(η6-Arene)tricarbonylchromium and ferrocene complexes linked to binaphthyl derivatives

Article abstract of DOI:10.1021/om700586z

Palladium-catalyzed coupling reactions of 6,6′-dihydroxyboron-2, 2′-dimethoxy-1,1′-binaphthyl 5g and chloroarenetricarbonylchromium complexes 6a - c afforded complexes 7a - c with the binaphthyl residue directly linked to the (η⁶-arene)tricarbonylcriromium entity. Coupling reactions of 2,2′-dimethoxy, 3,3′diodo, and 6,6′-diodo-1, 1′-binaphthyl 3h and 5h with ethynylarenetricarbonylchromium derivatives 6d - f and ethynylferrocene 9 yielded binaphthyl compounds linked to arenetricarbonylchromium and feirocenyl derivatives 8a - c, 11a - c, 10, and 12 through a triple bond. Condensation of 2,2′-dimethylrriethoxy, 3-formyl, 1,1′-binaphthyl 2a with (η⁶-phenyl) methyltriphenylphosphonium tricarbonylchromium 13 and ferrocenylmethyltriphenylphosphonium 18 gave binaphthyl compounds linked to arenetricarbonylchromium and ferrocenyl derivatives 14 and 19, respectively, through a double bond. X-ray analyses of the dinuclear chromium complex 8a and of the mononuclear chromium complex 17-Z are described.

Full text of DOI:10.1021/om700586z

Organometallics 2007, 26, 6139-6149
6139
(η6-Arene)tricarbonylchromium and Ferrocene Complexes Linked to
Binaphthyl Derivatives
Romain Germaneau,† Rene´ Chavignon,† Jean-Philippe Tranchier,† Franc¸oise Rose-Munch,*,†
Eric Rose,*,† Mayeul Collot,† and Carine Duhayon‡
Laboratoire de Chimie Organique, UMR CNRS 7611, UniVersite´ Pierre et Marie Curie-Paris6, Tour 44 -
1er e´tage, 4, Place Jussieu, 75252 Paris Cedex 05, France, and Laboratoire de Chimie de Coordination,
CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 04, France
ReceiVed June 14, 2007
Palladium-catalyzed coupling reactions of 6,6′-dihydroxyboron-2,2′-dimethoxy-1,1′-binaphthyl 5g and
chloroarenetricarbonylchromium complexes 6a-c afforded complexes 7a-c with the binaphthyl residue
directly linked to the (η6-arene)tricarbonylchromium entity. Coupling reactions of 2,2′-dimethoxy, 3,3′-
diodo, and 6,6′-diodo-1,1′-binaphthyl 3h and 5h with ethynylarenetricarbonylchromium derivatives 6d-f
and ethynylferrocene 9 yielded binaphthyl compounds linked to arenetricarbonylchromium and ferrocenyl
derivatives 8a-c, 11a-c, 10, and 12 through a triple bond. Condensation of 2,2′-dimethylmethoxy,
3-formyl, 1,1′-binaphthyl 2a with (η6-phenyl)methyltriphenylphosphonium tricarbonylchromium 13 and
ferrocenylmethyltriphenylphosphonium 18 gave binaphthyl compounds linked to arenetricarbonylchromium
and ferrocenyl derivatives 14 and 19, respectively, through a double bond. X-ray analyses of the dinuclear
chromium complex 8a and of the mononuclear chromium complex 17-Z are described.
complexes.4,5c Our final goal was to associate chiral ortho or
meta disubstituted-arenetricarbonylchromium complexes with
helico¨ıdal binaphthyl residues and to know if the combination
of the planar and helico¨ıdal chiralities could enhance NLO
activities. To our knowledge, only a few examples of binaphthyl
derivatives substituted by organometallic complexes have been
described in the literature. One implied cationic diiron com-
plexes obtained by condensation of ortho monoaldehyde 1a and
dialdehyde 3a and the cationic dinuclear complex [Fe2(η5-
C5H5)2(CO)2(µ-CO)(µ-C-CH3)]+[BF4]-,5a another one con-
cerned the benzannulation of axial chiral biscarbene complexes
of Cr,5b and a third one involved the combination of planar
chirality and axial chirality by reaction of (S)-2-amino-2′-
methoxy-1,1′-binaphthyl with the (S)- or (R)-ferrocenylpropenal.
Here, we report efficient syntheses of (η6-arene)tricarbonyl-
chromium and ferrocene complexes linked to 2,2′-dialkoxy-1,1′-
binaphthyl derivatives either directly or through different spacers
such as a triple or a double bond.
Introduction
Carbon-bridged bimetallic π-conjugated complexes have
attracted considerable interest due to their physical and chemical
properties leading to potential application as a material with
nonlinear optical properties.1 In our laboratory, we have prepared
such complexes by creating C-C bonds via different method-
ologies associating organic derivatives and η5- and η6-organo-
metallic complexes.2 Being involved in organometallic com-
plexes and recently in 2,2′-dimethoxy-1,1′-binaphthyl compounds,3
we combined the two experiences to prepare binapthyl deriva-
tives associated with arenetricarbonylchromium and ferrocene
* To whom correspondence should be addressed. E-mail: rose@
ccr.jussieu.fr (E.R.); rosemun@ccr.jussieu.fr (F.R.-M.).
† Universite´ Pierre et Marie.
‡ CNRS.
(1) (a) Oudar, J. L.; Chemla, D. S. J. Chem. Phys. 1977, 66, 2664-
2668. (b) Chemla, D. S., Zyss, J., Eds. Nonlinear Optical Properties of
Organic Molecules and Crystals; Academic Press: San Diego, CA, 1987;
Vols. 1 and 2. (c) Marder, S. R.; Beratan, D. N.; Cheng, L. T. Science
1991, 252, 103. (d) Goovaerts, E.; Wenseleers, W. E.; Garcia, M. H.; Cross,
G. H. In Handbook of AdVanced Electronic and Photonic materials and
DeVices; Nalwa, H. S., Ed.; Academic Press: New York, 2001; Vol. 9,
Chapter 3, pp 127-191. (e) Heck, J.; Dabek, S.; Meyer-Fridrieschen, T.;
Wong, H. Coord. Chem. ReV. 1999, 190-192, 1217. (f) Di Bella, S. Chem.
Soc. ReV. 2001, 30, 355. (g) Zhou, W.; Kuebler, S. M.; Braun, K. L.; Yu,
T.; Cammack, J. K.; Ober, C. K.; Perry, J. W.; Marder, S. R. Science 2002,
296, 1106. (h) Marder, S. R. Chem. Commun. 2006,131-134.
(2) (a) Auffrant, A.; Prim, D.; Rose-Munch, F.; Rose, E.; Vaissermann,
J. Organometallics 2003, 22, 1898-1913. (b) Garcia, M. H.; Royer, S.;
Robalo, M. P.; Dias, A. R.; Tranchier, J.-P.; Chavignon, R.; Prim, D.;
Auffrant, A.; Rose-Munch, F.; Rose, E.; Vaissermann, J.; Persoons, A.;
Asselberghs, I. Eur. J. Inorg. Chem. 2003, 3895-3904. (c) Jacques, B.;
Tranchier, J.-P.; Rose-Munch, F.; Rose, E.; Stephenson, G. R. Organome-
tallics 2004, 23, 184-193. (d) Schouteeten, S.; Jacques, B.; Auffrant, A.;
Tranchier, J.-P.; Rose-Munch, F.; Rose, E.; Stephenson, G. R. Organome-
tallics 2004, 23, 4308-4316. (e) Prim, D.; Andrioletti, B.; Rose-Munch,
F.; Rose Couty, F. Tetrahedron 2004, 60, 3325-3347. (f) Roy, A.-L.;
Chavarot, M.; Rose, E.; Rose-Munch, F.; Attias, A.-J.; Kre´her, D.; Fave,
J.-L.; Kamierszky, C. C. R. Chimie 2005, 8, 1256-1261. (g) Jacques, B.;
Chavarot, M.; Rose-Munch, F.; Rose, E. Angew. Chem., Int. Ed. 2006, 45,
3481. (h) Eloi, A.; Munch-Rose, F.; Jonathan, D.; Tranchier, J. P.; Rose,
E. Organometallics 2006, 25, 4554. (i) Li, M.; Riache, N.; Tranchier, J. P.;
Rose-Munch, F.; Rose, E. Synthesis 2007, 2, 277.
Results and Discussion
The general strategy for the preparation of arenetricarbon-
ylchromium or ferrocene derivatives linked to binaphthyl
compounds was based on palladium-catalyzed coupling reactions
such as Stille, Negishi, or Sonogashira reactions. Thus, we
(3) (a) Rose, E.; Quelquejeu, M.; Kossanyi, A.; Boitrel, B. Coord. Chem.
ReV. 1998, 178-180, 1407. (b) Rose, E.; Quelquejeu, M.; Pandian, R. P.;
Lecas-Nawrocka, A.; Vilar, A.; Ricart, G.; Collman, J. P.; Wang, Z.;
Straumanis, A. Polyhedron 2000, 19, 581. (c) Rose, E.; Ren, Q.-Z.;
Andrioletti, B. Chem.-Eur. J. 2004, 10, 224-230. (d) Rose, E.; Andrioletti,
B.; Zrig, S.; Quelquejeu-Etheve, M. Chem. Soc. ReV. 2005, 34, 573.
(4) Chavignon, R. Ph.D. Thesis, Universite´ Pierre et Marie Curie, Paris6,
July 08, 2005.
(5) (a) Hudson, R. D. A.; Manning, A. R.; Gallagher, J. F.; Garcia, M.
H.; Lopes, N.; Asselberghs, I.; Van Boxel, R.; Persoons, A.; Lough, A. J.
J. Organomet. Chem. 2002, 655, 70-88. (b) Tomnschatt, P.; Kro¨ner, L.;
Steckhan, E.; Nieger, M.; Do¨tz, K.-H. Chem. ReV. 1995, 5, 700-707. (c)
Kno¨lker, H.-J.; Hermann, H. Angew. Chem., Int. Ed. Engl. 1996, 35, 341-
344.
10.1021/om700586z CCC: $37.00 © 2007 American Chemical Society
Publication on Web 10/30/2007

6140 Organometallics, Vol. 26, No. 25, 2007
Germaneau et al.
Scheme 2. Synthesis of the Dinuclear Complex 3e
Scheme 1. Binaphthyl Derivatives 1, 2, and 3
complex 3e efficiently. Alternatively, condensation of the tin
derivative 3f9 and bromobenzenetricarbonylchromium10 was
undertaken, but it was revealed to be also unsuccessful. Suzuki
arylation of chlorobenzenetricarbonylchromium 6a10 with the
boronic acid 3g in the presence of Pd(PPh3)4 and Ba(OH)2 as a
base gave a mixture of compounds, but the expected complex
3e was obtained as a minor product, Scheme 2. If K2CO3 was
used as a base and if the reaction mixture was performed in
acetone, complex 3e was obtained in only 28% yield and was
shown to be very unstable. We tried also to perform ipso
nucleophilic aromatic substitution SNAr11 with fluorobenzen-
etricarbonylchromium12 and the bis(naphthyllithium) derivative
3c. Unfortunately, we recovered the starting material probably
because the protons ortho to the fluoro group were too acidic
and likely lithiated by 3c and then hydrolyzed.
In view of these results, we investigated what could be the
influence of steric hindrance of the boronic derivative on the
course of the reaction by performing the reaction on a less
hindered carbon. Consequently, we repeated an analogous
experiment starting from the less crowded boronic acid at the
C6 carbon 5g. Thus, in the presence of Pd(PPh3)4, Na2CO3, and
chloroderivatives 6a-c,13e we successfully obtained the corre-
sponding binaphthyl derivatives 7a-c directly substituted by
(η6-arene)Cr(CO)3 entities in 71%, 72%, and 74% yield,
respectively, Scheme 3. A well-resolved 1H NMR spectrum of
the ortho derivative 7b was obtained. Indeed, the four protons
H13, H14, H15, and H16 of the η6 complex resonate at 5.18, 5.50,
5.18, and 5.62 ppm, respectively, in agreement with a major
conformation of the Cr(CO)3 tripod13 in solution eclipsing the
C12 carbon bearing the methyl group and the C14 and C16
carbons. The differences of chemical shift δ(H14) - δ(H13) )
0.32 and δ(H16) - δ(H15) ) 0.44 ppm are noticeable, Table 1.
