Synthesis and structure of (η5-cyclohexadienyl)Mn(CO) 3 and cationic (η6-arene)Mn(CO)3 complexes comprising a double bond conjugated to the π system

Article abstract of DOI:10.1021/om7010672

Addition of a Grignard reagent to keto-substituted (η⁵- cyclohexadienyl)Mn(CO)₃ complexes leads to the corresponding alcohols in very good yields. After acidic treatment, dehydration occurs, which gives rise to the formation of unprecedented (η⁵-cyclohexadienyl)Mn(CO) ₃ complexes substituted by a double bond conjugated to the π system as the major compounds, along with uncoordinated trienones due to the rearrangement of the intermediate carbocation. The structure of one of these η⁵ complexes has been determined by X-ray crystallography as well as one of the corresponding cationic (η⁶-arene)Mn(CO) ₃ complexes formed upon hydride abstraction.

Full text of DOI:10.1021/om7010672

784
Organometallics 2008, 27, 784–788
Synthesis and Structure of (η5-cyclohexadienyl)Mn(CO)3 and
Cationic (η6-arene)Mn(CO)3 Complexes Comprising a Double Bond
Conjugated to the π System
Derya Cetiner,† Jean-Philippe Tranchier,† Françoise Rose-Munch,*,† Eric Rose,*,† and
Patrick Herson‡
Laboratoire de Chimie Organique (UMR CNRS 7611), Case 181, and Laboratoire de Chimie Inorganique
et Matériaux Moléculaires (UMR CNRS 7071), Case 42, UniVersité Pierre et Marie Curie–Paris 6, Institut
de Chimie Moléculaire (FR 2769), 4 Place Jussieu, F-75252 Paris Cedex 05, France
ReceiVed October 24, 2007
Addition of a Grignard reagent to keto-substituted (η5-cyclohexadienyl)Mn(CO)3 complexes leads
to the corresponding alcohols in very good yields. After acidic treatment, dehydration occurs, which
gives rise to the formation of unprecedented (η5-cyclohexadienyl)Mn(CO)3 complexes substituted
by a double bond conjugated to the π system as the major compounds, along with uncoordinated
trienones due to the rearrangement of the intermediate carbocation. The structure of one of these η5
complexes has been determined by X-ray crystallography as well as one of the corresponding cationic
(η6-arene)Mn(CO)3 complexes formed upon hydride abstraction.
Scheme 1
Introduction
Cationic (η6-arene)tricarbonylmanganese complexes consti-
tute an important class of organometallic compounds1 due to
the very electrophilic character of the arene ring coordinated to
the Mn(CO)3 entity, leading to useful synthons in organometallic
and organic syntheses.2 Ipso chloride substitutions in cationic
(η6-chloroarene)Mn(CO)3 allow clean nucleophile introductions,
restricted to amino, oxo, and thio nucleophiles.1 However the
main reactions described are addition reactions affording stable
neutral (η5-cyclohexadienyl)Mn(CO)3 complexes.1,3 The η5
complexes have recently received much attention thanks to the
discovery of two new methodologies for their functionalization,
which broaden the scope of their applications. Indeed, it has
* Corresponding author. E-mail: rosemun@ccr.jussieu.fr; rose@
ccr.jussieu.fr.
† Laboratoire de Chimie Organique.
been reported first that very efficient lithiation/electrophilic
quench gives rise to the formation of the corresponding diversely
substituted η5 complexes4 (Scheme 1, step a; in this scheme
are reported the more recent developments of η5 complex
chemistry that do not affect their hapticity). Second, when they
bear a halogen substituent on the π system, they are easily
transformed, by palladium-catalyzed cross-coupling reactions,
into the corresponding compounds due to the ipso substitution
of the halogen5 (Scheme 1, step b) or into the keto derivatives
if the coupling is achieved under carbonylative conditions
(Scheme 1, step c).6 Very recently, these η5 keto complexes
have been shown to undergo hydride reduction into the
corresponding alcohol derivatives, with an unexpected addition
of the nucleophile to an internal carbon atom of the π system.7
Finally, when the η5 complexes are substituted by a good leaving
‡ Laboratoire de Chimie Inorganique et Matériaux Moléculaires.
(1) (a) McDaniel, K. F. In ComprehensiVe Organometallic Chemistry
II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press:
Oxford, UK, 1995; Vol. 6, pp 93–107. (b) Pike, R. D.; Sweigart, D. A.
Coord. Chem. ReV. 1999, 187, 183. (c) Pape, A. R; Kaliappan, K. P.;
Kündig, E. P. Chem. ReV. 2000, 100, 2917. (d) Giner-Planas, J.; Prim, D.;
Rose-Munch, F.; Rose, E.; Monchaud, D.; Lacour, J. Organometallics 2001,
20, 4107. (e) Rose-Munch, F.; Rose, E. Eur. J. Inorg. Chem. 2002, 1269.
