. 5,15-Bis(9,9 -spirobifluoren-2-yl)porphyrinato
1
3
H
NMR (CDCl , ppm) (aa and ab): d 20.99 (CH t-BuNC,
8H); 8.01 (H porphyrin phenyl ring, m, 8H); 8.47 (H b
pyrrole, s, 8H).
3
3
s, 4.5H); 20.76 (CH t-BuCN, s, 9H); 20.64 (CH t-BuCN,
3
3
s, 4.5H); 6.86–7.77 (H spirobifluorene, m, 24H); 8.12 (H
spirobifluorene, m, 6H); 8.43 (HIII,VII,XIII,XVII b pyrrole, m,
4
meso, s, 2H).MS (ESI: CH Cl /MeOH: 9/1) (m/z): calcd for
H), 8.75 (HII,VIII,XII,XVIII, b pyrrole, d, 4H), 9.42 (HX,XX
Acknowledgements
2
2
1
02
zþ
C H N
Ru (M ):1204.3766. Found: 1204.3780. UV–
VIS (CH Cl ): l (log 1): 228 (5.10); 296 (4.73); 308
We thank MESRT support for CP. Dr. J. Rault-Berthelot
and Dr. A. Bondon were very helpful in the obtention and
discussionof voltammograms and NMR spectra, respectively.
8
0 58 6
2
2
max/nm
(
CH Cl , cm ): nCN 2219.
4.75); 411 (5.28); 525 (3.98); 560 (3.59). IR (liquid,
2
1
2
2
4.4.2. 5,15-Bis(2-methoxyphenyl) porphyrinato ruthe-
1
nium bis(t-butylisocyanide) 13. Yield: 85%. H NMR
References and notes
(
CDCl , ppm): aa isomer d 20.92 (CH t-BuNC, s, 9H);
3 3
2
0.21 (CH t-BuNC, s, 9H); 4.12 (CH methoxy, s, 6H);
3
1. Kim, Y. H.; Shin, D. C.; Kim, S. H.; Ko, C. H.; Yu, H. S.;
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3
7
.3–7.8 (H porphyrin phenyl ring, m, 8H); 8.91 (H b
3
3
pyrrole, d J¼4 Hz, 4H), 9.15 (H, b pyrrole, d J¼4 Hz,
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3
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1
02
zþ
calcd for C H N
1
Ru (M ): 1372.5671. Found:
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