No conclusion can be drawn for the major conformation of the
tripod Cr(CO)3 in solution for complexes 7a and 7c. For the
naphthyl part, the five aromatic protons H3, H4, H6, H8, and H9
resonate almost at the same frequencies for complexes 7a and
synthesized three series of compounds depending on the nature
of the link between the binaphthyl residue and the organome-
tallic entity: complexes 3e, 7a-c where the binaphthyl is
directly linked to the arenetricarbonylchromium derivatives,
complexes 8a-d, 10, 11a-c, and 12 in which the spacer is a
triple bond, and complexes 14-17 and 19 in which the spacer
is a double bond.
Synthesis of the Starting Binaphthyl Derivatives. Racemic
2,2′-dihydroxy-1,1′-binaphthyl (BINOL) treated with NaH and
MeI yielded the dimethoxy compound 3b.6 ortho-Lithiation of
the diether gave the 2,2′-dilithio compound 3c,3c which was
trapped with DMF, Br2, I2, ClSnBu3, and B(OEt)3 to yield the
dialdehyde 3a7 (71% yield), the dibromo 3d (30% yield), the
diodo 3h (33% yield), the stannous derivative 3f (38% yield),
and the diboronic acid 3g (37% yield), Scheme 1. Depending
on the experimental conditions, the monoaldehyde 1a and the
monobromo derivative 1d have been also recovered as byprod-
ucts. We prepared compound 2b, which appeared to be more
soluble in organic solvents in contrast to 1b, by protecting the
hydroxy groups of BINOL with a methyl methoxy group
(MOM).8 The choice of the protected methoxy methyl ether
MOM group was dictated not only by a solubility problem, but
also by the monolithiation/formylation sequence. Indeed, lithia-
tion of 1b required 3 equiv of n-BuLi, whereas lithiation of 2b
occurred with only 1 equiv of n-BuLi. DMF trapping gave the
monoaldehyde 2a in 60% yield together with the dialdehyde
4a in 22% yield. Thus, 2b was lithiated with n-BuLi into 2c
and trapped with I2, giving the monoiodo compound 2h in 49%
yield.
Direct Link between the Binaphthyl Derivatives and the
Arenetricarbonylchromium Complexes: Synthesis of 3e,
7a-c. We were first interested to test the addition of an
organometallic moiety at the 3 or at the 3,3′ positions of the
binaphthyl framework. Stille arylation of the bromo derivative
3d and tributyltinbenzenetricarbonylchromium9 failed to afford
(10) (a) Mahaffy, C. A. L. J. Organomet. Chem. 1984, 262, 33-37. (b)
Mu¨ller, T. J. J.; Lindner, H. J. Chem. Ber. 1996, 129, 607-613. (c) Muller,
T. J. J.; Ansorge, M.; Lindner, H. J. Chem. Ber. 1996, 129, 1433.
(11) (a) Rose-Munch, F.; Rose, E.; Semra, A.; Garcia-Oricain, Mignon,
L.; Knobler, C. J. Organomet. Chem. 1989, 363, 297. (b) Rose-Munch, F.;
Aniss, K.; Rose, E. J. Organomet. Chem. 1990, 385, C1. (c) Rose-Munch,
F.; Aniss, K. Tetrahedron Lett. 1990, 31, 6351. (d) Rose-Munch, F.; Aniss,
K.; Rose, E.; Vaisserman, J. J. Organomet. Chem. 1991, 415, 223. (e) Rose-
Munch, F.; Gagliardini, V.; Renard, C.; Rose, E. Coord. Chem. ReV. 1998,
178-180, 249-268. (f) Rose-Munch, F.; Rose, E. Curr. Org. Chem. 1999,
3, 445-467. (g) Rose-Munch, F.; Rose, E. Eur. J. Inorg. Chem. 2002, 6,
1269-1283. (h) Rose-Munch, F.; Rose, E. In Modern Arene Chemistry;
Astruc, D., Ed.; Wiley-VCH: New York, 2002; Chapter 11, p 368.
(12) Ghavshou, M.; Widdowson, D. A. J. Chem. Soc., Perkin Trans. 1
1983, 3065.
(13) (a) Solladie´-Cavallo, A.; Suffert, J. Org. Magn. Reson. 1980, 14,
426. (b) Boutonnet, J. C.; Le Martret, O.; Mordenti, L.; Precigoux, G.; Rose,
E. J. Organomet. Chem. 1981, 221, 147. (c) Boutonnet, J. C.; Levisalles,
J.; Rose, E.; Precigoux, G.; Courseille, C.; Platzer, N. J. Organomet. Chem.
1983, 255, 317. (d) Boutonnet, J. C.; Rose-Munch, F.; Jeannin, Y.; Rose,
E. J. Organomet. Chem. 1985, 297, 185. (e) Rose-Munch, F.; Rose, E.;
Semra, A.; Bois, C. J. Organomet. Chem. 1989, 363, 103.
(6) (a) See review on BINOL: Brunel, J. M. Chem. ReV. 2005, 105,
857-897. (b) Naruta, Y. Tetrahedron: Asymmetry 1991, 2, 533. (c)
Kossanyi, A.; Tani, F.; Nakamura, N.; Naruta, Y. Chem.-Eur. J. 2001, 7,
2862.
(7) (a) Naruta, Y.; Tani, F.; Ishihara, N.; Maruyama, K. J. Am. Chem.
Soc. 1991, 56, 6865. (b) Cox, P. J.; Wang, D.; Snieckus, V. Tetrahedron
Lett. 1992, 33, 2253.
(8) (a) Ba¨hr, A.; Droz, A. S.; Neidlein, H.; Anderson, S.; Seiler, P.;
Diederich, F. HelV. Chim. Acta 1998, 81, 1931-1963. (b) Matsunaga, S.;
Das, J.; Rolls, J.; Vogl, E.; Yamamoto, N.; Iida, T.; Yamagushi, K.;
Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 2252.
(9) Prim, D.; Tranchier, J.-P.; Chavignon, R.; Rose-Munch, F.; Rose, E.
Organometallics 2001, 20, 1279-1281.

(η6-Arene)tricarbonylchromium and Ferrocene Complexes
Organometallics, Vol. 26, No. 25, 2007 6141
Scheme 3. Synthesis of the Dinuclear Complexes 7
Scheme 4. Synthesis of the Dinuclear Complexes 8
1
Table 1. Selected H NMR Data of Complexes 7a-c
carbonylchromium complex 6a. For this purpose, we reacted
the diodo compound 3h with trimethysilylacetylene, which
afforded the trimethylsilylethynyl compound 3i in 62% yield
in the presence of PdCl2(PPh3)2, CuI, and Et3N. Cleavage of
the C-Si bond with NaOH, 2 N in MeOH occurred almost in
quantitative yield giving complex 3j.2a,10b Next, coupling
reaction using Pd2(dba)3, AsPh3, Et3N with chlorobenzenetri-
carbonylchromium 6a and 3j in THF (reflux 5h) yielded
complex 8a in 49% yield, Scheme 4. The reaction with the
organometallic entity bearing the triple bond is slightly more
efficient than the one involving the binaphthyl residue substi-
tuted by the triple bond. The yield of the coupling reaction was
improved by using the diiodo derivative 4h, which, heated with
the alkyne 6d in the presence of Pd2dba3, AsPh3 for 5 h, gave
complex 8d in 80% yield.
Crystals of 3,3′-(ethynylbenzenetricarbonylchromium), 2,2′-
dimethoxy, and 1,1′-binaphthyl 8a suitable for X-ray analysis
were obtained from a solution of the complex in a petroleum
ether/acetone mixture. CAMERON views and some selected
bond lengths are presented in Figures 1-3, and crystal data are
reported in Table 2. Three important features can be emphasized.
First, the neutral complex displays the well-known piano-stool
conformation found in half-sandwich tricarbonyl complexes.2a,d,e
The conformations adopted by the Cr(CO)3 entities with respect
to the aromatic carbons of the rings are unexpectedly different
for each half of the molecule. One is a staggered conformation
complex
H12
H13
H14
H15
H16
7a
7b
7c
5.77
5.49
5.18
5.34
5.50
5.58
5.49
5.18
5.58
5.77
5.62
5.58
5.17
H3
complex
H4
H6
H8
H9
7a
7b
7c
7.49
7.51
7.49
8.02
8.02
8.02
8.01
7.88
8.01
7.32
7.23
7.33
7.13
7.12
7.13
7c; however, the two protons H6 and H8 of complex 7b are
unexpectedly shielded, Table 1. According to these results, we
can assume that it is likely that the C3 and C3′ positions of the
binaphthyl moiety were not reactive for a direct substitution by
an arenetricarbonylchromium complex for steric reasons. Thus,
we tried to link these two parts through a spacer, a triple or a
double bond. The corresponding results are summarized next.
Binaphthyl Derivatives Linked to Arenetricarbonylchro-
mium and Ferrocene Complexes through a Triple Bond:
Synthesis of 8a-d, 10, 11a-c, and 12. Our first trial concerned
the introduction of a triple bond between the naphthyl ring and
the organometallic part by condensing the dibromo compound
3d and ethynylarenetricarbonyl chromium 6d2c,d using
PdCl2(PPh3)2, CuI, Et3N, THF or Pd2(dba)3, AsPh3, Et3N, THF
at 40 °C, but this did not yield the expected chromium complex
8a, Scheme 4. Repeating these condensations with the diiodo
compounds 3h and the alkyne 6d, we obtained complex 8a in
55% yield with PdCl2 (PPh3)2, CuI, Et3N, and THF and in 74%
yield with Pd2dba3, AsPh3 without CuI. This reaction has been
generalized with ortho and meta ethynyltoluenetricarbonyl-
chromium complexes 6e and 6f, which lead to the formation of
the di-substituted complexes 8b and 8c in 60% and 90% yield,
respectively, as diastereoisomer mixtures, Scheme 4.
of the tripod with dihedral angles O2′Cr1′CtC11′, O3′Cr1′CtC15′
,
and O1′Cr1′CtC13′ of 26°, 28°, and 31°, respectively, for the
tripod coordinated to the C11′-C16′ carbons, Ct being the center
of the six-membered ring, Figure 2, whereas the other one is
an almost eclipsed conformation with dihedral angles O21Cr1-
CtC11, O23Cr1CtC13, and O22Cr1CtC15 of 6°, 14°, and 18°,
respectively, Figure 1. These differences are probably due to
crystal packing effects. It is worthy to note that these two
conformations are associated with two opposite orientations of
Alternatively, complex 8a was also obtained by condensing
3,3′-diethynyl-binaphthyl compound 3j with chlorobenzenetri-

6142 Organometallics, Vol. 26, No. 25, 2007
Germaneau et al.
Table 2. Crystal Data for Complexes 8a (C44H26Cr2O8) and
17 (C35H28CrO7)
17
8a
formula
cryst class
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
C35H28CrO7
monoclinic
C2/c
22.541(5)
10.630(4)
26.26(1)
90
111.75(2)
90
5843(4)
8
C44H26Cr2O8
monoclinic
P21/n
10.610(2)
24.260(7)
14.354(4)
90
107.98(2)
90
3514(1)
4
Z
radiation type
wavelength (Å)
density
Mr
Mo KR
0.71073
1.39
612.60
0.442
Mo KR
0.71073
1.49
786.68
0.676
Figure 1. CAMERON views of complex 8a with the Cr1(CO)3
tripod projected onto the first arene ring. Selected bond lengths
(Å): Cr1C11 2.177(9); Cr1C12 2.191(11); Cr1C13 2.199(12); Cr1C14
2.182(11); Cr1C15 2.172(11); Cr1C16 2.192(10); C11C12 1.385(14);
C12C13 1.412(16); C13C14 1.368(16); C14C15 1.377(15); C15C16 1.398-
(15); C16C11 1.398(13).