(f) Sweigart, D. A.; Reingold, J. A.; Son, S. U. In ComprehensiVe
Organometallic Chemistry, 3rd ed.; Crabtree, R. H., Mingos, D. M. P., Eds.;
Elsevier: Oxford, 2006; Vol. 5, Chapter 10, pp 761–814,
(2) (a) See for example: Pearson, A. J.; Bruhn, P. R. J. Org. Chem.
1991, 56, 7092. (b) Miles, W. H.; Brinkman, H. R. Tetrahedron Lett. 1992,
33, 589. (c) Pearson, A. J.; Shin, H. Tetrahedron 1992, 48, 7527.
(3) (a) Pike, R. D.; Sweigart, D. A. Synlett. 1990, 565, 571. (b) Rose-
Munch, F.; Rose, E. Curr. Org. Chem. 1999, 3, 445.
(4) Jacques, B.; Chavarot, M.; Rose-Munch, F.; Rose, E. Angew. Chem.,
Int. Ed. 2006, 45, 3481.
(5) (a) Rose-Munch, F.; Aniss, K.; Rose, E. J. Organomet. Chem. 1990,
385, C1. (b) Auffrant, A.; Prim, D.; Rose-Munch, F.; Rose, E.; Vaissermann,
J. Organometallics 2001, 20, 3214. (c) Prim, D.; Planas, J. G.; Auffrant,
A.; Rose-Munch, F.; Rose, E.; Vaissermann, J. J. Organomet. Chem. 2003,
688, 273. (d) Jacques, B.; Tranchier, J.-P.; Rose-Munch, F.; Rose, E.;
Stephenson, R.; Guyard-Duhayon, C. Organometallics 2004, 23, 184. (e)
Schouteeten, S.; Tranchier, J.-P.; Rose-Munch, F.; Rose, E.; Auffrant, A.;
Stephenson, R. Organometallics 2004, 23, 4308.
(6) (a) Auffrant, A.; Prim, D.; Rose-Munch, F.; Rose, E.; Schouteeten,
S.; Vaissermann, J. Organometallics 2003, 22, 1898. (b) Prim, D.;
Andrioletti, B.; Rose-Munch, F.; Rose, E.; Couty, F. Tetrahedron 2004,
60, 3325.
(7) Eloi, A.; Rose-Munch, F.; Jonathan, D.; Tranchier, J.-P.; Rose, E.
Organometallics 2006, 25, 4554.
10.1021/om7010672 CCC: $40.75
2008 American Chemical Society
Publication on Web 02/01/2008

(η5-cyclohexadienyl)Mn(CO)3
Scheme 2
Organometallics, Vol. 27, No. 4, 2008 785
Scheme 3
Scheme 4
group R, such a methoxy, a chloride, or an amino group, they
can eliminate RX after an acidic treatment8 via cine9 and tele10
nucleophilic substitutions (Scheme 1, step d).
the ketone carbonyl group but also to the C2 carbon atom to
form a deuterated cyclohexadiene (Scheme 3).7 The observed
diastereoselectivity stresses out the importance of the nature of
the substituent on the sp3 carbon atom. It likely originates in
the relative size of the Mn(CO)3 tripod, which hinders one face
of the cyclohexadienyl ring and of the axial sp3 carbon atom
substituent. If one assumes that the keto group adopts the same
conformation in 3 and 4,11 the nucleophile could add either syn
or anti to the metal entity when no sterically demanding group
is present at the C6 carbon atom such as in 3, whereas the phenyl
group at C6 in the ketone 4 would favor the addition syn to the
Mn(CO)3 tripod, which could explain the observed limited de.
Here we report a preliminary study on the reactivity of (η5-
ketocyclohexadienyl) Mn(CO)3 complexes toward a Grignard
reagent and the behavior of the newly formed alcohol derivatives
in acidic medium.
Results and Discussion
The complexes 3 and 4 used as starting materials in this study
were readily obtained by Stille reaction of complexes 1 and 2
with ThSnBu3 (Th ) 2-thienyl) and Pd2dba3 and AsPh3 as the
catalytic system, after carbonylative conditions, Scheme 2.6 The
latter were obtained by nucleophilic addition of phenyl mag-
nesium chloride or lithium aluminum hydride onto the [(η6-
Complexes 5 and 6 reacted with HBF4 · OMe2 to afford
complexes 7 and 8 in 45 and 71% yield, respectively, together
with trienones 9 and 10 in 40 and 25% yield, respectively. The
formation of the different products could be explained with the
following mechanism (Scheme 4). In the presence of an acid,
a cationic intermediate could be formed after abstraction of the
hydroxy group, leading, on one side, to the double-bond
formation of complexes 7 or 8 and, on the other one, to organic
compounds 9 or 10 after decoordination and hydrolysis of the
trienol ether.12 Exposing isolated samples of 7 and 8 to the acidic
reaction conditions used for their preparation gave the dienones
9 and 10, in agreement with another possible pathway for the
formation of these dienones.
