New access to (η5-cyclohexadienyl)Mn(CO)3 and cationic (η6-arene)Mn(CO)3 complexes by Suzuki-Miyaura reaction

Article abstract of DOI:10.1039/c0dt01270j

First Suzuki-Miyaura coupling reactions applied to (η⁵- chloro-cyclohexadienyl)Mn(CO)₃ complexes are described and lead to the syntheses of (η⁵-aryl-cyclohexadienyl)Mn(CO)₃ and of cationic (η⁶-arene)M

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PAPER
New access to (g5-cyclohexadienyl)Mn(CO)3 and cationic
(g6-arene)Mn(CO)3 complexes by Suzuki–Miyaura reaction†
Franc¸oise Rose-Munch,* Alex Marti, Derya Cetiner, Jean-Philippe Tranchier and Eric Rose*
Received 21st September 2010, Accepted 18th November 2010
DOI: 10.1039/c0dt01270j
5
First Suzuki–Miyaura coupling reactions applied to (h -chloro-cyclohexadienyl)Mn(CO)3 complexes
5
are described and lead to the syntheses of (h -aryl-cyclohexadienyl)Mn(CO)3 and of cationic
6
(h -arene)Mn(CO)3 complexes after rearomatization. The structures of two of the new complexes have
been investigated by X-ray diffraction study.
cyclohexadienes (path c).1d,4a,6 Very recently the first resolution
Introduction
6
of h -arene-Mn complexes was reported, which permits an
6
6
5
Cationic (h -arene)tricarbonylmanganese complexes represent
easy access to enantiopure (h -arene)- and (h -cyclohexadienyl)-
tricarbonylmanganese complexes.7 This important discovery is
greatly expanding the area of applications of such complexes
in the field of enantioselective syntheses of organic compounds
like, for example, enantiopure cyclohexenones (path d)7 as well as
organometallic complexes like enantiopure phosphino-substituted
an important class of organometallic compounds due to
the electrophilic character of the arene ring coordinated
to the Mn(CO)3 tripod.1 Thus nucleophiles react easily
6
5
with these h -arene complexes to give stable neutral (h -
cyclohexadienyl)tricarbonylmanganese complexes (Scheme 1,
path a) which are versatile intermediates in organic as well as
in organometallic chemistry.1,2 For example, oxidative rearom-
atization can be achieved with formation of poly-substituted
arenes3–5 (path b) and addition of a nucleophile [R2]- followed by
decoordination of the metal entity gives rise to cis-functionalized
5
6
5
h
or h tricarbonylmanganese complexes. (h -R-substituted-
cyclohexadienyl)tricarbonylmanganese complexes, R being a leav-
ing group such as OMe, Cl, NR¢2, or SR¢¢, treated with a hydride
and an acid, eliminate HR via cine, tele-meta and tele-para
nucleophilic substitutions (path e).8–11 Two main functionalization
5
methods of (h -cyclohexadienyl)tricarbonylmanganese complexes
have been reported: the lithiation/electrophilic quench sequence
(path f) and the palladium-catalyzed coupling reactions (path
g). The first one used with chloro and/or methoxy-substituted
complexes gives rise to complexes substituted in the a or b position
of the substituent12 whereas with bromo-substituted complexes,
metal-bromide exchange reaction occurs and leads to complexes
bearing the electrophile at the ipso carbon which was substituted
5
by the bromide atom.13 The second one, developed with (h -
chloro-cyclohexadienyl)tricarbonylmanganese complexes, allows
the substitution of the halogen and leads to a large variety of
5
diversely substituted h complexes (path g) and, in particular,
to keto-derivatives when the reaction is performed under CO
atmosphere.14a,b,e It is worth noting that, in all cases where the
exo R1 substituent is a hydrogen, rearomatization is possible
with CPh3BF4 by easy hydride abstraction and the corresponding
6
substituted cationic (h -arene)tricarbonylmanganese complexes
5
can thus be recovered (path h).14b,c,d,15,16
Scheme 1 General reactivity patterns of (h -cyclohexadienyl)Mn(CO)3
complexes.
5
These palladium-catalyzed reactions in the h complex series
are all the more important as they allow the preparation of
6
h complexes substituted by a double or a triple bond, and by
strongly electron withdrawing groups (EWG) R2 (for example:
aldehyde, keto, ester, or nitrile groups) which are difficult or even
impossible to obtain by direct coordination of the Mn(CO)3 entity
to the substituted arenes17 (Scheme 2, path a). Furthermore it has
UPMC Univ Paris 06, IPCM, CNRS UMR 7201, Equipe de Chimie
Organique et Organome´tallique Case 181, 4 Place Jussieu, F-75252, Paris
Cedex 05, France. E-mail: francoise.rose@upmc.fr
† CCDC reference numbers 782848 and 782849. For crystallographic data
in CIF or other electronic format see DOI: 10.1039/c0dt01270j
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5
Scheme 3 Synthesis of h complexes 2a,b.
is directed to the meta position with respect to the methoxy group.
Furthermore, there is a synergic effect of the chlorine atom at the
same position, explaining why no other isomer was detected by
addition of a hydride or a phenyl group.
The Suzuki reaction is well precedented for chromium com-
plexes and numerous examples have been described in the
5
6
Scheme 2 Pd coupling reactions applied to h - and h -Mn complexes.