µ (cm-1
)
temp (K)
size (mm)
color
295
120
0.07 × 0.18 × 0.30
0.03 × 0.15 × 0.45
yellow
orange
shape
plate
stick
diffractometer
no. of rflns measd
no of indep rflns
θ (min,max)
index ranges
h
Nonius KappaCCD
14 876
4487
Nonius KappaCCD
22 217
5931
1, 25.51
1, 26.02
-27 19
-12 11
-31 31
on F
0.0744
0.0822
-12 12
-29 26
-17 17
on F
0.0842
0.0875
k
l
refinement
R ) ∑(|Fo| - |Fc|)/∑|Fo|
Rw ) [∑w(||Fo| -
|Fc||)2/∑wFo ]1/2
2
∆Fmin (e Å-3
)
)
-0.44
0.73
1529
3.0
178
1.144
-1.47
1.52
2885
3
227
1.047
∆Fmax (e Å-3
no. of rflns used
σ(I) limit
no. of params
GOF
Figure 2. CAMERON views of complex 8a with the Cr1′(CO)3
tripod projected onto the second arene ring. Selected bond lengths
(Å): Cr1′C11′ 2.212(8); Cr1′C12′ 2.199(8); Cr1′C13′ 2.200(9); Cr1′C14′
2.210(10); Cr1′C15′ 2.229(8); Cr1′C16′ 2.238(8); C11′C12′ 1.393(11);
Scheme 5. Synthesis of the Dinuclear Complex 10
C12′C13′ 1.414(12); C13′C14′ 1.393(13); C14′C15′ 1.392(12); C15′C16′
1.412(11); C16′C11′ 1.433(11).
we noticed some π-π stacking between two naphthyl groups
of two different molecules. A distance of 3.4 Å was observed
between one naphthyl group of a molecule parallel to another
naphthyl group of another molecule. The dihedral angle of the
plane of the metal-coordinated arene ring and the corresponding
naphthyl moiety is 29° for the complex bearing the Cr1 and
30° for the complex bearing the Cr31 atom.
Condensation of the diodo compound 3h with ethynylfer-
rocene14 9 under the same experimental conditions as those used
for the formation of 8d afforded the bis-ferrocenyl complex 10
in 80% yield, Scheme 5. We generalized these reactions with
the halogenated binaphthyl derivatives substituted at the C6
position. We first tried to react the dibromo compound 5d with
ethynylbenzenetricarbonylchromium 6d2d,10 and PdCl2(PPh3)2,
CuI, and Et3N but without any success. Next, we tested the
diiodo compound 5h obtained in 97% yield by lithiation of 5d
with n-BuLi at 78 °C and then by treatment with I2. Sonogashira
coupling in the presence of CuI, PdCl2(PPh3)2, and NEt3 with
6d afforded the expected yellow complex 11a in 64% yield,
confirming the much stronger reactivity of the iodo derivatives
Figure 3. Dihedral angle between the two binaphthyl planes and
proximal and distal positions of the MeO groups of complex 8a.
the methoxy groups of the binaphthyl residue as clearly shown
in Figure 3. Indeed, the tripod Cr(CO)3, which is almost eclipsed
by the C11, C13, and C15 carbon atoms of the arene ring, is
associated with a distal methoxy group anti to the first Cr atom,
and the almost staggered tripod Cr(CO)3 is associated with a
proximal methoxy group syn to the second Cr atom. Second,
the bond lengths of the Cr1 and the Cr1′ atoms to the aromatic
carbons have almost the same mean value, 2.185(11) Å (range
2.152-2.218) and 2.215(11) Å (range 2.182-2.248), respec-
tively. The dihedral angle between the naphthyl planes is 88°
as expected, Figure 3. This view clearly shows the proximal
and distal positions of the methyl of the methoxy groups. Finally,
(14) Polin, J.; Schottenberger, H. Org. Synth. 1996, 73, 262.

(η6-Arene)tricarbonylchromium and Ferrocene Complexes
Organometallics, Vol. 26, No. 25, 2007 6143
Scheme 6. Synthesis of the Dinuclear Complexes 11
Scheme 7. Synthesis of the Dinuclear Complexes 12
Scheme 8. Synthesis of the Dinuclear Complex 14
in both C3- and C6-substituted series, Scheme 6. We extended
phenylphosphonium bromide 1318b in 68% yield by treating the
tricarbonylchromium complex of benzylic alcohol10 with PPh3,
HBr17 in THF in the presence of 4 Å molecular sieves.
this reaction by using ortho and meta methylethynylbenzenet-
ricarbonylchromium complexes 6e,f and recovered complexes
11b and 11c in 57% and 43% yield, respectively, as orange
yellow and yellow compounds, Scheme 6. Alternatively, we
reacted the 6,6′-bis-ethynylbinaphthyl compound 5k and chlo-
robenzenetricarbonylchromium 6a with a catalytic amount of
PdCl2(PPh3)2 and CuI, in the presence of NEt3 to form 11a,
but the less satisfying yield 43% than the preceding one 64%
obtained with the triple bond linked to the organometallic partner
was in good agreement with the results obtained for the C3-
substituted complex 8a. Under the same conditions as the ones
used for the formation of 10, ethynylferrocene 9 and the 6,6′-
diodo compound 5h gave the bimetallic iron complex 12 in 69%
yield, Scheme 7.
Binaphthyl Derivatives and Arenetricarbonylchromium
and Ferrocene Complexes Linked through a Double Bond:
Synthesis of 14-17 and 19. The choice of a double bond as a
spacer was dictated for a synthetic point of view but also by
the pioneering work of Green15 and Marder et al.,16 showing
interesting properties of a (Z)-1-ferrocenyl-2-(4 nitrobenzene)-
ethylene crystal and of the iodide of a cationic complex of
(E)-1-ferrocenyl-2-(4 pyridinium) ethylene, respectively. Thus,
we prepared first the η6-(benzyl)tricarbonylchromiumtri-
Condensation of the ylide generated by treating the phos-
phonium 13 with tBuOK18 and the dialdehyde 3a7a in refluxing
THF for 4 h afforded three products 14, 15, and 16 in 44%,
33%, and 13% yield, respectively, Scheme 8. Unexpectedly,
the Z dinuclear complex 14 was not contaminated by the E
conformer. The two olefinic protons H17 and H18 of complex
14 resonate at 7.03 and 6.33 ppm, and the five aromatic protons
of the ring coordinated to the Cr(CO)3 fragment exhibit two
signals at 5.33 (H13 H14 H15, m) and at 5.47 ppm (H12 H16, d).
The monoaldehyde 15 corresponded to the condensation of only
one ylide to the dialdehyde 3a, and compound 16 was probably
recovered by decomplexation by light and (or) air of one of the
arene rings of 14. The chemical shifts of the two sets of olefinic
protons of complex 16 are interesting to compare. Indeed, for
the double bond linked to the arenetricarbonylchromium com-
plex, the chemical shifts of the H17 and H18 protons are 6.33
and 7.03 ppm, J ) 12 Hz, chemical shifts similar to the values
noted for complex 14. Yet for the other double bond conjugated
to the phenyl ring, a large 0.47 ppm deshielding was observed
for the R proton at 6.80 ppm and a small 0.09 ppm deshielding
(15) Green, M. L. H.; Marder, S. R.; Thompson, M. E.; Baudy, J. A.;
Bloor, D.; Kolinsky, P.; Jones, R. J. Nature 1987, 330, 300.
(16) Marder, S. R.; Perry, J. W.; Schaefer, W. P.; Tiemann, B. G.; Groves,
P. C.; Perry, K. J. PROC. SPIE-Int. Soc. Opt. Eng. 1989, 1147, 108.
(17) Hercovet, A.; Le Corre, M. Synthesis 1988, 157.
(18) (a) Justin Thomas, K. R.; Lin, J. T.; Wen, Y. S. Organometallics
2000, 19, 1008. (b) Zhang, J.-X.; Dubois, P.; Je´roˆme, R. Synth. Commun.
1996, 26, 3091.

6144 Organometallics, Vol. 26, No. 25, 2007
Germaneau et al.
Scheme 10. Synthesis of the Mononuclear Complex 19
1H NMR data confirm the Z and E nature of the double bonds.
Indeed, the Z ethylenic protons resonate at 6.36 and 7.06 ppm,
J ) 12 Hz, whereas for the E isomer, one proton is found at
6.93 ppm, J ) 16 Hz, and the other one is hidden by the
fingerprint of the naphthyl proton signal. The chemical shifts
of H13, H14, H15 meta and para aromatic protons of the
coordinated ring resonate as a multiplet at the same frequency
5.33 ppm, whereas H12 and H16 ortho protons show a doublet
at 5.47 ppm, J ) 6 Hz. These data are in good agreement with
an anti-eclipsed conformation of the tripod of the major
conformer in solution with respect to the double bond.13
Crystals of the isomer 17-Z were obtained by slow diffusion
of petroleum-ether into an acetone solution of the complex,
which confirmed the Z olefin configuration. Crystal data are
reported in Table 2, and Figures 4 and 5 show CAMERON
views of the complex along with some selected bond lengths.
It is worthy to note a nearly anti-eclipsed conformation of the
Cr(CO)3 tripod with respect to the double bond in the solid state,
the dihedral angles of the projected Cr-CO with respect to the
aromatic carbon atoms being equal to 14-20°, Figure 4. The
MOM group OCH2OCH3 adopts a position that avoids interac-
tions with the arenetricarbonylchromium part. The bond lengths
Cr-Ci (i ) 11-16) between the Cr atom and the carbons of
the coordinated ring are almost equal, mean value 2.213(11)
Å. The length of the double bond is 1.324(14) Å. Furthermore,
the dihedral angle between the arene bearing the chromium
entity and the corresponding binaphthyl entity is 115.2°. These
two features rule out a strong conjugation between the two
aromatic parts in the solid state. We observed an unexpected
small dihedral angle between the naphthyl groups of 78°, Figure
5, and some π-π stacking between naphthyl groups of two
molecules lying at 3.6 Å.
Figure 4. CAMERON view of complex 17-Z with the Cr1(CO)3
tripod projected onto the arene ring. Selected bond lengths (Å):
CrC11 2.235(11); CrC12 2.188(10); CrC13 2.218(12); CrC14 2.207-
(13); CrC15 2.227(13); CrC16 2.201(12); C11C12 1.417(14); C12C13
1.409(15); C13C14 1.386(16); C14C15 1.392(16); C15C16 1.401(15);
C16C11 1.401(14).
Figure 5. CAMERON view of complex 17-Z showing the dihedral
angle between the binaphthyl groups.
Scheme 9. Synthesis of the Mononuclear Complex 17
For the E isomer, the H12, H13, and H14 protons resonate at
frequencies that are much more differentiated than the ones in
the Z isomer. Indeed, the H12, H16 protons resonate at 5.67 ppm,
d, J ) 6 Hz, whereas the H13H15 and H14 protons resonate at
5.50, t, J ) 6 Hz and 5.36 ppm, t, J ) 6 Hz, respectively.
Finally, we undertook a Wittig reaction between the ferro-
cenyl ylide21 of 18 and the monoaldehyde 2a, which afforded
the mononuclear iron complex 19 (Table 3) in 45% yield. The
Z isomer was the major isomer, the ratio E:Z being 1:3, Scheme
10. We recovered also methylferrocene as a byproduct (5%)
whose formation can be explained with the same mechanism
as the one involved for toluenetricarbonylchromium complex
formation vide supra.
for the â proton at 6.95 ppm, corresponding to a more electron-
rich olefin due to the decoordination of the Cr(CO)3 entity.