-
para-chloroanisole)Mn(CO)3]+BF4 complex.8 When com-
plexes 3 and 4 reacted with methyl magnesium chloride, the
two alcohols 5 and 6 corresponding to the regioselective addition
of the Grignard reagent to the keto function were formed in 72
and 86% yield, respectively, Scheme 2. For each alcohol, two
diastereoisomers, due to the planar chirality of the complexes,
were formed with no diastereoselectivity for alcohol 5 and with
40% de for 6 according to crude mixture 1H NMR spectra. The
two sets of diastereoisomers were carefully purified by silica
gel chromatography, and their 1H NMR spectra showed for the
H2, H3, and H5 proton signals, chemical shifts specific for 1,5-
disubstituted η5 systems.
Thus, the π system remains intact with no incorporation of
the nucleophile at an internal position of the cyclohexadienyl
ring, unlike the deuteride addition, which occurs not only to
Taking advantage of the rearomatization procedure by exo-
hydride abstraction already successfully exploited in our
group,5b,c,6 we submitted complex 7 to the action of CPh3BF4
and isolated the cationic (η6-arene)Mn(CO)3 complex 11 in 30%
yield (Scheme 2). The 1H NMR spectrum exhibits two doublets
at 6.55 and 7.30 ppm for the H2, H3, H5, and H6 protons, in
good agreement with the presence of a para-disubstituted arene
ring. The olefinic H9 proton signals show two singlets at 5.86
and 5.83 ppm, at higher frequencies than the corresponding ones
of complex 7 (two singlets at 5.33 and 5.28 ppm), stressing the
strong electron-withdrawing effect of the arene ring coordinated
to the Mn(CO)3 entity.
(8) Balssa, F.; Gagliardini, V.; Rose-Munch, F.; Rose, E. Organome-
tallics 1996, 15, 4373.
(9) (a) For cine nucleophilic substitutions in (arene)Cr(CO)3, see for
example: Rose-Munch, F.; Rose, E.; Semra, A. Chem. Commun. 1986, 1551.
(b) Rose-Munch, F.; Rose, E.; Semra, A.; Jeannin, Y.; Robert, F. J.
Organomet. Chem. 1988, 353, 53. (c) Rose-Munch, F.; Rose, E.; Semra,
A.; Bois, C. J. Organomet. Chem. 1989, 363, 103. (d) Rose-Munch, F.;
Rose, E.; Semra, A. J. Organomet. Chem. 1989, 377, C9. (e) Djukic, J. P.;
Rose-Munch, F.; Rose, E. Chem. Commun. 1991, 22, 1634. (f) Rose-Munch,
F.; Bellot, O.; Mignon, L.; Semra, A.; Robert, F.; Jeannin, Y. J. Organomet.
Chem. 1991, 402, 1.
(10) (a) For tele nucleophilic substitutions in (arene)Cr(CO)3, see for
example: Boutonnet, J. C.; Rose-Munch, F.; Rose, E. Tetrahedron Lett.
1985, 26, 3989. (b) Rose-Munch, F.; Rose, E.; Semara, A. Chem. Commun.
1986, 1108. (c) Rose-Munch, F.; Rose, E. Chem. Commun. 1987, 942. (d)
Rose-Munch, F.; Rose, E.; Semra, A.; Garcia-Oricain, J.; Knobler, C J.
Organomet. Chem. 1989, 363, 297. (e) Djukic, J. P.; Rose-Munch, F.; Rose,
E. Organometallics 1995, 14, 2027.
(11) A preferred conformation of the keto function, “anti” to the sp3
carbon atom, has been confirmed by preliminary theoretical investigations
currently in progress.
(12) For examples of neutral iron methylenecyclohexadiene complexes,
see: Howell, J. A. S.; Thomas, M. J. Organometallics 1985, 4, 1054.

786 Organometallics, Vol. 27, No. 4, 2008
Cetiner et al.
arene ring substituents on the Mn(CO)3 tripod conformation.