6
literature involving (h -chloroarene)Cr(CO)3 complexes and dif-
ferent catalytic systems such as Pd2dba3, PR3 or Pd(PPh3)4.20–22
The first attempts of coupling were performed with complex
2a and PhB(OH)2, using Pd2dba3 and AsPh3 as the catalytic
system,23 which was successfully used in the case of the Stille
been reported that Pd coupling reactions performed directly with
h complexes as starting materials failed. Instead, the oxidative
addition of a stoichiometric amount of Pd(PPh3)4 to the C–
Cl bond of (h -4-chloro-anisole)tricarbonylmanganese complex18
was observed and proceeded readily at room temperature to give
the Mn/Pd complex with two phosphorus ligands (Scheme 2,
path b). At this stage, in contrast with the tricarbonylchromium
analogue,2a this dinuclear Mn/Pd complex was unreactive toward
a nucleophile with or without a CO atmosphere (Scheme 2,
path c).
6
6
5
and Sonogashira reactions applied to h -Mn complex series.14,15
Unfortunately, even by changing the base (Na2CO3, K2CO3), the
nature of the solvent (acetone, MeOH–H2O) and the reaction
temperature, we recovered the starting material and only traces of
the expected coupling complex.
Under the following experimental conditions, Pd(PPh3)4,
Na2CO3 as base, in MeOH–H2O (9/1) at room temperature for
Thus, palladium catalyzed coupling reactions (Sonogashira,
Stille, Heck, Negishi reactions) have been successfully performed
5
20 min, (h -cyclohexadienyl)Mn(CO)3 complex 2a reacted with
a boronic acid to afford the expected product 3a in 72% yield
(Scheme 4 and Table 1, entry 1). A by-product 4 was formed due
to the insertion of a molecule of the MeOH solvent into the Pd–
C bond of the intermediate. It seems that the nature of the base
slightly influences the course of the reaction, with a yield of 65%
obtained with K2CO3 and of 55% with Cs2CO3 (Table 1, entries 2,
3) but the formation of by-product 4 is again observed. Changing
the MeOH–H2O solvent mixture into THF–H2O allowed us to
avoid the formation of by-product 4 but gave unsatisfying results
due to the presence of degradation products and low conversion
yields.
5
starting from (h -chloro-cyclohexadienyl)Mn(CO)3 complexes
easily obtained by addition of a nucleophile Nu- (Scheme 2, paths
d and e). After rearomatization, the corresponding derivatives lead
6
to unprecedented (h -arene)Mn(CO)3+ complexes (Scheme 2, path
f).14b,c,d,5,19
In the case of Stille coupling reactions, the use of toxic
stannylated reagents and the need to perform some reactions
in DMF, a solvent in which manganese complexes are not very
stable, lead us to turn our attention toward a more environmentally
friendly reaction. Within this context, we report for the first time on
5
the use of (h - cyclohexadienyl)Mn(CO)3 complexes in a Suzuki–
Miyaura-type cross-coupling reaction as well as the synthesis
6
of unprecedented cationic (h -arene)Mn(CO)3 biaryl complexes
containing the Mn(CO)3 moiety coordinated to one of the arene
rings.
Results and Discussion
5
The chloro-substituted h complexes chosen as starting materials
6
for the present study were prepared from two regioisomer h
6
+
complexes: the (h -1-chloro-4-methoxybenzene)Mn(CO)3 and
6
+
the (h -1-chloro-2-methoxybenzene)Mn(CO)3 complexes.
Coupling reactions with g5 complexes derived from
Scheme 4 Suzuki coupling applied to complex 2a.
(g6-1-chloro-4-methoxybenzene)Mn(CO)3 complex 1
+
Finally, Pd(PPh3)4 was kept as catalyst to generalise the reaction
under the following experimental conditions: Na2CO3, MeOH–
H2O (9/1) and room temperature (Scheme 5, Tables 2 and 3)
The reaction time depends on the nature of the substituent on
the boronic acid arene ring. Indeed, with an electron donating
group, such as a methoxy group, the reaction was complete after
Complexes 2a and 2b were readily obtained by regioselective hy-
dride addition of LiAlH4 and PhMgBr (91% and 96% yield, respec-
6
tively) to the cationic (h -1-chloro-4-methoxybenzene)Mn+(CO)3
complex 1, ortho to the chloride atom (Scheme 3).14a,8 Indeed, due
to the electron-donating properties of the methoxy group, addition
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Table 1 Influence of the nature of the base in the coupling reaction of 2a
Table 4 Selected 1H NMR data (ppm, CDCl3) of complexes 3a,b–9a,b
Entry
Base
Temp.
Time
Yield (%)a
Complex
Ar
H2
H3
H5
1
2
3
Na2CO3
K2CO3
Cs2CO3
r.t.
r.t.
r.t.
20 min
20 min
20 min
3a (72%)
3a (65%)
3a (55%)
3a
3b
5a
5b
6a
6b
7a
7b
8a
8b
9a
9b
R = H
5.19
5.50
5.15
5.52
5.19
5.59
5.29
5.64
4.96
5.39
5.50
5.75
5.78
5.61
5.81
5.71
5.85
5.76
5.90
5.78
5.82
5.84
5.89
5.85
3.01
3.59
3.06
3.62
3.07
3.65
3.12
3.67
3.01
3.56
3.26
3.75
R = H
R = p-MeO
R = p-MeO
R = p-F
a By-product 4 was also obtained (5–10% yield)
R = p-F
R = p-Cl
Table 2 Coupling reactions of 2a at room temperature
R = p-Cl
R = o-Cl
Yield (%)a
R = o-Cl
Entry
ArB(OH)2
Time
Ar = 4-formyl-thienyl
Ar = 4-formyl-thienyl
1
2
3
4
5
6
R = H
20 min
15 min
30 min
30 min
50 min
30 min
3a (72)
5a (76)
6a (81)
7a (71)
8a (68)
9a (76)
R = p-MeO
R = p-F
R = p-Cl
temperature no reaction occurred and only starting material 2b
was recovered. It seems likely that the steric bulk of the phenyl
group at the sp3 carbon atom of the (h -cyclohexadienyl) ring
R = o-Cl
Ar = 4-formyl-thienyl
5
a By-product 4 was also obtained (5–10% yield).
inhibits the course of the reaction at this temperature. When the
reaction was refluxed, the coupling reaction was achieved and the
expected complexes were obtained in 64 to 79% yields (Table 3)
with no notable influence of the electronic properties of the arene
ring substituents of the boronic acids as observed with complex 2a.