To selectively synthesize a binaphthyl complex monosubsti-
tuted by the styrene chromium derivative, we chose the
monoaldehyde 2a19 as the starting material, taking advantage
of its easy and selective formation from the diether 2b. We
reacted the ylide of 13 with the aldehyde 2a and obtained the
Z and E olefins 17-E and 17-Z in 15% and 66% yield,
respectively, Scheme 9. Toluenetricarbonylchromium complex
was recovered as a byproduct in 3% yield and characterized by
NMR spectroscopy.20 Its formation can be explained by hy-
drolysis of the phosphorus hydroxide ArCr(CO)3CH2Ph3P-OH
into Ph3PdO and the benzylic carbanion, which is protonated
into the toluene Cr complex. The Z and the E isomers could be
separated by silica gel chromatography column as yellow and
orange compounds. The last more intense color might be
explained by the conjugation of the π-system of the E isomer
probably being better than the one for the Z isomer.
Conclusion
We have developed an efficient strategy to substitute binaph-
thyl derivatives with (η6-arene)tricarbonylchromium and fer-
rocene complexes. Thus, palladium-catalyzed coupling of 3,3′
and 6,6′-boronic acid-2,2′-dialkoxy-1,1′-binaphthtyl and chlo-
roarenetricarbonylchromium derivatives yielded (η6-arene)-
(19) Bougauchi, M.; Watanabe, S.; Arai, T.; Sasai, H.; Shibasaki, M. J.
Am. Chem. Soc. 1997, 119, 2329.
(20) Kotzian, M.; Kreiter, C. G.; Ozkar, S. J. Organomet. Chem. 1982,
229, 29.
(21) (a) Dotsevi, G.; Sogah, Y.; Cram, D. J. J. Am. Chem. Soc. 1979,
11, 3035. (b) Ostrowski, J.; Hudack, R. A.; Robinson, M. R.; Wang, S.;
Bazan, G. C. Chem.-Eur. J. 2001, 7, 4500.

(η6-Arene)tricarbonylchromium and Ferrocene Complexes
Organometallics, Vol. 26, No. 25, 2007 6145
1
Table 3. Selected H NMR Data of Complexes 14, 15, 17, and 19
complex
H4
H6
H7
H8
H9
H12
H13
5.45
H14
H17
H18
14
15
7.97
8.02
8.63
7.93
7.93
8.23
8.01
7.92
8.02
8.08
7.88
7.93
7.87
7.83
7.83i
8.20
7.80
7.69
7.93
7.92g
7.93
7.78
7.82
7.69
7.78
7.69h
7.33
7.45
7.20
5.30
5.30
6.33a
6.34
7.03a
7.10c
6.95a
7.25-7.49b
5.31-5.44b
7.41
7.28
6.80a
7.60-7.20b
7.19-7.49
7.19-7.49
7.21-7.45b
7.21-7.45b
7.07-7.29b
5.30
5.67
5.45
5.50
5.30
5.36
6.33a
6.93
7.03a
d
17E
17Z
19E
19Z
5.47
5.28-5.37
6.36a
d
7.06a
7.05
7.07-7.29b
7.07-7.29b
6.40a
6.62a
a or. b m. c J ) 12 Hz. d Under naphthyl fingerprint. e 5.28-5.37. H3′ 7.63. H3′ 7.60. H3′ 7.50. i CHO 10.59.
f
g
h
3H, H7), 5.05 (td, J ) 6.2 Hz, J ) 1.0 Hz, 1H, H5), 5.11 (d, J )
6.2 Hz, 1H, H6), 5.24 (td, J ) 6.2 Hz, J ) 1.0 Hz, 1H, H4), 5.49
(d, J ) 6.2 Hz, 1H, H3). 13C NMR (50 MHz, CDCl3): 0.0 (C10),
19.9 (C7), 88.9 (C6), 89.6 (C9), 91.9 (C8), 92.3-96.5 (C4, C5), 98.4
(C3), 99.6 (C1), 110.6 (C2), 232.4 (CO). Anal. Calcd for C15H16-
CrO3Si: C, 55.55; H, 4.98. Found: C, 55.71; H, 5.03. The silylated
complex (3.02 g, 9.7 mmol) was dissolved in 60 mL of methanol.
A 2 N aqueous solution of sodium hydroxide (10.7 mL, 21.3 mmol)
was added, and the mixture was stirred for 3 h. After 30 mL of
water was added, the solution was extracted with 3 × 50 mL of
diethyl ether. The organic layers were dried over anhydrous
magnesium sulfate, filtered through Celite, and the solvents were
evaporated under reduced pressure. Compound 6e was purified by
a short silica gel chromatography column (15-40 µm, eluant EP/
Et2O: 96/4) and obtained as a yellow solid in 87% yield (2.13 g).
tricarbonylchromium complexes directly linked to the binaphthyl
residue. Coupling reactions of 3,3′ and 6,6′-diiodo-2,2′-dialkoxy-
1,1′-binaphthtyl derivatives with ethynylarenetricarbonylchro-
mium and ethynylferrocene complexes yielded (η6-arene)-
tricarbonylchromium and ferrocene complexes linked to
binaphthyl derivatives via a triple bond. Similarly, condensing
methyltriphenylphosphonium bromide of arenetricarbonylchro-
mium and ferrocene with binaphthylaldehydes afforded com-
plexes with a double bond as spacer. X-ray analyses of two
chromium complexes with a double and a triple bond as spacers
were also presented, showing clearly the conformations of the
tricarbonyl tripods with respect to the aromatic rings.
Experimental Section
1
F ) 80 °C. H NMR (200 MHz, CDCl3): 2.25 (s, 3H, H7), 3.00
General Procedures. All reactions and manipulations were
routinely performed under a dry nitrogen atmosphere using Schlenk
tube techniques. THF and diethyl ether were dried over sodium
benzophenone ketyl and distilled. CH2Cl2 was dried over calcium
hydride and distilled. Infrared spectra were measured on a Perkin-
Elmer 1420 spectrometer. 1H, 31P{1H}, and 13C{1H} NMR spectra
were obtained on a Bruker AC200, ARX400, or DRX500 spec-
trometer. Elemental analyses were performed by Le Service de
Microanalyses de l’Universite´ Pierre et Marie Curie.
Synthesis of 2,2′-Dimethoxy-3-η6-(phenyltricarbonylchromium)-
1,1′-binaphthyl (3e). 2,2′-Dimethoxy-1,1′-binaphthyl-3,3′-boronic
acid, 3g (0.2 g; 0.50 mmol), chlorobenzene tricarbonylechromium
(0.273 g; 1.1 mmol), K2CO3 (0.207 g; 1.5 mmol), and Pd(PPh3)4
(0.029 g; 0.025 mmol) in 15 mL of acetone were introduced in a
flask under N2. The reaction mixture was heated for 21 h under
reflux and filtered on Celite. After evaporation of the solvents, the
crude mixture was purified by silica gel 15-40 µm chromatography
column (petroleum ether/Et2O: 6/4, 300 mL then PE/Et2O: 4/6).
Complex 3e (0.105 g) was obtained as an orange solid in 28% yield.
1H NMR (200 MHz, CDCl3): 3.18 (s, 6H, H15), 5.60 (m, 4H, H10,
H14), 6.01 (m, 6H, H11, H12, H13), 7.27-7.41-7.75-7.99 (m, 8H, H5,
H6, H7, H8), 8.11 (s, 2H, H4). IR (neat, cm-1): 1863, 1956 (CO).
Anal. Calcd for C40H26Cr2O8: C, 65.04; H, 3.55. Found: C, 65.21;
H, 3.61. MS (FAB m/z): calcd, 738.0; found, 738.0 (M+).
Synthesis of o-Ethynyltoluene Tricarbonylchromium (6e). In
a flask, 2-chlorotoluenetricarbonylchromium (0.610 g, 2.32 mmol),
CuI (0.023 g, 0.012 mmol), and PdCl2(PPh3)2 (0.085 g, 0.012 mmol)
were dissolved in 20 mL of THF and 10 mL of Et3N. At room
temperature, ethynyltrimethylsilane (0.50 mL, 3.52 mmol) in 10
mL of THF was slowly added. The resulting mixture was then
refluxed for 6 h. After being cooled, the dark solution was filtered
through Celite, and the solvents were evaporated under reduced
pressure. The orange oil was purified by a silica gel chromatography
column (15-40 µm, eluant EP/Et2O: 96/4). The silylated complex
6e, R:CC-SiMe3, was obtained as an orange solid in 99% yield
(0.745 g). 1H NMR (200 MHz, CDCl3): 0.16 (s, 9H, H10), 2.22 (s,
(s, 1H, H9), 5.05 (dd, J ) 6.0 Hz, J ) 0.9 Hz, 1H, H6), 5.10 (t, J
) 6.0 Hz, 1H, H5), 5.30 (td, J ) 6.0 Hz, J ) 0.9 Hz, 1H, H4), 5.55
(dd, J ) 6.0 Hz, J ) 0.9 Hz, 1H, H3). 13C NMR (50 MHz,
CDCl3): 19.8 (C7), 78.6 (C9), 80.1 (C1), 87.9 (C8), 88.7-91.7-93.0-
96.9 (C3, C4, C5, C6), 111.1 (C2), 232.1 (CO). Anal. Calcd for C12H8-
CrO3: C, 57.15; H, 3.20. Found: C, 57.01; H, 3.02.
Synthesis of m-Ethynyltoluene Tricarbonylchromium (6f).
The same methodology as 6e was used to obtained complex 6f.
Silylated-6f (86%), 1H NMR (200 MHz, CDCl3): 0.21 (s, 9H, H10),
2.12 (s, 3H, H7), 5.03 (d, J ) 6.8 Hz, 1H, H4), 5.23 (d, J ) 6.8 Hz,
1H, H6), 5.25 (s, 1H, H2), 5.37 (t, J ) 6.8 Hz, 1H, H5). 13C NMR
(50 MHz, CDCl3): 0.0 (C10), 20.6 (C7), 90.6 (C8), 91.9 (C6), 93.0
(C2), 94.9-96.5 (C4-C5), 98.4 (C9), 100.6 (C1), 111.6 (C3), 232.6
(CO). Anal. Calcd for C15H16CrO3Si: C, 55.55; H, 4.98. Found:
1
C, 55.67; H, 5.14. 6f (99%): F ) 90 °C. H NMR (200 MHz,
CDCl3): 2.12 (s, 3H, H7), 2.89 (s, 1H, H9), 5.02 (d, J ) 6.2 Hz,
1H, H6), 5.22 (d, J ) 6.2 Hz, 1H, H4), 5.23 (s, 1H, H2), 5.32 (t, J
) 6.2 Hz, 1H, H5). 13C NMR (50 MHz, CDCl3): 20.6 (C7), 77.8
(C1), 79.7 (C9), 89.9 (C8), 91.1 (C2), 92.3 (C5), 92.6-95.2 (C4-C6),
107.9 (C3), 232.3 (CO). IR (neat): 1870, 1957 (CO), 2165 (C8C9).
Anal. Calcd for C12H8CrO3: C, 57.15; H, 3.20. Found: C, 57.06;
H, 3.03.
Synthesis of 6,6′-Di(phenyltricarbonylchromium)-2,2′-di-
methoxy-1,1′-binaphthyl (7a). In a 50 mL two-necked flask,
compound 5g (0.201 g, 0.5 mmol), chlorobenzene tricarbonylchro-
mium (0.264 g, 1.1 mmol), Pd(PPh3)4 (0.030 g, 0.025 mmol), and
Na2CO3 (0.212 g, 2.0 mmol) were placed in 10 mL of methanol
and 1.0 mL of water. The solution was heated to reflux. After 0.5
h, the mixture was cooled to room temperature, and the solvents
were evaporated under reduced pressure. The residue was dissolved
in 10 mL of CH2Cl2 and dried over anhydrous MgSO4, then filtered
through Celite, and the solvent was evaporated under reduced
pressure. Compound 7a was obtained as a yellow solid in 71%
yield (262 mg). Fdec ) 197 °C. 1H NMR (200 MHz, CDCl3): 3.79
(s, 6H, OMe), 5.34 (t, J ) 6 Hz, 2H, H14), 5.49 (t, J ) 6 Hz, 4H,

6146 Organometallics, Vol. 26, No. 25, 2007
Germaneau et al.