The value of the torsion angles C1-C100-Mn-C14, C3-
C100-Mn-C16, and CC100-Mn-C15 (C100 being the center
of the six-membered ring) are 37.08°, 39.43°, and 37.79°,
respectively. The C8dC9 double bond, oriented toward the
metal, is in the [C1C8C9] plane, which makes a dihedral angle
of 40° with the arene ring plane, the thiophene plane being
oriented away from the metal. Thus in the solid state, the double
bond is not conjugated to the π system in the η5 and in the η6
complexes 7 and 11. In both of them, the double-bond length
is roughly the same: 1.344 and 1.342 Å, respectively. Further-
more, there is a distortion of the aromatic ring of complex 11;
indeed the Mn-C4 bond (2.282 Å) that is substituted by the
methoxy group is longer than the five other Mn-C bonds
(2.206, 2.190, 2.212, 2.196, 2.171 Å), in good agreement with
what has been reported for arenetricarbonylchromium com-
plexes20 and the bending effect opposite the metal moiety of
the OMe π donor substituent.
Conclusion
We have shown that (η5-cyclohexadienyl)Mn(CO)3 com-
plexes substituted by a keto group react with a Grignard reagent
to yield the corresponding alcohols as the sole products in high
yield. The low de observed in one case gives some hope to
explore more deeply the diastereoselection of this reaction. The
dehydration of these alcohols in acidic medium affords, as the
major compounds, unprecedented η5 complexes with the double
bond conjugated to the π system, whose formation mechanism
and reactivity are currently under investigation.
Figure 1. ORTEP representations of complexes 7 and 11 with
thermal ellipsoids at the 30% probability level. Selected bond
lengths for 7 (Å): C8-C9 1.344(4), C1-C8 1.484(3), C8-C10
1.497(4), C1-C2 1.415(3), C2-C3 1.431(3), C3-C4 1.427(4),
C4-C5 1.409(3), C5-C6 1.518(4), C6-C1 1.528(3), Mn-C1
2.285(2), Mn-C2 2.148(2), Mn-C3 2.148(2), Mn-C4 2.215(3),
Mn-C5 2.229(2). For 11: C8-C9 1.342(3), C1-C8 1.499(3),
C8-C10 1.470(3), C1-C2 1.431(3), C2-C3 1.406(3), C3-C4
1.423(3), C4-C5 1.408(3), C5-C6 1.420(3), Mn-C1 2.206(2),
Mn-C2 2.1713(19), Mn-C3 2.196(2), Mn-C4 2.282(2), Mn-C5
2.212(2), Mn-C6 2.190(2).
Experimental Section
All reactions were routinely performed under a dry nitrogen
atmosphere using standard Schlenk techniques. THF was dried over
sodium benzophenone ketyl and distilled. N,N,N′,N′-Tetramethyl-
ethylenediamine (TMEDA) was distilled over KOH and stored
under nitrogen over 4 Å molecular sieves. Acetone and benzalde-
hyde were distilled over K2CO3. NMR spectra were recorded on a
Very few examples of η6 Mn complexes substituted by a
conjugated double bond have been described in the literature,13–15
whereas the analogous derivatives of the isoelectronic neutral
chromium complexes have been known for many years.16 In
contrast, to the best of our knowledge, no synthesis of an η5
Mn complex with the π system conjugated to a double bond
has been reported so far.
Bruker ARX 200 MHz or AC 400 MHz spectrometer. 1H and 13
C
signals of NMR solvents were used as internal standard respectively
at δ ) 7.26 ppm and δ ) 77.36 ppm in CDCl3 and at δ ) 2.09
ppm and δ ) 30.60 ppm in acetone. Infrared spectra were measured
on a Bruker Tensor 27 spectrometer. Elemental analyses were
performed by the Service Central d’Analyze du CNRS. Mass spectra
were performed by the Laboratory of Mass Spectroscopy, Université
des Sciences et Techniques, Lille, by the Groupe de Spectrométrie
de Masse (UMR 7613, UPMC), and by the Service de Spectrométrie
de Masse de l’ENS (Chemistry Dept, Paris).
Pleasingly, we obtained monocrystals of complexes 7 and
11 suitable for radiocrystallographic analyses, and ORTEP views
are presented Figure 1 as well as some selected bond lengths.
The η5 structure of complex 717 is confirmed by the five
coplanar carbon atoms of the π system, while the remaining
sp3 C6 carbon atom is located 40° above this plane. The C8dC9
double bond is in the [C1C8C9] plane, which makes a dihedral
angle of 31° away from the metal with the five coplanar carbon
atoms.