As in the case of complex 2a, the ortho-chloro-substituted boronic
acid needs a longer reaction time (50 min) (Table 3, entry 5) for a
complete conversion and the yield corresponds to the lowest one
(64%). In contrast to the previous case, no formation of the minor
complex 4 was detected.
Table 3 Coupling reactions of 2b at reflux
Entry
ArB(OH)2
Time
Yield (%)
1
2
3
4
5
6
R = H
40 min
30 min
40 min
30 min
50 min
30 min
3b (79)
5b (75)
6b (74)
7b (74)
8b (64)
9b (69)
R = p-MeO
R = p-F
R = p-Cl
R = o-Cl
Ar = 4-formyl-thienyl
Selected 1H NMR data reported in Table 4 are consistent
5
with the general signal patterns reported for disubstituted h -Mn
complexes.14b The chemical shifts of H2, H3 and H5 protons of
complexes 6a, 7a and 9a are slightly deshielded (except for H2
of complex 6a) in good agreement with the presence of electron
5
withdrawing groups conjugated to the h -cyclohexadienyl rings.
The difference of chemical shifts between protons of complex 3a
and the corresponding ones in complexes 6a and 7a (dHcomplex –
dHcomplex3a) is small, at around 0.1 ppm, except for complex 9a
(Dd (H2) = 0.31 ppm and Dd (H5) = 0.25 ppm) due to the strong
electron-accepting effect of the aldehyde group. With the ortho-
chloro phenyl group (complex 8a), the H2 proton is shielded (Dd
(H2) = -0.23 ppm) probably due to a spacial arrangement of this
phenyl ring creating an anisotropic effect. Analogous differences
of chemical shifts are observed with complexes 6b, 7b, 8b and 9b
(Table 4).
Coupling reactions with g5 complexes derived from
+
(g6-1-chloro-2-methoxybenzene)Mn(CO)3 complex 10
We then extended this methodology to complexes 11 and 12, easily
obtained by addition of PhMgCl to complex 10, in 39 and 46%
yield, respectively (Scheme 6).13
Scheme 5 Generalization of Suzuki couplings to various boronic acids.
15 min stirring (Table 2, entry 2), but with an electron withdrawing
group, such as a halogen atom (Table 2, entries 3, 4) or the
thienyl aldehyde (entry 6), a complete conversion was obtained
after 30 min. In all cases, the yields were satisfying, ranging from
68 to 81%. It is worth noting that the lowest yield (68%) and
the longest reaction time (50 min) were observed for the steri-
cally demanding ortho-chloro-substituted boronic acid (Table 2,
entry 5).
5
(h -Cyclohexadienyl)Mn(CO)3 complex 2b (Scheme 5) was also
5
tested under the same experimental conditions but at room
Scheme 6 Synthesis of h complexes 11 and 12.
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5
These regioisomers 11 and 12 were both submitted to Suzuki
reaction conditions with two different boronic acids, the para
methoxy-phenyl boronic acid and the ortho chloro-phenyl boronic
acid, in order to compare the influence of the steric hindrance of
the boronic reagent (Scheme 7).
(h -cyclohexadienyl)Mn(CO)3 complexes 11 and 12 noticeably
decreased the yields. Thus, complexes 14 and 16 were isolated
only in 18 and 46% yields, respectively. These data highlight the
steric constraint of the C1 position between the methoxy group
and the phenyl-substituted C6 carbon, in particular for complex
11.
Pleasingly, complex 15† crystallized from diethyl ether by a two-
well diffusion procedure (petroleum ether in the outer well), and
the ORTEP view is presented in Fig. 1 as well as selected bond
lengths. Crystallographic data are reported Table 5. The ORTEP
5
view shows that the (h -cyclohexadienyl) ring exhibits the classical
five coplanar carbon geometry (C1–C5) with carbon C6 lying out
of this plane. The dihedral angle between the C1–C5 and C1C6C5
planes reaches 42◦. The plane of the phenyl group at the C6 position
makes a 48◦ dihedral angle with the bisecting Mn1C3C6 plane of
the C1–C5 ring. The dihedral angle between the C1–C5 and C8–C13
planes reaches 25◦.