H13 and H15), 5.77 (d, J ) 6 Hz, 4H, H12 and H16), 7.13 (d, J ) 9
Hz, 2H, H9), 7.32 (d, J ) 9 Hz, 2H, H8), 7.49 (d, J ) 9 Hz, 2H,
H3), 8.01 (s, 2H, H6), 8.02 (d, J ) 9 Hz, 2H, H4). 13C NMR (100
MHz, CDCl3): 56.7 (OMe), 91.5 (C14), 92.2 (C12, C16), 92.3 (C11),
92.5 (C13, C15), 114.7 (C3), 125.2 (C9), 125.9 (C8), 126.4 (C4), 130.0
(C6), 155.8 (C2), 232.8 (CO), 118.9, 128.7, 131.3, 133.9 (C1, C5,
C7, C10). IR (neat, cm-1): 1952, 1847 (CO). UV-vis (CH3CN) λ
786.1). Anal. Calcd for C44H26Cr2O8: C, 67.17; H, 3.33. Found:
C, 67.31; H, 3.55.
Synthesis of 2,2′-Dimethoxy-3,3′-di(o-tolylethynyltricarbonyl-
chromium)-1,1′-binaphthyl (8b). The same methodology as the
one for 8a was used. Compound 8b was obtained as an orange
1
solid in 60% yield. F ) 138 °C. H NMR (200 MHz, CDCl3):
2.46 (s, 3H, H20), 3.66 (s, 6H, H19), 5.18 (t, J ) 6.3 Hz, 2H, H15),
5.23 (m, 2H, H16), 5.41 (m, 2H, H14), 5.77 (m, 2H, H13), 7.12 (d,
J ) 8.0 Hz, 2H, H9), 7.29 (t, J ) 8.0 Hz, 2H, H8), 7.43 (t, J ) 8.0
Hz, 2H, H7), 7.88 (d, J ) 8.0 Hz, 2H, H6), 8.22 (s, 2H, H4). 13C
NMR (50 MHz, C6D6): 19.8 (C20), 61.3 (C19), 88.7 (C16), 89.5-
89.2 (C11-C17-C18), 91.8 (C13), 92.8 (C15), 95.1 (C12, C14), 116.8
(C1), 125.7 (C3), 125.8-126.1 (C7,C9), 128.2 (C6, C8), 130.6 (C10),
134.7 (C5), 135.1 (C4), 156.3 (C2), 232.0 (CO). IR (neat): 1880,
1960 (CO); 2210 (C17-C18). MS (FAB, m/z): calcd 814.2 (found:
814.1). UV-vis (CH3CN) λ ) 273 nm, ꢀ ) 77 100; (CH2Cl2) λ )
280 nm, ꢀ ) 77 220, λ ) 309 nm, ꢀ ) 47 500, λ ) 327 nm, ꢀ )
45 210 L mol-1 cm-1. Anal. Calcd for C46H30Cr2O8: C, 67.81; H,
3.71. Found: C, 67.59; H, 3.53.
) 271 nm, ꢀ ) 64 200, λ ) 321 nm, ꢀ ) 28 600 L mol-1 cm-1
;
(CH2Cl2) λ ) 276 nm, ꢀ ) 79 400 L mol-1 cm-1. Anal. Calcd for
C40H26Cr2O8: C, 65.04; H, 3.55. Found: C, 65.01; H, 3.61.
Synthesis of 6,6′-Di(2-methylphenyltricarbonylchromium)-
2,2′-dimethoxy-1,1′-binaphthyl (7b). Compound 7b was synthe-
sized using the same methodology as 7a starting from 2-chloro-
toluene tricarbonylchromium (0.288 g, 1.1 mmol). It was obtained
as a yellow solid in 74% yield (284 mg). Fdec ) 159 °C. 1H NMR
(200 MHz, CDCl3): 2.16 (s, 6H, H17), 3.81 (s, 6H, OMe), 5.18
(m, 4H, H13 and H15), 5.50 (t, J ) 6 Hz, 2H, H14), 5.62 (d, J ) 6
Hz, 2H, H16), 7.12 (d, J ) 9 Hz, 2H, H9), 7.23 (d, J ) 9 Hz, 2H,
H8), 7.51 (d, J ) 9 Hz, 2H, H3), 7.88 (s, 2H, H6), 8.02 (d, J ) 9
Hz, 2H, H4). 13C NMR (100 MHz, CDCl3): 20.0 (C17), 56.7 (OMe),
88.3 (C15), 91.7 (C12), 114.7 (C3), 125.2 (C9), 125.4 (C8), 129.6
(C4), 129.8 (C6), 155.6 (C2), 233.3 (CO), 110.0, 113.0 (C11, C13),
119.0, 128.5, 131.5, 133.4 (C1, C5, C7, C10). IR (neat, cm-1): 1952,
1859 (CO). UV-vis (CH3CN) λ ) 271 nm, ꢀ ) 42 400, λ ) 321
nm, ꢀ ) 21 250 L mol-1 cm-1; (CH2Cl2) λ ) 275 nm, ꢀ ) 79 000
L mol-1 cm-1. Anal. Calcd for C42H30Cr2O8: C, 65.80; H, 3.94.
Found: C, 66.01; H, 4.07.
Synthesis of 2,2′-Dimethoxy-3,3′-di(m-tolylethynyltricarbonyl-
chromium)-1,1′-binaphthyl (8c). The same methodology as the
one for 8a was used. Compound 8c was obtained as an orange
1
solid in 90% yield. F ) 146 °C. H NMR (200 MHz, CDCl3):
2.16 (s, 3H, H20), 3.65 (s, 6H, H19), 5.05 (m, 2H, H12), 5.36 (m,
6H, H14, H15, H16), 7.03 (d, J ) 8.0 Hz, 2H, H9), 7.21 (t, J ) 8.0
Hz, 2H, H8), 7.35 (t, J ) 8.0 Hz, 2H, H7), 7.79 (d, J ) 8.0 Hz, 2H,
H6), 8.13 (s, 2H, H4). 13C NMR (50 MHz, C6D6): 20.1 (C20), 61.4
(C19), 87.5-90.2 (C17-C18), 90.8 (C12), 91.8 (C13), 91.9 (C16), 92.8
(C14), 94.9 (C15), 108.1 (C11), 116.6 (C1), 125.7 (C3), 125.8-126.1
(C7,C9), 128.1 (C6 et C8), 130.7 (C10), 134.8 (C5), 135.5 (C4), 156.4
(C2), 232.2 (CO). IR (neat): 1879, 1960 (CO); 2218 (C17-C18).
UV-visible (CH3CN) λ 274 (ꢀ ) 47 600 L mol-1 cm-1); λ 307 (ꢀ
) 43 100 L mol-1 cm-1); λ 322 (ꢀ ) 36 900 L mol-1 cm-1); (CH2-
Cl2) λ 279 (ꢀ ) 67 100 L mol-1 cm-1); λ 307 (ꢀ ) 40 400 L mol-1
cm-1); λ 325 (ꢀ ) 38 200 L mol-1 cm-1). MS (FAB, m/z): calcd
814.2 (found: 814.2). Anal. Calcd for C46H30Cr2O8: C, 67.81; H,
3.71. Found: C, 67.65; H, 3.58.
Synthesis of 6,6′-Di(3-methylphenyltricarbonylchromium)-
2,2′-dimethoxy-1,1′-binaphthyl (7c). Compound 7c was synthe-
sized using the same methodology as 7a starting from 3-chloro-
toluene tricarbonylchromium (0.288 g, 1.1 mmol). It was obtained
as a yellow solid in 72% yield (276 mg). Fdec ) 167 °C. 1H NMR
(200 MHz, CDCl3): 2.29 (s, 6H, H17), 3.79 (s, 6H, OMe), 5.17 (d,
J ) 3 Hz, 2H, H12), 5.58 (m, 6H, H14, H15, H16), 7.13 (d, J ) 9 Hz,
2H, H9), 7.33 (d, J ) 9 Hz, 2H, H8), 7.49 (d, J ) 9 Hz, 2H, H3),
8.01 (s, 2H, H6), 8.02 (d, J ) 9 Hz, 2H, H4). 13C NMR (100 MHz,
CDCl3): 20.9 (C17), 56.7 (OMe), 89.3 (C16), 91.4 (C12), 92.7 (C15),
94.1 (C14), 114.7 (C3), 125.3 (C9), 125.8 (C8), 126.6 (C4), 130.0
(C6), 155.7 (C2), 233.3 (CO), 109.2, 112.1 (C11, C13), 118.9, 128.6,
131.4, 133.9 (C1, C5, C7, C10). IR (neat, cm-1): 1951, 1860 (CO).
UV-vis (CH3CN) λ ) 273 nm, ꢀ ) 60 000, λ ) 321 nm, ꢀ )
29 400 L mol-1 cm-1; (CH2Cl2) λ ) 274 nm, ꢀ ) 73 700 L mol-1
cm-1. Anal. Calcd for C42H30Cr2O8: C, 65.80; H, 3.94. Found: C,
65.91; H, 4.01.
Synthesis of 2,2′-Dimethoxymethyl-3,3′-di(phenylethynyltri-
carbonylchromium)-1,1′-binaphthyl (8d). 8d was obtained as a
red solid in 80% yield, using the same methodology as the one
used for 8a. F ) 86 °C. 1H NMR (200 MHz, CDCl3): 3.65 (s, 6H,
H20), 4.91 (d, J ) 6.0 Hz, 2H, H19), 5.11 (d, J ) 6.0 Hz, 2H, H19),
5.32 (m, 6H, H13, H14, H15), 5.56 (m, 4H, H12, H16), 7.20 (d, J )
7.0 Hz, 2H, H9), 7.32 (td, J ) 7.0 Hz, J ) 1.3 Hz, 2H, H8), 7.42
(td, J ) 7.0 Hz, J ) 1.3 Hz, 2H, H7), 7.86 (d, J ) 7.0 Hz, 2H, H6),
8.21 (s, 2H, H4). 13C NMR (50 MHz, CDCl3): 56.1 (C20), 86.6-
89.4-89.8 (C11-C17-C18), 91.1 (C14), 91.2 (C12, C16), 95.0 (C13, C15),
115.8 (C1), 124.8 (C3), 125.7-126.5 (C7, C9), 127.7 (C6, C8), 130.1
(C10), 134.0 (C5), 135.0 (C4), 152.9 (C2), 232.0 (CO). IR (neat):
1880, 1962 (CO); 2360 (C17-C18). UV-visible (CH2Cl2) λ 277 (ꢀ
) 43 120 L mol-1 cm-1); λ 306 (ꢀ ) 34 130 L mol-1 cm-1); λ
410 (ꢀ ) 6614 L mol-1 cm-1); (CH3CN) λ 275 (ꢀ ) 47 830 L
mol-1 cm-1); λ 304 (shoulder); λ 410 (ꢀ ) 7491 L mol-1 cm-1).
MS (FAB, m/z): calcd 846.1 (found: 846.2). Anal. Calcd for
C46H30Cr2O10: C, 65.24; H, 3.57. Found: C, 65.37; H, 3.71.