(17) Crystal data of 7 and 11. Data were recorded at room temperature
on a Kappa-CCD Enraf-Nonius diffractometer with graphite-monochromated
Mo KR radiation (λ ) 0.71073 Å) and the ω-scan technique. The structure
was solved by direct methods and refined with full-matrix least-squares
technique on F using the Crystals18 programs. Molecular structures were
drawn with the program Cameron.19 Complex 7: C16H13MnO4S, M )
356.27; monoclinic, a ) 6.7948(6) Å, b ) 19.899(3) Å, c ) 12.1956(15)
Å, U ) 1613.3(3) Å3, T ) 250 K, space group P21/n, Z ) 4, 15 998
reflections measured, 4629 unique (Rint ) 0.043), which were used in all
calculations. The final wR(F2) was 0.054 (all data). Complex 11:
C16H12BF4MnO4S, M ) 442.07; monoclinic, a ) 16.8079(7) Å, b )
7.1173(3) Å, c ) 29.7749(17) Å, U ) 3558.1(3) Å3, T ) 150 K, space
The structure of complex 1117 shows a staggered conforma-
tion of the Mn(CO)3 tripod with respect to the carbon atoms of
the arene ring. It is noteworthy that an almost anti-eclipsed
conformation was found in the related para-disubstituted
complex where the methylene group is replaced by an oxygen
atom,6a stressing the importance of the electronic effect of the
(13) Lee, S. S.; Lee, T. Y.; Lee, J. E.; Lee, I. S.; Chung, Y. K.
Organometallics 1996, 15, 3664.
(14) Son, S. U.; Lee, S. S.; Chung, Y. K. J. Am. Chem. Soc. 1997, 119,
7711–7715.
group P21/c, Z ) 8, 52 256 reflections measured, 10 041 unique (Rint )
0.040), which were used in all calculations. The final wR(F2) was 0.053
(all data).
(15) Zhang, X.; Yu, K.; Carpenter, G. B.; Sweigart, D. A. Organome-
tallics 2000, 19, 1201.
(18) Betteridge, P. W.; Carruthers, J. R.; Cooper, R. I.; Prout, K.; Watkin,
D. J. J. Appl. Crystallogr. 2003, 36, 1487.
(16) (a) Drehfahl, G.; Horhold, H. H.; Kuhne, K. Chem. Ber. 1965, 98,
1826. (b) Rausch, M. D.; Moser, G. A.; Zaiko, E. L.; Lipman, A. L. J.
Organomet. Chem. 1970, 23, 185.
(19) Watkin, D. J.; Prout, C. K.; Pearce, L. J. CAMERON;Chemical
Crystallography Laboratory: Oxford, UK, 1996.

(η5-cyclohexadienyl)Mn(CO)3
Organometallics, Vol. 27, No. 4, 2008 787
Preparation of Complex 5. To a solution of (η5-ketocyclo-
hexadienyl)Mn(CO)3 (3) (0.250 g, 0.70 mmol) in THF (15 mL)
was added MeMgCl (0.93 mL, 2.8 mmol, 3 N) at 0 °C. The yellow
solution was stirred at 0 °C for 20 min. Then water (30 mL) was
added and the aqueous phase was extracted with Et2O (3 × 30
mL). The organic phase was washed with water (50 mL) and a
saturated solution of NaCl (50 mL). After drying over MgSO4 the
solvent was removed under reduced pressure and the desired product
was dried in Vacuo. The yellow oil was purified on a silica gel
chromatography column (Merck silica gel 60, 15–40 µm, petroleum
ether/Et2O). Two diastereoisomers were obtained (0.185 g, 72%).
Complex 5a: 105 mg, 40% yield. IR (neat): 2004 [Mn(CO)3],
1909 [Mn(CO)3], 2940 [OH]. 1H NMR (200 MHz, CDCl3): δ 1.94
(m, 4H, H6exo and H9), 2.87 (m, 2H, H5 and H6endo), 3.45 (s, 3H,
and the desired product was dried in Vacuo. The yellow oil was
purified on a silica gel chromatography column (Merck silica
gel 60, 15–40 µm, petroleum ether/Et2O). Two compounds (7
and 9) were obtained.
Complex 7: 51 mg, 45% yield. IR (neat): 2010 [Mn(CO)3], 1925
1
2
[Mn(CO)3]. H NMR (200 MHz, CDCl3): δ 2.45 (d, 1H, J6exo-6endo
) 11.1 Hz, H6exo), 3.04 (m, 2H, H5 et H6endo), 3.52 (s, 3H, H7),
3
4.87 (d, 1H, J2–3 ) 5.9 Hz, H2), 5.33 (s, 1H, H9a), 5.28 (s, 1H,
3
4
H9b), 5.65 (dd, 1H, J3–2 ) 5.9 Hz, J3–5 ) 2.52 Hz, H3), 6.81 (d,
1H, J ) 2.2 Hz, HTh), 6.83–6.79 (m, 2H, HTh). 13C NMR (100
3
MHz, CDCl3): δ 29.9 (C6), 36.2 (C5), 54.5 (C7), 65.2 (C3), 70.8
(C8), 77.4 (C1), 93.3 (C2), 117.3 (C9), 125.1, 125.7, 126.8 (C11,
C12, C13), 142.1 (C4), 143.7 (C10). HRMS (ESI) m/z: calcd for
C16H13MnO4S, 354.9837; found, 354.9831 [M - H]–. Anal. Calcd
for C16H13MnO4S: C, 53.93; H, 3.68. Found: C, 54.25; H, 3.81.