Synthesis of g6 cationic biaryl complexes
As some of the new h complexes kept the methylene C6 carbons
5
Scheme 7 Coupling reactions of complexes 11 and 12.
intact, all the conditions were gathered to try their rearomatisation
by exo hydride abstraction16 already successfully exploited in
our group.14b,c,d Thus, the four complexes 3a, 6a, 7a and 9a
were subjected to the action of CPh3BF4 and delivered cationic
complexes 17, 18, 19 and 20 in excellent yields ranging from 90 to
99% (Schemes 8 and 9). The synthesis of such biaryl complexes
is noteworthy because they are difficult or even impossible to
prepare by direct complexation. Indeed this method would have
introduced the Mn(CO)3 entity on one of each ring and on both
The para methoxy-phenyl boronic acid reacted with complexes
11 and 12 in the presence of Pd(PPh3)4, Na2CO3, in MeOH–
H2O (9/1), at reflux for 40 min to give the desired complexes
13 (70%) and 15 (70%), respectively (Scheme 7). When the
ortho chloro-phenyl boronic acid was used, the steric hindrance
between the chloro atom at the ortho position of the boronic
acid group and the phenyl and/or the methoxy groups of the
1
Fig. 1 ORTEP representation of complex 15 with thermal ellipsoids at 50% probability. Selected bond lengths (A): Mn–C 2.1934(14); Mn–C2
2.1818(14); Mn–C3 2.1719(15); Mn–C4 2.1190(15); Mn–C5 2.2183(16); C1–C2 1.401(2); C2–C3 1.442(2), C3–C4 1.437(2); C4–C5 1.386(2); C5–C6 1.507(2);
C6–C1 1.521(2).
˚
1570 | Dalton Trans., 2011, 40, 1567–1575
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Table 5 Crystallographic data and structure refinement for complexes 15 and 18
Complex 15
Complex 18
Empirical formula
Formula weight
T/K
C23H19MnO5
430.32
200(2)
C16H11BF5MnO4,1/2CH3OH
444.00
200(2)
0.71073
˚
Wavelength/A
0.71073
Crystal system
Space group
Monoclinic
C2/c
Monoclinic
C2/c
18.588(2)
9.4450(11)
20.1140(17)
90
90.137(8)
˚
a/A
34.311(5)
˚
b/A
10.0678(18)
11.3809(4)
90
93.870(8)
90
˚
c/A
a (◦)
b (◦)
g (◦)
90
3531.3(6)
3
˚
Volume/A
3922.5(9)
Z
8
8
Density (calculated)/Mg m-3
Absorption coefficient/mm-1
F(000)
1.457
0.705
1776
0.3 ¥ 0.3 ¥ 0.1
3.60 to 30.00◦
-48 £ h £ 48
-14 £ k £ 14
-15 £ l £ 16
30153
1.663
0.822
1768
0.2 ¥ 0.1 ¥ 0.1
2.02 to 30.00◦
-22 £ h £ 26
-13 £ k £ 13
-28 £ l £ 25
14629
Crystal size/mm3
q range for data collection/◦
Index ranges
Reflections collected
Independent reflections
Completeness to q = 30.00◦
Absorption correction
Max. and min. transmission
Refinement method
5677 [R(int) = 0.0378]
4856 [R(int) = 0.0582]
99.2%
94.1%
Semi-empirical from equiv.
0.932 and 0.391
Full-matrix least-squares F2
5677/0/268
1.013
R1 = 0.0336, wR2 = 0.0804
R1 = 0.0568, wR2 = 0.0915
0.323 and -0.325
None
—
Full-matrix least-squares F2
4856/0/259
1.064
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2s(I)]
R indices (all data)
R1 = 0.0601, wR2 = 0.1740
R1 = 0.0962, wR2 = 0.2009
1.445 and -0.576
-3
˚
Largest diff. peak and hole/e.A
graphic data are reported in Table 5. The Mn(CO)3 tripod adopts
an almost syn-eclipsed conformation with respect to the methoxy
group (4.6◦) and an anti-eclipsed to the para fluorobenzene group.
This anti-eclipsed conformation of the tripod with respect to an
electron-withdrawing substituent is relevant to other examples
described in the literature concerning anisole derivative complexes
substituted by a keto14b or an ester group14a at the para position,
where exactly the same conformations were found. Five Mn–C
Scheme 8 Rearomatization of complexes 3a, 6a, 7a.
6
˚
distances of the h system lie around 2.18 A but a longer distance
4
˚
of 2.279 A is observed for the Mn–C bond leading to a small
distortion in the sense that the C4 carbon atom is displaced by
˚
0.09 A from the plane of the 5 other carbon atoms in a direction
opposite to the Mn(CO)3 entity and the dihedral angle between
the C3C2C1C6C5 and the C3C4C5 planes reaches 6◦. It is in good
6
agreement with what is known for (h -arene)tricarbonylchromium
complexes where distortions of the arene ligands are influenced by
the electronegativity, the inductive and the resonance effects of the
arene substituents.24 The para fluoro◦aryl ring is not coplanar with
Scheme 9 Rearomatization of complex 9a.
6
rings at the same time, thus delivering three cationic complexes
whose charges would have prevented any purification by silica gel
column chromatography.
the h system, since it deviates by 17 from the coordinated ring.
6
The 1H NMR spectra of the new cationic h complexes in
Conclusion
acetone-d6 all exhibit two sets of doublets for H2, H3, H5 and H6
protons at high frequencies, in good agreement with the presence
of a para-disubstituted positively charged arene ring.
5
We have reported the first Suzuki–Miyaura couplings of (h -
cyclohexadienyl)Mn(CO)3 complexes leading to unprecedented
5
Complex 18† crystallized from methanol by a two-well diffusion
procedure (diethyl ether in the outer well), and the ORTEP view
is presented in Fig. 2 as well as selected bond lengths. Crystallo-
(h -aryl-cyclohexadienyl)Mn(CO)3 complexes. The yields depend
5
on the position of the halogen group on the h system, on steric
hindrances of the boronic acids and of the substituent at the sp3
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-
Fig. 2 ORTEP view of complex 18 with thermal ellipsoids at 50% probability level. The CH3OH and BF4 molecules have been omitted for clarity.