Synthesis of 2,2′-Dimethoxy-3,3′-di(phenylethynyltricarbonyl-
chromium)-1,1′-binaphthyl (8a). In a flask, compound 3h (0.283
g, 0.50 mmol) and complex 6d2c,d (0.262 g, 1.1 mmol), Pd2dba3
(0.023 g, 0.025 mmol), and AsPh3 (0.023 g, 0.075 mmol) were
dissolved in 15 mL of Et3N distilled and kept over KOH. The
mixture was heated at 40 °C for 6 h. The dark solution was then
filtered trough Celite at room temperature, and the solvent was
evaporated under reduced pressure. Compound 8a was purified by
silica gel chromatography column (15-40 µm, eluant EP/Et2O: 6/4,
300 mL and then 4/6) and obtained as an orange solid in 74% yield
(0.291 g). F ) 210 °C. 1H NMR (200 MHz, CDCl3): 3.65 (s, 6H,
H19), 5.34 (m, 6H, H13, H14, H15), 5.60 (m, 4H, H12, H16), 7.10 (d,
J ) 8.0 Hz, 2H, H9), 7.28 (td, 3J ) 8.0 Hz, 4J ) 1.3 Hz, 2H, H8),
7.42 (td, 3J ) 8.0 Hz, 4J ) 1.3 Hz, 2H, H7), 7.86 (d, 3J ) 8.0 Hz,
2H, H6), 8.20 (s, 2H, H4). 13C NMR (50 MHz, CDCl3): 61.4 (C19),
86.6-89.5-90.1 (C11-C17-C18), 91.1 (C14), 91.3 (C12, C16), 95.1 (C13,
C15), 115.9 (C1), 124.8 (C3), 125.5 (C7, C9), 127.7-127.9 (C6, C8),
130.0 (C10), 134.0 (C5), 134.9 (C4), 155.5 (C2), 232.1 (CO). IR
(neat): 1889, 1966 (CO); 2364 (C17-C18). UV-visible (CH2Cl2)
λ 279 (ꢀ ) 58 930 L mol-1 cm-1); λ 305 (ꢀ ) 41 300 L mol-1
cm-1); λ 409 (ꢀ ) 4970 L mol-1 cm-1); (CH3CN) λ 274 (ꢀ )
44 100 L mol-1 cm-1); λ 302 (ꢀ ) 34 100 L mol-1 cm-1); λ 406
(ꢀ ) 7445 L mol-1 cm-1). MS (FAB, m/z): calcd 786.0 (found:
Synthesis of 2,2′-Dimethoxy-3,3′-di(ferrocenylethynyl)-1,1′-
binaphthyl (10). The same methodology as the one for 8a was
used. Ethynylferrocene 9 (0.231 g, 1.1 mmol) was used instead of
the complex 6d. Compound 10 was obtained as an orange solid in
1
80% yield. H NMR (200 MHz, CDCl3): 3.72 (s, 6H, H19), 4.25
(m, 14H, H13, H14, H16), 4.54 (m, 4H, H12, H15), 7.11 (d, J ) 7.5
Hz, 2H, H9), 7.25 (t, J ) 7.5 Hz, 2H, H8), 7.39 (t, J ) 7.5 Hz, 2H,
H7), 7.84 (d, J ) 7.6 Hz, 2H, H6), 8.16 (s, 2H, H4). 13C NMR (50
MHz, CDCl3): 61.0 (C19), 65.3 (C11), 68.9 (C12, C15), 69.9 (C16),
71.4 (C13, C14), 82.6-92.9 (C17-C18), 117.9 (C1), 124.9 (C3), 125.2-
125.7 (C7-C9), 127.6-128.4 (C6-C7), 130.0 (C10), 133.0 (C5), 133.5
(C4), 155.6 (C2). IR (neat): 2211 (C17-C18). UV-visible (CH2-

(η6-Arene)tricarbonylchromium and Ferrocene Complexes
Organometallics, Vol. 26, No. 25, 2007 6147
Cl2) λ 266 (ꢀ ) 55 908 L mol-1 cm-1); λ 290 (sh); λ 443 (ꢀ )
1273 L mol-1 cm-1); (CH3CN) λ 269 (ꢀ ) 47 509 L mol-1 cm-1);
λ 285 (sh); λ 446 (ꢀ ) 1156 L mol-1 cm-1). MS (FAB, m/z): calcd
730.1 (found: 730.2). Anal. Calcd for C46H34Fe2O2: C, 75.60; H,
4.69. Found: C, 75.48; H, 4.52.
Synthesis of 6,6′-Di(ferrocenylethynyl)-2,2′-dimethoxy-1,1′-
binaphthyl (12). In a 50 mL two-necked flask, compound 5h (0.283
g, 0.5 mmol), ethynylferrocene, 9 (0.252 g, 1.2 mmol), PdCl2(PPh3)2
(0.018 g, 0.025 mmol), and CuI (0.005 g, 0.025 mmol) were placed
in 15 mL of THF and 15 mL of Et3N. The solution was then
refluxed. After 3 h, the mixture was cooled to room temperature
and filtered through Celite. The solvents were evaporated under
reduced pressure. The residue was washed with a solution of K2-
CO3 to eliminate triethylammonium salts, and compound 12 was
purified by crystallization in a hot mixture of CH2Cl2 and
cyclohexane. It was obtained as a brown solid in 69% yield (252
Synthesis of 6,6′-Di(phenylethynyltricarbonylchromium)-2,2′-
dimethoxy-1,1′-binaphthyl (11a). In a 50 mL two-necked flask,
compound 5h (0.283 g, 0.5 mmol), phenylacetylide tricarbonyl-
chromium, 6d (0.263 g, 1.1 mmol), PdCl2(PPh3)2 (0.018 g, 0.025
mmol), and CuI (0.005 g, 0.025 mmol) were placed in 10 mL of
THF and 10 mL of Et3N. The solution was then refluxed and
became red. After 3 h, the mixture was cooled to room temperature
and filtered through Celite. The solvents were evaporated under
reduced pressure. The residue was purified by silica gel chroma-
tography column (60 µm, eluent cyclohexane/CH2Cl2: from 100/0
to 50/50 by portions of 50 mL and increment of 5%) and obtained
as a yellow solid in 64% yield (289 mg). Fdec ) 193 °C. 1H NMR
(200 MHz, CDCl3): 3.77 (s, 6H, OMe), 5.25 (t, J ) 6 Hz, 2H,
H16), 5.36 (t, J ) 6 Hz, 4H, H15 and H17), 5.53 (d, J ) 6 Hz, 4H,
H14 and H18), 7.02 (d, J ) 9 Hz, 2H, H9), 7.26 (d, J ) 9 Hz, 2H,
H8), 7.46 (d, J ) 9 Hz, 2H, H3), 7.95 (d, J ) 9 Hz, 2H, H4), 8.06
(d, J ) 2 Hz, 2H, H6). 13C NMR (100 MHz, CDCl3): 56.6 (OMe),
84.9 (C13), 90.4 (C12, C16), 91.0 (C11), 91.7 (C15, C17), 94.7 (C14,
C18), 114.4 (C3), 125.2 (C9), 128.4 (C8), 128.7 (C4), 129.7 (C6),
155.9 (C2), 232.2 (CO), 114.4, 118.8, 128.3, 133.6 (C1, C5, C7,
C10). IR (neat, cm-1): 1873, 1964, (CO). UV-visible (CH2Cl2) λ
285 (ꢀ ) 86 450 L mol-1 cm-1); λ 341 (ꢀ ) 37 100 L mol-1 cm-1);
(CH3CN) λ 281 (ꢀ ) 76 900 L mol-1 cm-1); λ 319 (ꢀ ) 48 300 L
mol-1 cm-1). MS (FAB, m/z): calcd 786.0 (found: 786.1). Anal.
Calcd for C44H26Cr2O8: C, 67.17; H, 3.33. Found: C, 67.41; H,
3.59.
1
mg). Fdec ) 161 °C. H NMR (200 MHz, CDCl3): 3.77 (s, 6H,
OMe), 4.23 (m, 14H, H18, H15, H16), 4.51 (m, 4H, H14, H17), 7.03
(d, J ) 9 Hz, 2H, H9), 7.26 (d, J ) 9 Hz, 2H, H8), 7.45 (d, J ) 9
Hz, 2H, H3), 7.93 (d, J ) 9 Hz, 2H, H4), 8.02 (d, J ) 2 Hz, 2H,
H6). 13C NMR (100 MHz, CDCl3): 56.7 (OMe), 65.5 (C13), 68.7
(C15, C16), 69.9 (C18), 71.3 (C14, C17), 86.2, 88.0 (C11, C12), 114.5
(C3), 125.1 (C9), 128.9 (C8), 129.3 (C4), 131.0 (C6), 155.4 (C2). IR
(neat, cm-1): 2208 (C11C12). UV-visible (CH2Cl2) λ 273 (ꢀ )
71 900 L mol-1 cm-1); λ 321 (ꢀ ) 44 300 L mol-1 cm-1); (CH3-
CN) λ 271 (ꢀ ) 75 700 L mol-1 cm-1); λ 321 (ꢀ ) 36 500 L mol-1
cm-1). Anal. Calcd for C46H34Fe2O2: C, 75.64; H, 4.69. Found:
C, 75.36; H, 4.47.
Synthesis of η6-(Benzyltricarbonylchromium)triphenyl-
phosphonium Bromide (13). In a flask equipped with a Dean-
Stark apparatus, tricarbonylchromiumbenzylalcohol (0.448 g, 2.0
mmol) and triphenylphosphonium hydrobromide (0.618 g, 1.8
mmol) were dissolved in CH2Cl2 (30 mL) under N2. The solution
was refluxed for 2 h and heated until dryness over 30 min. The
resulting solid was dissolved in CH2Cl2 (15 mL) and precipitated
by adding dry diethyl ether (10 mL per amount until persistence
of the yellow precipitate). After decanting, the liquid layer was
removed with a syringe and the solid was washed twice with 10
mL of dry diethyl ether. After being dried under reduced pressure,
compound 13 was obtained as a yellow solid in 68% yield (0.696
Synthesis of 6,6′-Di(2-methylphenylethynyltricarbonyl-
chromium)-2,2′-dimethoxy-1,1′-binaphthyl (11b). Compound 11b
was synthesized using the same methodology as 11a and compound
6e (0.278 g, 1.1 mmol). It was obtained as a yellow solid in 43%
yield (175 mg). Fdec ) 148 °C. 1H NMR (200 MHz, CDCl3): 2.40
(s, 6H, H19), 3.78 (s, 6H, OMe), 5.19 (t, J ) 6 Hz, 2H, H15), 5.23
(d, J ) 6 Hz, 2H, H16), 5.35 (t, J ) 6 Hz, 2H, H14), 5.70 (d, J )
6 Hz, 2H, H13), 7.03 (d, J ) 9 Hz, 2H, H9), 7.26 (d, J ) 9 Hz, 2H,
H8), 7.47 (d, J ) 9 Hz, 2H, H3), 7.96 (d, J ) 9 Hz, 2H, H4), 8.06
(d, J ) 2 Hz, 2H, H6). 13C NMR (100 MHz, CDCl3): 26.9 (C19),
56.6 (OMe), 85.0, 90.4, 90.5, 91.1, 91.7, 94.7 (C13-C18), 114.6 (C3),
125.3 (C9), 128.8 (C8), 129.7 (C4), 132.4 (C6), 156.0 (C2), 232.2
(CO), 116.6, 119.0, 128.5, 133.7 (C1, C5, C7, C10). IR (neat, cm-1):
1871, 1957 (CO), 2202 (C11C12). UV-visible (CH2Cl2) λ 276 (ꢀ
) 115 000 L mol-1 cm-1); λ 321 (ꢀ ) 48 200 L mol-1 cm-1);
(CH3CN) λ 277 (ꢀ ) 90 100 L mol-1 cm-1); λ 319 (ꢀ ) 48 900 L
mol-1 cm-1). Anal. Calcd for C46H30Cr2O8: C, 67.81; H, 3.71.
Found: C, 67.52; H, 3.44.
1
g). H NMR (400 MHz, CDCl3): 5.03 (d, J ) 13 Hz, 2H, CH2),
5.18 (s large, 3H, ArCr), 5.38 (s arge, 2H, ArCr), 7.71-7.83 (m,
15H, Ph). 13C NMR (100 MHz, CDCl3): 59.4 (CH2), 90.8 (Cpara
-
ArCr), 91.5 (CorthoArCr), 93.2 (Cme´taArCr), 97.8 (CipsoArCr), 115.6
(d, J ) 85 Hz, CipsoPh), 129.6 (d, J ) 13 Hz, CmetaPh), 133.5 (d,
J ) 10 Hz, CparaPh), 134.7 (d, J ) 2.6 Hz, CparaPh), 230.8 (CO).
31P NMR (160 MHz, CDCl3): 24.1. IR (neat): 1858, 1885, 1955
(CO). MS (MALDI-TOF, m/z): calcd for C28H22CrO3P+, 489;
found, 489 (C+), 1058 (M + 1 + C+). Anal. Calcd for C28H22-
CrO3PBr: C, 59.16; H, 3.90. Found: C, 59.01; H, 3.79.