This compound was crystallized in a petroleum-ether/ether mixture
giving yellow crystals.
3
4
H7), 5.29 (dd, 1H, J2–3 ) 6.0 Hz, J2–6endo ) 1.0 Hz, H2), 5.69
3
4
(dd, 1H, J3–2 ) 6.0 Hz, J3–5 ) 2.72 Hz, H3), 6.85 (m, 2H, HTh),
7.16 (d, 1H, J ) 4.4 Hz, HTh). 13C NMR (100 MHz, CDCl3): δ
3
Compound 9 (mixture of E and Z): 26 mg, 40% yield. IR
28.1 (C6), 30.6 (C9), 36.8 (C5), 54.5 (C7), 65.6 (C3), 74.2 (C8), 76.6
(C1), 91.5 (C2), 123.8, 124.9, 126.7 (C11, C12, C13), 143.4 (C4), 149.9
(C10). HRMS (ESI) m/z: calcd for C16H15NaMnO5S, 396.9918;
found, 396.9912 [M + Na]+. Anal. Calcd for C16H15MnO5S: C,
51.34; H, 4.04. Found: C, 51.08; H, 3.91.
1
(neat): 1680 [CO]. H NMR (200 MHz, CDCl3): δ 2.27 (s, 3H,
H8E or H8Z), 2.30 (s, 3H, H8E or H8Z), 2.47 (t, 1H, 3J ) 7.0 Hz, H6E
3
3
or H6Z), 2.59 (t, 1H, J ) 7.0 Hz, H6E or H6Z), 2.85 (t, 1H, J )
6.7 Hz, H5E or H5Z), 2.99 (t, 1H, 3J ) 6.6 Hz, H5E or H5Z), 5.87 (d,
1H, 3J ) 10.1 Hz, H3E or H3Z), 5.98 (d, 1H, 3J ) 10.1 Hz, H3E or
H3Z), 6.87 (m, 4H, HTh), 7.35 (m, 2H, HTh), 7.47 (d, 1H, 3J ) 10.2
Hz, H2E or H2Z), 7.56 (d, 1H, 3J ) 10.2 Hz, H2E or H2Z). 13C NMR
(100 MHz, CDCl3): δ 21.8 (C8E or C8Z), 22.6 (C8E or C8Z), 27.2
(C5E or C5Z), 28.9 (C5E or C5Z), 37.0 (C6E or C6Z), 37.4 (C6E or
C6Z), 125.7–128.3 (CThE, CThZ, C3E, C3Z, C7E, C7Z), 129.7 (C1E or
C1Z), 130.5 (C1E or C1Z), 134.2 (C9E or C9Z), 135.3 (C9E or C9Z),143.9
(C2E or C2Z), 145.9 (C2E or C2Z), 199.8 (C4E or C4Z), 200.0 (C4E or
C4Z). HRMS (ESI) m/z: calcd for C12H12ONaS, 227.0501; found,
227.0507 [M + Na]+. Anal. Calcd for C12H12OS: C, 70.57; H, 5.93.
Found: C, 70.71; H, 6.11.
Complex 5b: 80 mg, 32% yield. IR (neat): 2004 [Mn(CO)3],
1909 [Mn(CO)3], 2940 [OH]. 1H NMR (200 MHz, CDCl3): δ
1.58 (s, 3H, H9), 1.94 (d, 1H, 3J6exo-6endo ) 12.6 Hz, H6exo), 3.02
3
(m, 2H, H5 and H6endo), 3.45 (s, 3H, H7), 5.06 (d, 1H, J2–3
)
3
4
6.0 Hz, H2), 5.71 (dd, 1H, J3–2 ) 6.0 Hz, J3–5 ) 2.5 Hz, H3),
6.81–7.15 (m, 2H, HTh), 7.17 (d, 1H, 3J ) 1.2 Hz, HTh). 13C
NMR (100 MHz, CDCl3): δ 26.6 (C6), 29.8 (C9), 37.2 (C5), 54.5
(C7), 65.4 (C3), 74.7 (C8), 77.6 (C1), 91.5 (C2), 123.2, 124.4,
126.9 (C11, C12, C13), 143.6 (C4), 150.1 (C10). HRMS (ESI) m/z:
calcd for C16H15NaMnO5S, 396.9918; found, 396.9912 [M +
Na]+. Anal. Calcd for C16H15MnO5S: C, 51.34; H, 4.04. Found:
C, 51.01; H, 3.89.