1
2
3
4
5
6
1
2
2
3
˚
Selected bond lengths (A): Mn–C 2.201(3); Mn–C 2.155(3); Mn–C 2.191(3); Mn–C 2.279(3); Mn–C 2.202(3); Mn–C 2.167(3); C –C 1.424(5); C –C
1.394(5); C3–C4 1.400(5); C4–C5 1.414(5); C5–C6 1.389(5); C6–C1 1.414(4).
carbon atom of the cyclohexadienyl rings. It broadens the scope
The pure products were isolated as yellow solids by flash column
chromatography on silica gel with petroleum ether as eluent.
5
of h -Mn complexes which can now be functionalized by any
of the main Pd coupling reactions. When the sp3 carbon atom
of the six-membered ring is substituted by two hydrogen atoms,
hydride abstraction by CPh3BF4 easily occurs giving rise to the
formation of new directly linked bis aryl complexes whose one
cycle is selectively coordinated to the Mn(CO)3 moiety.
g5-(1-4-Dimethoxycyclohexadienyl)Mn(CO)3 4. 1H NMR
(400 MHz, CDCl3): d = 2.77 (d, 2J = 12.7 Hz, 1 H, H6exo), 3.30 (m,
2 H, H5 and H6endo), 3.35 (s, 3 H, MeO), 3.55 (s, 3 H, MeO), 3.88
(d, 3J = 6.0 Hz, 1 H, H2), 5.30 (dd, 3J = 6.0 Hz, 4J = 2.6 Hz, 1 H,
H3) ppm. 13C NMR (100 MHz, CDCl3): d = 32.0 (C6), 35.2 (C5),
54.6 (MeO), 54.6 (MeO), 56.5 (C3), 66.2 (C2), 121.5 (C1), 140.9
(C4) ppm. IR (ATR Diamond): n = 2001, 1905 (Mn(CO)3) cm-1.
Experimental Section
g5-(1-Phenyl-4-methoxycyclohexadienyl)Mn(CO)3 3a. Yield:
0.070 g, 72%. H NMR (200 MHz, CDCl3): d = 2.57 (d, J =
12.7 Hz, 1 H, H6exo), 3.01 (dd, 3J = 6.3 Hz, 4J = 2.3 Hz, 1 H, H5),
General Procedures
1
2
All reactions were routinely performed under a dry nitrogen
atmosphere with standard Schlenk techniques. THF was dried
over sodium benzophenone ketyl and distilled. CH2Cl2 and DMF
were distilled over CaH2. NMR spectra were recorded on a Bruker
2
3
3.22 (dd, J = 12.7 Hz, J = 6.3 Hz, 1 H, H6endo), 3.47 (s, 3 H,
MeO), 5.19 (d, J = 5.8 Hz, 1 H, H2), 5.78 (d, J = 5.8 Hz, J =
2.3 Hz, 1 H, H3), 7.1 (m, 5 H, H-Ph) ppm. 13C NMR (100 MHz,
CDCl3): d = 28.8 (C6), 35.1 (C5), 53.4 (MeO), 64.8 (C3), 66.0 (C1),
91.9 (C2), 123.6–127.4 (Ph), 139.0, 142.2 (C4, C7) ppm. IR (ATR
Diamond): n = 2003, 1907 (Mn(CO)3) cm-1. ESI for C16H12MnO4:
m/z (calcd.) = 323.0105 (323.0116) [M - H].
3
3
4
ARX 200 MHz or Avance 400 MHz spectrometer. H and 13C
1
signals of NMR solvents were used as internal standards at 7.26
and 77.36 ppm, respectively, in CDCl3 and at 2.09 and 30.60 ppm in
acetone-d6. The Mn(CO)3 carbonyl signal is known to be difficult
to observe, especially when only low quantities of complex are
available. Infrared spectra were measured on a Bruker Tensor 27
spectrometer. Mass spectra were performed for ES-MS by the
Groupe de Spectrome´trie de Masse (IPCM, UMR 7201 UPMC).
Complexes 2a, 2b, 11 and 12 were synthesized according to the
procedures described in the literature. 2a: 91% yield (Lit.14a yield:
53%). 2b: 96% yield (Lit.8 yield: 78%). 11: 39% yield (Lit.13 yield
39%). 12: 46% yield (Lit.13 yield 46%).
g5-(1-Phenyl-4-methoxycyclohexadienyl)Mn(CO)3 3b. Yield:
1
0.095 g, 79%. H NMR (200 MHz, CDCl3): d = 3.41 (s, 3 H,
MeO), 3.59 (dd, 3J = 6.6 Hz, 4J = 2.6 Hz, 1 H, H5), 4.42 (d, 3J =
3
4
6.6 Hz, 1 H, H6), 5.50 (dd, J = 6.1 Hz, J = 1.3 Hz, 1 H, H2),
5.61 (dd, J = 6.1 Hz, J = 2.6 Hz, 1 H, H3), 6.80–7.04 (m, 10
H, H-Ph) ppm. 13C NMR (100 MHz, CDCl3): d = 44.1 (C5), 45.2
(C6), 54.63 (MeO), 66.2 (C3), 72.4 (C1), 92.2 (C2), 125.2–128.8 (Ph),
139.4–146.2 (C4, C7, C11) ppm. IR (ATR Diamond): n = 2010, 1919
(Mn(CO)3) cm-1. ESI for C22H16MnO4: m/z (calcd.) = 399.04236
(399.0429) [M - H].