Synthesis of 2,2′-Dimethoxy-3,3′-η6-(ethenylphenyltricarbonyl-
chromium)-1,1′-binaphthyl (14). 3,3′-Diformyl-2,2′-dimethoxy-
1,1′-binaphthyl7a (0.129 g, 0.35 mmol) in THF (20 mL) and t-BuOK
(0.77 mL, 0.77 mmol) were introduced into a flask under N2 and
stirred at room temperature for 1 h. Next, the phosphonium 13 (0.40
g, 0.77 mml) was added, and the orange solution was heated for 4
h under reflux. At room temperature, NH4Cl (20 mL) and 10 mL
of Et2O were added. The aqueous phase was extracted by Et2O (3
× 40 mL). The organic phase was dried over MgSO4 and filtered
on Celite. The solvent was removed under reduced pressure. The
crude product was purified on a silica gel chromatography column
(Merck silica gel 60, 15-40 µm, petroleum ether/AcOEt 8/2). After
evaporation under reduced pressure and drying in vacuo, three
complexes were obtained: the dinuclear complex 14, 0.122 g, in
44% yield, the mononuclear complex 15, 0.067 g, in 33% yield.
The third one recovered in 13% yield corresponded to the
decoordination of one of the Cr(CO)3 entities of 14.
Synthesis of 6,6′-Di(3-methylphenylethynyltricarbonyl-
chromium)-2,2′-dimethoxy-1,1′-binaphthyl (11c). Compound 11c
was synthesized using the same methodology as the one for 11a
starting from compound 6f (0.278 g, 1.1 mmol). It was obtained
as a yellow solid in 57% yield (232 mg). Fdec ) 117 °C. 1H NMR
(200 MHz, CDCl3): 2.22 (s, 6H, H19), 3.77 (s, 6H, OMe), 5.06
(d, J ) 6 Hz, 2H, H16), 5.38 (m, 6H, H14, H17, H18), 7.03 (d, J )
9 Hz, 2H, H9), 7.26 (d, J ) 9 Hz, 2H, H8), 7.46 (d, J ) 9 Hz, 2H,
H3), 7.95 (d, J ) 9 Hz, 2H, H4), 8.00 (d, J ) 2 Hz, 2H, H6). 13C
NMR (100 MHz, CDCl3): 20.7 (C19), 56.6 (OMe), 77.3 (C11), 85.1
(C12), 90.6 (C16), 91.9 (C17), 92.5 (C13), 93.1 (C18), 94.9 (C14), 108.3
(C15), 114.5 (C3), 125.2 (C9), 128.4 (C8), 128.8 (C4), 129.7 (C6),
155.9 (C2), 232.8 (CO), 116.5, 118.9, 128.5, 133.7 (C1, C5, C7,
C10). IR (neat, cm-1): 1871, 1957 (CO), 2213 (C11C12). UV-visible
(CH2Cl2) λ 280 (ꢀ ) 115 100 L mol-1 cm-1); (CH3CN) λ 277 (ꢀ
) 90 100 L mol-1 cm-1); λ 319 (ꢀ ) 48 900 L mol-1 cm-1). Anal.
Calcd for C46H30Cr2O8: C, 67.81; H, 3.71. Found: C, 67.62; H,
3.49.
1
Complex 14. H NMR (200 MHz, CDCl3): δ ) 7.97 (s, 2H,
H4), 7.81 (d, J ) 7.5, 2H, H6), 7.44 (m, 2H, H8), 7.35 (m, 2H, H7),
7.21 (d, J ) 8.3, 2H, H9), 7.03 (d, J ) 12, 2H, H17), 6.33 (d, J )
12, 2H, H18), 5.47-5.28 (m, 10H, ArCr), 3.50 (s, 6H, OCH3). 13
C
NMR (100 MHz, CDCl3): δ ) 232.8 (CO-Cr), 154.3 (C2), 133.8,

6148 Organometallics, Vol. 26, No. 25, 2007
Germaneau et al.
130.3, 129.5, 125.3 (C1, C3, C5, C10), 130.1 (C4), 128.9 (C12), 128.1
(C6), 127.8 (C13), 126.8 (C7), 125.5 (C9), 125.2 (C8), 105.4 (C14),
J ) 9.0 Hz, 1H, H3′), 7.78 (d, J ) 8.0 Hz, 1H, H6′), 7.92 (s, 1H,
H4), 7.93 (d, J ) 8.8 Hz, 1H, H6), 8.02 (d, J ) 8.8 Hz, 1H, H4′).
13C NMR (100 MHz, CDCl3): 54.9 (C20′), 55.7 (C20), 90.4 (C14),
91.3 (C13), 92.3 (C11), 92.5 (C12), 94.0 (C19′), 98.2 (C19), 115.6 (C3′),
123.2-124.2-124.5-124.9-125.3-126.5 (C7, C8, C9, C7′, C8′, C9′),
119.3 (C3), 125.6-129.0-129.5-132.7-132.8 (C1, C5, C10, C1′, C5′,
C10′), 125.7 (C17 or C18), 126.9 (C6, C6′), 128.6 (C17 or C18), 129.0
(C4, C4′), 150.8 (C2), 151.8 (C2′), 233.3 (C21, C22, C23). IR (neat):
ν (cm-1) 1621 (CdC), 1880, 1962 (CO). UV-visible (CHCl3) λ
267 (ꢀ ) 22 867 L mol-1 cm-1), λ 330 (ꢀ ) 978 L mol-1 cm-1);
(CH2Cl2) λ 265 (ꢀ ) 32 533 L mol-1 cm-1); (CH3CN) λ 313 (ꢀ )
23 602 L mol-1 cm-1); λ 386 (ꢀ ) 4073 L mol-1 cm-1). Anal.
Calcd for C35H28CrO7: C, 68.61; H, 4.61. Found: C, 68.50; H,
4.49. MS (FAB m/z): calcd for C35H28CrO7, 612.1; found, 612.1
(M+).
Complex 17-E. 1H NMR (400 MHz, CDCl3): 2.83 (s, 3H, H20),
3.20 (s, 3H, H20′), 4.65 (d, J ) 5.6 Hz, 1H, H19), 4.71 (d, J ) 5.6
Hz, 1H, H19), 5.07 (d, J ) 6.9 Hz, 1H, H19′), 5.19 (d, J ) 6.9 Hz,
1H, H19′), 5.36 (t, J ) 6.2 Hz, 1H, H14), 5.50 (t, J ) 6.2 Hz, 2H,
H13), 5.67 (d, J ) 6.2 Hz, 2H, H12), 6.93 (d, J ) 16.2 Hz, 1H, H17
or H18), 7.19-7.49 (m, 6H, H7, H8, H9, H7′, H8′, H9′), 7.60 (d, J )
5.7 Hz, 1H, H3′), 7.92 (d, J ) 6.0 Hz, 1H, H6′), 7.93 (d, J ) 8.8
Hz, 1H, H6), 8.01 (d, J ) 5.7 Hz, 1H, H4′), 8.23 (s, 1H, H4). 13C
NMR (50 MHz, CDCl3): 55.0 (C20), 55.7 (C20′), 89.8 (C14), 90.3
(C13), 91.7 (C11), 94.0 (C12), 98.2 (C19′), 105.1 (C19), 115.6 (C3′),
123.2-123.4-124.4-124.9-125.7-126.8 (C7, C8, C9, C7′, C8′, C9′),
119.6 (C3), 125.6-128.9-130.4-132.9-136.7 (C1, C5, C10, C1′, C5′,
93.5, 93.2, 92.2, 92.0, 91.6 (ArCr), 61.3 (C11). IR (neat): ν (cm-1
)
1872, 1958 (CO-Cr). UV (CH3CN): λ 272 nm (ꢀ 86 100 L mol-1
cm-1). UV (CH2Cl2): λ 273 nm (ꢀ 139 600 L mol-1 cm-1). MS
(MALDI-TOF, m/z): calcd for C44H30Cr2O8, 790.1; found, 813.1
(M + Na+), 677.1 (M + Na+ - Cr(CO)3).
2-2′-Dimethoxy-3-η6-(ethenylphenyltricarbonylchromium)-3′-
1
formyl-1,1′-binaphthyl (15). H NMR (200 MHz, CDCl3): δ )
10.60 (s, 1H, CHO), 8.63 (s, 1H, H4′), 8.10 (d, J ) 8, 1H, H6′),
8.02 (s, 1H, H4), 7.83 (d, J ) 8, 1H, H6), 7.53-7.15 (m, 6H, H7,
H8, H9, H7′, H8′, H9′), 7.03 (d, J ) 12, 1H, H18), 6.35 (d, J ) 12,
1H, H17), 5.44-5.30 (m, 5H, ArCr), 3.53 (s, 3H, OCH3), 3.43 (s,
3H, OCH3′). 13C NMR (100 MHz, CDCl3): δ ) 232.7 (CO-Cr),
190.5 (CHO), 156.4, 154.5 (C2, C2′), 137.0, 133.7, 130.2, 129.9,
129.5, 128.4, 125.8, 124.4 (C1, C3, C5, C10, C1′, C3′, C5′, C10′, C14′),
131.8, 130.5, 130.4, 129.3, 128.8, 128.2, 127.9, 127.1, 125.9, 125.6,
125.4, 125.3 (C4, C6, C7, C8, C9, C12, C13, C4′, C6′, C7′, C8′, C9′),
105.3 (C14), 93.5, 93.1, 92.1, 91.9, 91.6 (ArCr), 63.0, 61.4 (C11,
C11′). IR (neat): ν (cm-1) 1689 (CHO), 1877, 1960 (CO-Cr). UV
(CH3CN): λ 271 nm (ꢀ 63 700 L mol-1 cm-1). UV (CH2Cl2): λ
274 nm (ꢀ 114 900 L mol-1 cm-1). MS (MALDI-TOF, m/z): calcd
for C34H24CrO6, 580.1; found, 603.1 (M + Na+), 467.1 (M + Na+
- Cr(CO)3).
2,2′-Dimethoxy-3-η6-(ethenylphenyltricarbonylchromium)-3′-
ethenylphenyl)-1,1′-binaphthyl (16). 1H NMR (200 MHz,
CDCl3): δ ) 7.95 (s, 1H, H4 or H4′), 7.91 (s, 1H, H4 or H4′), 7.80
(d, J) 7, 1H, H6 or H6′), 7.69 (d, J) 8, 1H, H6 or H6′), 7.50-7.20
(m, 11H, H7, H8, H9, H7′, H8′, H9′, Ph), 7.04 (d, J ) 12, 1H, H18),
6.95 (d, J ) 12, 1H, H18′), 6.80 (d, J ) 12, 1H, H17′), 6.33 (d, J )
12, 1H, H17), 5.50-5.20 (m, 5H, ArCr), 3.53 (s, 3H, OCH3), 3.50
(s, 3H, OCH3′). 13C NMR (100 MHz, CDCl3): δ ) 232.8 (CO-
Cr), 154.7, 154.5 (C2, C2′), 137.0, 136.9, 134.0, 133.6, 133.4, 131.0,
130.4, 130.2, 129.5 (C1, C3, C5, C10, C1′, C3′, C5′, C10′, C14′), 131.3,
131.1, 130.0, 129.9, 129.8, 129.1, 128.9, 128.3, 128.1, 128.0, 127.6,
127.3, 126.7, 126.3, 125.7, 125.1, 124.8 (C4, C6, C7, C8, C9, C12,
C13, C4′, C6′, C7′, C8′, C9′, C12′, C13′, Ph), 105.6 (C14), 93.5, 93.2,
C10′), 125.7 (C17 or C18), 126.7 (C6, C6′), 128.8 (C17 or C18), 129.5
(C4, C4′), 150.3 (C2), 151.9 (C2′), 231.9 (C21, C22, C23). IR (neat):
1652 CdC, 1887, 1962 (CO). UV-visible (CHCl3) λ 264 (ꢀ )
21 692 L mol-1 cm-1); (CH2Cl2) λ 290 (ꢀ ) 44 281 L mol-1 cm-1),
λ 427 (ꢀ ) 792 L mol-1 cm-1); (CH3CN) λ 266 (ꢀ ) 28 234 L
mol-1 cm-1), λ 309 (ꢀ ) 20 064 L mol-1 cm-1). Anal. Calcd for
C35H28CrO7: C, 68.61; H, 4.61. Found: C, 68.42; H, 4.43. MS
(FAB m/z): calcd for C35H28CrO7, 612.1; found, 612.1 (M+).