Complex 8: 109 mg, 71% yield. IR (neat): 2008 [Mn(CO)3],
1914 [Mn(CO)3]. 1H NMR (200 MHz, CDCl3): δ 3.48 (s, 3H, H7),
3.61 (dd, 1H, 3J5–6endo ) 6.4 Hz, 4J5–3 ) 2.7 Hz, H5), 4.50 (d, 1H,
Complex 6a: 45 mg, 30% yield. IR (neat): 2008 [Mn(CO)3],
1912 [Mn(CO)3], 2978 [OH]. 1H NMR (200 MHz, CDCl3): δ 1.69
(s, 3H, H9), 3.36 (dd, 1H, 3J5–6 ) 6.4 Hz, 4J5–3 ) 2.6 Hz, H5), 3.40
(s, 3H, H7), 4.4 (dd, 1H, 3J6–5 ) 6.3 Hz, 3J6–2 ) 1.1 Hz, H6), 5.36
3J6endo-5 ) 6.3 Hz, H6endo), 5.20 (dd, 1H, 3J2–3 ) 6.0 Hz, 4J2–6endo
)
1.5 Hz, H2), 5.27 (s, 1H, H9), 5.51 (s, 1H, H9′), 5.58 (dd, 1H, 3J3–2
4
(dd, 1H, 3J2–3 ) 5.9 Hz, 4J2–6 ) 1.3 Hz, H2), 5.66 (dd, 1H, 3J3–2
)
) 6.0 Hz, J3–5 ) 2.5 Hz, H3), 6.87–7.21 (m, 8H, HPh and HTh).
13C NMR (100 MHz, CDCl3): δ 43.5 (C6), 44.2 (C5), 54.6 (C7),
65.5 (C3), 74.9 (C1), 92.3 (C2), 117.7 (C9), 125.2–128.6 (CPh and
CTh), 140.3 (C4), 142.5 (C10), 145.7 (C14). HRMS (ESI) m/z: calcd
for C22H18MnO4S, 433.0306; found, 433.0300 [M + H]+. Anal.
Calcd for C22H18MnO4S: C, 61.11; H, 3.97. Found: C, 61.37; H,
4.15.
6.0 Hz, 4J3–5 ) 2.5 Hz, H3), 6.55–7.26 (m, 8H, HPh and HTh) ppm.
13C NMR (100 MHz, CDCl3): δ 31.8 (C9), 44.4 (C6), 44.7 (C5),
54.5 (C7), 64.8 (C3), 74.6 (C8), 87.3 (C1), 91.8 (C2), 124.5, 126.5,
127.0, 128.4 (CTh and CPh), 142.0 (C4), 146.0 (C10), 146.4 (C14).
HRMS (MALDI-TOF) m/z: calcd for C22H17MnO4S, 432.023;
found, 432.003 [M - H2O]+. Anal. Calcd for C22H19MnO5S: C,
58.66; H, 4.25. Found: C, 58.43; H, 4.04.
Compound 10 (mixture of E and Z): 25 mg, 25% yield.
10a: IR (neat): 1658 [CO]. 1H NMR (200 MHz, CDCl3): δ 2.22
(s, 3H, H8), 2.92 (d, 1H, 2J5exo-5endo ) 8.1 Hz, H5exo), 3.09 (dd, 1H,
Complex 6b: 133 mg, 56% yield. IR (neat): 2008 [Mn(CO)3],
1912 [Mn(CO)3], 2978 [OH]. 1H NMR (200 MHz, CDCl3): δ 1.54
3
2J5endo-5exo ) 8.1 Hz, J5endo-6endo ) 3.2 Hz, H5endo), 4.44 (d, 1H,
3
4
(s, 3H, H9), 3.33 (dd, 1H, J5–6endo ) 6.3 Hz, J5–3 ) 2.4 Hz, H5),
3
3J6endo-5endo ) 3.2 Hz, H6endo), 5.92 (d, 1H, J3–2 ) 5.1 Hz, H3),
3
3.39 (s, 3H, H7), 4.3 (s, 1H, J6endo-5 ) 6.3 Hz, H6endo), 5.41 (d,
7.04–7.43 (m, 8H, HPh and HTh), 7.62 (d, 1H, 3J2–3 ) 5.2 Hz, H2).
13C NMR (100 MHz, CDCl3): δ 22.8 (C8), 43.0 (C6), 44.3 (C5),
89.1 (C1), 126.6 (C3), 126.8–127.6 (CPh and CTh), 145.3 (C2), 132.5,
137.7, 141.5, 143.4 (CQ), 196.4 (C4). HRMS (ESI) m/z: calcd for
C18H16ONaS, 303.0814; found, 303.0820 [M + Na]+.