3
4
General procedure for Suzuki–Miyaura cross-couplings of
g5-(cyclohexadienyl)Mn(CO)3 complex
In a dry round-bottom-flask containing boronic acid (0.36 mmol,
1.2 eq.), the h -(cyclohexadienyl)Mn(CO)3 complex (0.3 mmol,
g5 -(1-p-Methoxyphenyl-2-methoxycyclohexadienyl)Mn(CO)3
5a. Yield: 0.075 g, 71%. 1H NMR (200 MHz, CDCl3): d = 2.63
5
2
3
4
1 eq.), Pd(PPh3)4 (0.015 mmol, 0.05 eq.) and Na2CO3 under
argon was added the solvent mixture of water–methanol (1/9)
previously degassed with a stream of nitrogen for 5 min. The
mixture was stirred for periods varying between 15 and 50 min.
The reaction mixture was then extracted with diethyl ether (50 mL)
and the organic layer was washed with water (3 ¥ 30 mL). The
organic layers were dried over MgSO4 and the organic solvents
were removed under reduced pressure to afford yellow solids.
(d, J = 12.8 Hz, 1 H, H6exo), 3.06 (dd, J = 6.3 Hz, J = 2.4 Hz,
1 H, H5), 3.30 (ddd, 2J = 12.8 Hz, 3J = 6.3 Hz, 4J = 1.6 Hz, 1 H,
H6endo), 3.55 (s, 3 H, MeO), 3.80 (s, 3 H, MeO), 5.15 (d, 3J = 5.8 Hz,
1 H, H2), 5.81 (dd, 3J = 5.8 Hz, 4J = 2.4 Hz, 1 H, H3), 6.83 (d, 3J =
3
8.8 Hz, 2 H, H-Ar), 7.06 (d, J = 8.8 Hz, 2 H, H-Ar) ppm. 13C
NMR (100 MHz, CDCl3): d = 30.0 (C6), 35.9 (C5), 54.5 (MeO),
55.4 (MeO), 65.3 (C3), 68.9 (C1), 91.4 (C2), 114.1, 126.0 (CHAr),
132.2, 143.1, 158.7 (C4, C7, C10) ppm. IR (ATR Diamond):
1572 | Dalton Trans., 2011, 40, 1567–1575
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n = 2001, 1906 (Mn(CO)3) cm-1. ESI for C17H14MnO5: m/z
(calcd.) = 353.02162 (353.0222) [M - H].
(m, 9 H, HAr) ppm. 13C NMR (100 MHz, CDCl3): d = 44.2 (C5),
45.2 (C6), 54.7 (MeO), 66.4 (C3), 70.4 (C1), 92.3 (C2), 125.6, 126.4,
127.1, 128.8 (CAr), 132.7, 138.2, 142.1, 145.8 (C4, C7, C11, C14)
ppm. IR (ATR Diamond): n = 2010, 1921 (Mn(CO)3) cm-1. ESI
for C22H15ClMnO4: m/z (calcd.) = 433.0029 (432.0039) [M - H].
g5 -(1-p-Methoxyphenyl-4-methoxycyclohexadienyl)Mn(CO)3
5b. Yield: 0.097 g, 75%. 1H NMR (200 MHz, CDCl3): d = 3.47
(s, 3 H, MeO), 3.62 (dd, 3J = 6.5 Hz, 4J = 2.5 Hz, 1 H, H5), 3.75 (s,
3 H, MeO), 4.55 (d, 3J = 6.5 Hz, 1 H, H6), 5.52 (dd, 3J = 5.9 Hz,
4J = 1.3 Hz, 1 H, H2), 5.71 (dd, 3J = 5.9 Hz, 4J = 2.5 Hz, 1 H, H3),
6.75 (d, 3J = 8.9 Hz, 2 H, H13), 6.97 (d, 3J = 7.0 Hz, 2 H, H8), 7.09
g5-(1-o-Chlorophenyl-4-methoxycyclohexadienyl)Mn(CO)3 8a.
Yield: 0.073 g, 68%. 1H NMR (200 MHz, CDCl3): d = 2.87 (m, 2
H, H6), 3.01 (dd, 4J = 2.3 Hz, 3J = 4.6, 1 H, H5), 3.52 (s, 3 H, MeO),
4.96 (d, 3J = 5.9 Hz, 1 H, H2), 5.82 (dd, 4J = 2.3 Hz, 3J = 5.9 Hz,
1 H, H3), 7.21 (m, 3 H, HAr), 7.52 (m, 1 H, HAr) ppm. 13C NMR
(100 MHz, CDCl3): d = 32.1 (C6), 35.3 (C5), 53.3 (MeO), 63.9
(C3), 71.7 (C1), 96.1 (C2), 126.1, 127.7, 128.5, 132.4 (CAr), 132.6,
138.2, 142.1 (C12, C7, C4) ppm. IR (ATR Diamond): n = 2008, 1915
(Mn(CO)3) cm-1. ESI for C16H12ClMnO4: ESI for C16H11ClMnO4:
m/z (calcd.) = 356.9711 (356.9726) [M - H].
3
3
(d, J = 8.9 Hz, 2 H, H12), 7.14 (d, J = 7.0 Hz, 1 H, H10), 7.20
(t, 3J = 7.0 Hz, 2 H, H9) ppm. 13C NMR (100 MHz, CDCl3): d =
43.8 (C5), 45.3 (C6), 54.6 (MeO), 55.4 (MeO), 65.4 (C3), 74.1 (C1),
90.7 (C2), 114.2 (C13), 125.7 (C8), 126.5 (C12), 126.9 (C10), 128.7
(C9), 131.4, 141.8, 146.2, 158.8 (C4, C7, C11, C14) ppm. IR (ATR
Diamond): n = 2003, 1905 (Mn(CO)3) cm-1. ESI for C23H18MnO5:
m/z (calcd.) = 429.05292 (429.0535) [M - H].
g5-(1-p-Fluorophenyl-4-methoxycyclohexadienyl)Mn(CO)3 6a.