Synthesis of Ferrocenylmethanol.22 A solution of ferrocen-
ecarboxaldehyde (1.07 g, 5.0 mmol) in methanol (50 mL) was
cooled at 0 °C. NaBH4 (0.95 g, 25 mmol) dissolved in an aqueous
solution of sodium hydroxide (2 N) was then added via a canula,
and the resulting mixture was stirred and allowed to warm to room
temperature overnight. The methanol was evaporated with vigorous
stirring, and the resulting aqueous solution was extracted with
diethyl ether (3 × 30 mL). The organic layer was washed with
water (2 × 30 mL), dried over anhydrous MgSO4, filtered through
Celite, and evaporated under reduced pressure. The treatment led
to the ferrocenylmethanol in quantitative yield. 1H NMR (200 MHz,
CDCl3): 1.65 (t, J ) 6.1 Hz, 1H, OH), 4.24 (s, 7H, C5H5 and C5H4),
4.29 (m, 2H, C5H4), 4.37 (d, J ) 6.1 Hz, 2H, CH2). 13C NMR (50
MHz, CDCl3): 61.2 (C5H4), 68.4-68.9 (C5H4), 68.7 (C5H5), 88.7
(CH2).
Synthesis of (Ferrocenylmethyl)triphenylphosphonium Bro-
mide (18).22 Ferrocenylmethanol (0.432 g, 2.0 mmol) was dissolved
in CH2Cl2 (10 mL) with triphenylphosphonium hydrobromide,
PPh3‚HBr18b (0.618 g, 1.8 mmol), in the presence of activated
molecular sieve (4 Å). The solution was refluxed during 1 h. After
being cooled at room temperature, the mixture was filtered under
N2 and dry diethyl ether was added until persistence of a yellow
precipitate. After decanting, the liquid layer was removed with a
syringe, and the solid was washed twice with dry diethyl ether (10
mL). The (ferrocenylmethyl)triphenylphosphonium bromide, 18,
was obtained in 80% yield (0.779 g). For C29H26BrFeP M ) 541.
1H NMR (400 MHz, CDCl3): 3.94 (sb, 2H, C5H4), 4.02 (sb, 2H,
C5H4), 4.33 (s, 5H, C5H5), 5.05 (d, J ) 11.7 Hz, 2H, CH2), 7.60-
7.73 (m, 15H, C6H5). 13C NMR (100 MHz, CDCl3): 31.3 (d, J )
92.2, 92.0, 91.6 (ArCr), 61.2, 61.1 (C11, C11′). IR (neat): ν (cm-1
)
) 1888 (CO-Cr), 1964 (CO-Cr). MS (MALDI-TOF, m/z): calcd
for C41H30CrO5, 654.1; found, 677.3 (M + Na+), 541.2 (M + Na+
- Cr(CO)3).
Synthesis of 2,2′-Dimethoxymethyl-3-η6-(ethenylphenyltri-
carbonylchromium)-1,1′-binaphthyl (17). Under N2, compound
13 (0.152 g, 0.27 mmol) prepared in a way similar to that described
t
in the literature18b was dissolved in 15 mL of THF. BuOK (c )
1.0 mol L-1 in THF, 0.324 mL, 0.324 mmol) was slowly added,
and the mixture was stirred for 1 h at room temperature. Compound
2a was then added at once to the orange solution of ylide, and the
mixture was refluxed for 4 h. After being cooled at room
temperature, the solution was hydrolyzed with 20 mL of an aqueous
saturated ammonium chloride solution and extracted with dichlo-
romethane (2 × 20 mL). The joined organic layers were washed
with 20 mL of water, dried over anhydrous magnesium sulfate,
filtered through Celite, and the solvent was evaporated under
reduced pressure. The resulting yellow oil was purified by a silica
gel chromatography column (15-40 µm, eluent EP/ethyl acetate:
from 100/0 to 86/14 by portions of 50 mL and increment of 2%).
Two compounds were separated corresponding to 17-Z (66%, 0.109
g) and 17-E (15%, 0.025 g), respectively, as a yellow and an orange
solid.
Complex 17-Z. MS (FAB, m/z): calcd, 612.1; found, 612.1. 1H
NMR (200 MHz, CDCl3): 2.86 (s, 3H, H20), 3.22 (s, 3H, H20′),
4.66 (d, J ) 5.8 Hz, 1H, H19), 4.76 (d, J ) 5.8 Hz, 1H, H19), 5.09
(d, J ) 7.0 Hz, 1H, H19′), 5.18 (d, J ) 7.0 Hz, 1H, H19′), 5.28-
5.37 (m, 3H, H13, H14, H15), 5.47 (d, J ) 6.3 Hz, 2H, H12, H16),
6.36 (d, J ) 12.2 Hz, 1H, H17 or H18), 7.06 (d, J ) 12.2 Hz, 1H,
(22) (a) Kalita, D.; Morisue, M.; Kobuke, Y. New J. Chem. 2006, 30,
77. (b) Thomas, K. R. J.; Lin, J. T.; Wen, Y. S. J. Organomet. Chem. 1999,
575, 301.
H18 or H17), 7.21-7.45 (m, 6H, H7, H8, H9, H7′, H8′, H9′), 7.63 (d,

(η6-Arene)tricarbonylchromium and Ferrocene Complexes
Organometallics, Vol. 26, No. 25, 2007 6149
48 Hz, CH2), 69.2-71.0 (C5H4), 70.4 (C5H5), 70.9 (d, J ) 2 Hz,
C5H4), 118.5 (d, J ) 85 Hz, CPh-P+), 130.5 (d, J ) 12.0 Hz, CPh-
P+), 134.7 (d, J ) 10 Hz, CPh-P+), 135.3 (d, J ) 3.5 Hz, CPh-
P+). Anal. Calcd for C29H26PFeBr: C, 61.10; H, 5.60. Found: C,
61.18; H, 5.51. MS (MALDI-TOF, m/z): calcd for C+, 461; found,
461 C+ (M - Br), 1002 (M + 1 + C+).
H17 or H18), 6.62 (d, J ) 11.8 Hz, 1H, H18 or H17), 7.07-7.29 (m,
6H, H7, H8, H9, H7′, H8′, H9′), 7.50 (d, J ) 9.1 Hz, 1H, H3′), 7.69
(d, J ) 8.3 Hz, 1H, H6′), 7.78 (d, J ) 8.1 Hz, 1H, H6), 7.87 (d, J
) 9.1 Hz, 1H, H4′), 7.93 (s, 1H, H4). 13C NMR (50 MHz, CDCl3):
55.9 (C20), 56.2 (C20′), 69.3 (C16), 69.4-69.7 (C12-C15 and C13-C14),
95.1 (C19′), 98.8 (C19), 116.9 (C3′), 121.5-124.1-124.9-125.7-125.9-
129.5-130.7-131.3-131.1-132.1-133.0-133.3-134.1 -134.2 (C1, C3,
C5, C7, C8, C9, C10, C11, C1′, C5′, C7′, C8′, C9′, C10′), 123.5 (C17 or
C18), 127.8 (C6), 127.9 (C6′), 129.4 (C18 or C17), 129.6 (C4), 129.8
Synthesis of 2,2′-Dimethoxymethyl-3-ferrocenylethenyl-1,1′-
binaphthyl (19-E and -Z). (Ferrocenylmethyl) triphenylphospho-
nium bromide,18a 18 (0.171 g, 0.50 mmol), was dissolved under
N2 in THF (15 mL). The solution was cooled at 0 °C, and a solution
1
(C4′), 151.9 (C2), 152.9 (C2′). 19-E. H NMR (400 MHz, CDCl3):
t
of BuOK in THF (c ) 1.0 mol L-1, 0.60 mL, 0.60 mmol) was
2.68 (s, 3H, H20), 2.98 (s, 3H, H20′), 4.08 (m, 2H, H12 and H15 or
H13 and H14), 4.10 (s, 5H, H16), 4.10 (m, 2H, H12 and H15 or H13
and H14), 4.57 (d, J ) 5.7 Hz, 1H, H19), 4.62 (d, J ) 5.7 Hz, 1H,
H19), 4.93 (d, J ) 6.8 Hz, 1H, H19′), 5.07 (d, J ) 6.8 Hz, 1H, H19′),
7.05 (d, J ) 15.9 Hz, 1H, H17 or H18), 7.07-7.29 (m, 6H, H7, H8,
H9, H7′, H8′, H9′), 7.51 (d, J ) 9.1 Hz, 1H, H3′), 7.69 (d, J ) 8.3
Hz, 1H, H6′), 7.82 (d, J ) 8.1 Hz, 1H, H6), 7.88 (d, J ) 9.1 Hz,
1H, H4′), 8.08 (s, 1H, H4). 13C NMR (50 MHz, CDCl3): 55.9 (C20),
56.7 (C20′), 68.9 (C12-C15 and C13-C14), 69.3 (C16, C12-C15 and
slowly added. The mixture was stirred at 0 °C for 1 h. In another
flask, compound 2a (0.201 g, 0.50 mmol) was dissolved in THF
(10 mL). The suspension was cooled at -78 °C. The red solution
of ylide was then cooled at the same temperature, and the suspension
of 2a was added via a canula. The resulting mixture was stirred at
-40 °C. After 2 h, the solution was hydrolyzed with 20 mL of an
aqueous saturated ammonium chloride solution at room temperature
and extracted twice with 20 mL of dichloromethane. The joined
organic phases were washed with 20 mL of water, dried over
anhydrous magnesium sulfate, filtered through Celite, and the
solvents evaporated under reduced pressure. The residue was
purified by silica gel chromatography column (15-40 µm, eluent
EP/Et2O: from 100/0 to 90/10 by portions of 50 mL and increment
of 2%). A mixture of red complexes 19-Z and 19-E that could not
be separated by silica gel chromatography column was obtained in
C13-C14), 95.0 (C19′), 99.1 (C19), 116.8 (C3′), 121.5-124.1-124.9-
125.7-125.9-129.5-130.7-131.3-131.1-132.1-133.0-133.3-134.1-
134.2 (C1, C3, C5, C7, C8, C9, C10, C11, C1′, C5′, C7′, C8′, C9′, C10′),
121.3 (C17 or C18), 127.8 (C6), 127.9 (C6′), 128.9 (C17 or C18), 129.7
(C4, C4′), 151.1 (C2), 152.9 (C2′).
Acknowledgment. We thank Ce´line Chadefaux for partial
synthesis of complexes 14-16 and the CNRS for financial
support.
45% yield, 132 mg (Z/E: 3/1, NMR ratio). IR (neat): ν (cm-1
)
1624 (CdC: C17-C18). MS (FAB m/z): calcd for C36H32FeO4,
584.2; found, 584.2 (M+). Anal. Calcd for C36H32FeO4: C, 73.95;
H, 5.52. Found: C, 74.14; H, 5.61.
Supporting Information Available: Tables of crystal data,
atomic coordinates, and bond distances and angles for complexes
8a and 17Z. Crystallographic data as CIF files. This material is
available free of charge via the Internet at http://pubs.acs.org.
1
19-Z. H NMR (400 MHz, CDCl3): 2.53 (s, 3H, H20), 2.98 (s,
3H, H20′), 4.04 (s, 5H, Cp), 4.13 (m, 2H, H12 and H15 or H13 and
H14), 4.19 (m, 2H, H13 and H14 or H12 and H15), 4.65 (d, J ) 5.7
Hz, 1H, H19), 4.71 (d, J ) 5.7 Hz, 1H, H19), 4.94 (d, J ) 6.8 Hz,
1H, H19′), 5.07 (d, J ) 6.8 Hz, 1H, H19′), 6.40 (d, J ) 11.9 Hz, 1H,
OM700586Z