1H, 3J2–3 ) 6.1 Hz, H2), 5.70 (dd, 1H, 3J3–2 ) 6.0 Hz, 4J3–5 ) 2.5
Hz, H3), 6.62–7.28 (m, 8H, HPh and HTh). 13C NMR (100 MHz,
CDCl3): δ 33.1 (C9), 44.1 (C6), 45.2 (C5), 54.5 (C7), 64.7 (C3),
75.2 (C8), 86.7 (C1), 91.9 (C2), 124.1, 126.7, 127.0, 128.4 (CTh and
CPh), 141.4 (C4), 146.8 (C10), 151.7 (C14). HRMS (MALDI-TOF)
m/z: calcd for C22H17MnO4S, 432.023; found, 432.003 [M - H2O]+.
Anal. Calcd for C22H19MnO5S: C, 58.66; H, 4.25. Found: C, 58.39;
H, 4.02.
10b: IR (neat): 1658 [CO] cm-1.1H NMR (200 MHz, CDCl3):
2
δ 2.43 (s, 3H, H8), 2.85 (d, 1H, J5exo-5endo ) 8.1 Hz, H5exo), 2.99
2
3
(dd, 1H, J5endo-5exo ) 8.1 Hz, J5endo-6endo ) 3.0 Hz, H5endo), 4.62
(d, 1H, 3J6endo-5endo ) 3.0 Hz, H6endo), 5.99 (d, 1H, 3J3–2 ) 5.1 Hz,
H3), 7.04–7.43 (m, 8H, HPh and HTh), 7.71 (d, 1H, 3J2–3 ) 5.1 Hz,
H2). 13C NMR (100 MHz, CDCl3): δ 22.7 (C8), 44.3 (C6), 45.0
(C5), 89.1 (C1), 126.4 (C3), 125.5–127.5 (CPh and CTh), 143.7 (C2),
131.5, 136.0, 142.7, 143.4 (CQ), 196.6 (C4).
Preparation of Complex 7 and Compound 9. To a solution
of (η5-alcohol cyclohexadienyl)Mn(CO)3 (5) (0.121 g, 0.32
mmol) in CH2Cl2 (5 mL) was dropped slowly HBF4 · OMe2
(0.185 mL, 1.79 mmol) at -35 °C. The brown solution was
stirred at -35 °C for 1 h 30 min. Then water (10 mL) was added
at room temperature and the aqueous phase was extracted with
Et2O (4 × 10 mL). The organic phase was washed with water
(10 mL) and a saturated solution of NaCl (10 mL). After drying
over MgSO4 the solvent was removed under reduced pressure
Preparation of Complex 11. To a solution of complex 7 (0.077
g, 0.21 mmol) in CH2Cl2 (5 mL) was added CPh3BF4 (0.072 g,
0.21 mmol) in 5 mL of CH2Cl2. The mixture was stirred at room
temperature for 30 min. The η6-cationic (arene)Mn(CO)3 was

788 Organometallics, Vol. 27, No. 4, 2008
Cetiner et al.
precipitated by adding 30 mL of dry Et2O, filtered, washed with
Et2O, and dried in Vacuo. A yellow solid was obtained (0.028 g,
0.06 mmol, 30%).
C16H12MnO4SBF4: C, 43.44; H, 2.74. Found: C, 43.21; H, 2.57.
This compound was crystallized in a mixture of ether and acetone,
giving yellow crystals.
Complex 11: 30% yield. IR (neat): 2064 [Mn(CO)3], 2000
1
[Mn(CO)3]. H NMR (200 MHz, (C2D6CO): δ 4.23 (s, 3H, H7),
Acknowledgment. Financial support by CNRS is kindly
acknowledged. We thank Dayana Jonathan for preliminary
results and the Ministère de l’Education Nationale et de la
Recherche for a MENRT grant to D.C.
3
5.96 (s, 1H, H9a), 5.94 (s, 1H, H9b), 6.55 (d, 2H, J ) 7.6 Hz, H3
3
et H5), 7.14–7.20 (m, 2H, HTh), 7.30 (d, 2H, J ) 7.6 Hz, H2 et
H6), 7.63 (d, 1H, 3J ) 3.9 Hz, HTh). 13C NMR (100 MHz,
(CD3)2CO): δ 59.1 (C7), 74.2 (C8), 79.1 (C1), 83.0 (C3 et C5), 104.4
(C2 et C6), 121.9 (C9), 128.1, 128.7, 130.1 (C11, C12, C13), 140.8
(C4), 150.4 (C10). HRMS (ESI) m/z: calcd for C16H12MnO4S,
354.9837; found, 354.9831 [M - BF4]+. Anal. Calcd for
Supporting Information Available: Text giving X-ray crystal-
lographic data for complexes 7 and 11. This material is available
free of charge via the Internet at http://pubs.acs.org.
(20) Djukic, J. P.; Rose-Munch, F.; Rose, E.; Vaissermann, J. Eur.
J. Inorg. Chem. 2000, 1295.
OM7010672