Yield: 0.083 g, 81%. H NMR (200 MHz, CDCl3): d = 2.63 (d,
g5-(1-o-Chlorophenyl-4-methoxycyclohexadienyl)Mn(CO)3 8b.
Yield: 0.083 g, 64%. 1H NMR (200 MHz, CDCl3): d = 3.56 (m, 1
H, H5), 3.58 (s, 3 H, MeO), 4.33 (d, 3J = 6.0 Hz, 1 H, H6), 5.39 (dd,
4J = 0.9 Hz, 3J = 6.0 Hz, 1 H, H2), 5.84 (dd, 4J = 2.5 Hz, 3J = 6.1 Hz,
1
2J = 12.6 Hz, 1 H, H6exo), 3.07 (dd, 3J = 6.3 Hz, 4J = 2.3 Hz, 1 H,
H5), 3.26 (ddd, 2J = 12.6 Hz, 3J = 6.3 Hz, 4J = 1.4 Hz, 1 H, H6endo),
3.54 (s, 3 H, MeO), 5.19 (d, 3J = 5.9 Hz, 1 H, H2), 5.85 (dd, 3J =
5.9 Hz, 4J = 2.3 Hz, 1 H, H3), 7.06 (m, 4 H, H8,9) ppm. 13C NMR
(100 MHz, CDCl3): d = 29.2 (C6), 35.0 (C5), 35.6 (MeO), 64.9
(C3), 66.3 (C1), 91.8 (C2), 114.6 (d, 2J = 21.4 Hz, C9), 125.3 (d, 3J =
7.7 Hz, C8), 135.3 (C7), 142.3 (C4), 161.0 (d, 1J = 246 Hz, C10) ppm.
4
1 H, H3), 6.78 (m, 2 H, HAr), 7.15 (m, 6 H, HAr), 8.00 (dd, J =
1.4 Hz, 3J = 7.7 Hz, 2 H, HAr) ppm. 13C NMR (100 MHz, CDCl3):
d = 45.1 (C5), 50.6 (C6), 54.7 (MeO), 65.0 (C3), 77.7 (C1), 95.9
(C2), 126.3 (C9), 128.3 (C8), 127.2, 127.4, 128.5, 130.2, 133.7 (CAr),
134.1, 138.4, 142.8, 145.0 (C4,7,11,12) ppm. IR (ATR Diamond): n =
2008, 1938, 1910 (Mn(CO)3) cm-1. ESI for C22H16ClMnO4Na: m/z
(calcd.) = 457.00098 (457.0015) [M + Na].
◦
4
19F NMR (400 MHz, CDCl3, 20 C): -117.6 (3J = 6.0 Hz, J =
9.0 Hz) ppm. IR (ATR Diamond): n = 2004, 1907 (Mn(CO)3) cm-1.
ESI for C16H11FMnO4: m/z (calcd.) = 341.00164 (341.0022) [M -
H].
g5 - (5¢ - Formyl - 1 - thiophene - 4 - methoxycyclohexadienyl) Mn
(CO)3 9a. Yield: 0.082 g, 76%. 1H NMR (200 MHz, CDCl3): d =
2.60 (m, 1 H, H6exo), 3.26 (m, 2 H, H6endo, H5), 3.52 (s, 3 H, MeO),
5.50 (d, 3J = 6.1 Hz, 1 H, H2), 5.89 (dd, 3J = 6.1 Hz, 4J = 2.1 Hz, 1
H, H3), 6.86 (d, 3J = 4.0 Hz, 1 H, H8), 7.58 (d, 3J = 4.0 Hz, 1 H, H9),
9.78 (s, 1 H, H11) ppm. 13C NMR (100 MHz, CDCl3): d = 30.5 (C6),
37.5 (C5), 54.7 (MeO), 57.6 (C1), 67.8 (C3), 93.4 (C2), 122.4 (C8),
137.5 (C9), 141.5 (C10), 143.7 (C4), 157.4 (C7), 182.4 (C11) ppm. IR
(ATR Diamond): n = 2010, 1923 (Mn(CO)3), 1659 (CHO) cm-1.
ESI for C15H10MnO5S: m/z (calcd.) = 356.96240 (356.9629) [M -
H].
g5-(1-p-Fluorophenyl-4-methoxycyclohexadienyl)Mn(CO)3 6b.
1
Yield: 0.093 g, 74%. H NMR (200 MHz, CDCl3): d = 3.48 (s,
3
4
3 H, MeO), 3.65 (dd, J = 6.4 Hz, J = 2.4 Hz, 1 H, H5), 4.52 d,
3J = 6.4 Hz, 1 H, H6), 5.59 (d, 3J = 6.0 Hz, 1 H, H2), 5.76 (dd, 3J =
6.0 Hz, J = 2.4 Hz, 1 H, H3), 6.86–7.23 (m, 9 H, HAr) ppm. 13C
4
NMR (100 MHz, CDCl3): d = 44.0 (C5), 45.5 (C6), 54.6 (MeO),
66.0 (C3), 71.7 (C1), 92.0 (C2), 115.7 (d, 2J = 21.4 Hz, C13), 125.7
(C9), 126.9 (d, 3J = 7.7 Hz, C12), 127.1 (C10), 128.8 (C8), 135.5 (d,
4J = 3.4 Hz, C11), 142.0, 145.9 (C7, C4), 161.8 (d, J = 245.9 Hz,
1
C14) ppm. IR (ATR Diamond): n = 2007, 1913 (Mn(CO)3) cm-1.
g5-(5¢-Formyl-1-thiophene-4-methoxycyclohexadienyl)Mn(CO)3
9b. Yield: 0.090 g, 69%. 1H NMR (200 MHz, CDCl3): d = 3.49
(s, 3 H, MeO), 3.75 (dd, 4J = 2.3 Hz, 3J = 6.3 Hz, 1 H, H5), 4.48
ESI for C22H15FMnO4: m/z (calcd.) = 417.0319 (417.0335) [M -
H].
g5-(1-p-Chlorophenyl-4-methoxycyclohexadienyl)Mn(CO)3 7a.
(d, J = 6.3 Hz, 1 H, H6), 5.75 (dd, J = 1.4 Hz, J = 6.1 Hz, 1
H, H2), 5.85 (dd, 4J = 2.3 Hz, 3J = 6.1 Hz, 1 H, H3), 6.89 (d, 3J =
3
4
3
1
Yield: 0.076 g, 71%. H NMR (200 MHz, CDCl3): d = 2.64 (d,
2J = 12.5 Hz, 1 H, H6exo), 3.12 (d, 3J = 6.1 Hz, 1 H, H5), 3.28 (dd,
4.0 Hz, 1 H, H12), 6.96–7.24 (m, 5 H, HPh), 7.50 (d, J = 4.0 Hz,
3
2
3J = 6.1 Hz, J = 12.5 Hz, 1 H, H6endo), 3.58 (s, 3 H, MeO), 5.29
1 H, H13), 9.75 (s, 1 H, H15) ppm. 13C NMR (100 MHz, CDCl3):
d = 45.5 (C5), 46.2 (C6), 54.8 (MeO), 64.2 (C1), 67.5 (C3), 92.5 (C2),
122.8 (C12), 125.8 (C9), 127.4 (C10), 128.8 (C8), 137.4 (C13), 141.4–
156.7 (C4,7,11,14), 182.3 (C15) ppm. IR (ATR Diamond): n = 2012,
1925 (Mn(CO)3) cm-1. ESI for C21H15MnO5SNa: m/z (calcd.) =
456.99129 (456.9918) [M + Na].
(d, 3J = 5.6 Hz, 1 H, H2), 5.90 (d, 3J = 5.6 Hz, 1 H, H3), 7.05 (d,
3
3J = 7.8 Hz, 2 H, H9), 7.29 (d, J = 7.8 Hz, 2 H, H8) ppm. 13C
NMR (100 MHz, CDCl3): d = 29.9 (C6), 36.3 (C5), 54.6 (MeO),
65.1 (C1), 66.3 (C3), 93.2 (C2), 125.9 (C8), 128.8 (C9), 132.6 (C10),
139.0 (C7), 143.4 (C4) ppm. IR (ATR Diamond): n = 2008, 1918
(Mn(CO)3) cm-1. ESI for C16H11ClMnO4: m/z (calcd.) = 356.9713
(356.9726) [M - H].
g5 -(1-p-Methoxyphenyl-2-methoxycyclohexadienyl)Mn(CO)3
13. Yield: 0.090 g, 70%. 1H NMR (200 MHz, CDCl3): d = 3.55
g5-(1-p-Chlorophenyl-4-methoxycyclohexadienyl)Mn(CO)3 7b.
(tapp, J = 6.2 Hz, J = 6.5 Hz, J = 0.78, 1 H, H5), 3.87 (s, 3 H,
3
3
4
1
3
Yield: 0.096 g, 74%. H NMR (200 MHz, CDCl3): d = 3.48 (s,
MeO), 3.91 (s, 3 H, MeO), 4.30 (d, J = 6.2 Hz, 1 H, H6), 4.83
3
4
3
3
3 H, MeO), 3.67 (dd, J = 6.5 Hz, J = 2.5 Hz, 1 H, H5), 4.52
(t, J = 6.5 Hz, 1 H, H4), 5.67 (d, J = 6.5 Hz, 1 H, H3), 6.74
(d, J = 6.5 Hz, 1 H, H6), 5.64 (dd, J = 6 Hz, J = 1.5 Hz, 1
(d, J = 8.8 Hz, 2 H, HAr), 6.94 (d, J = 6.1 Hz, 2 H, HAr), 6.99–
7.26 (m, 5 H, HPh) ppm. 13C NMR (100 MHz, CDCl3): d = 48.1
3
3
4
3
3
H, H2), 5.78 (dd, J = 6 Hz, J = 2.5 Hz, 1 H, H3), 6.95–7.25
3
4
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©

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(C6), 55.3 (2 MeO), 57.2 (C5), 62.5 (C1), 63.8 (C3), 77.4 (C2), 90.5
(C4), 113.2 (C13), 125.9 (CAr), 126.9 (C10), 128.7, 130.2 (CAr), 139.8,
146.7, 158.3 (C14, C11, C7) ppm. IR (ATR Diamond): n = 2004,
1907 (Mn(CO)3) cm-1. ESI for C23H19MnO5Na: m/z (calcd.) =
453.05052 (453.0511) [M + Na].
C10), 216.3 (Mn(CO)3) ppm. 19F NMR (400 MHz, (CD3)2CO,
20 ◦C): d = -111.4 (m) ppm. IR: (ATR Diamond): n = 2072; 2005;
1933 ((Mn(CO)3) cm-1. ESI for C16H11FMnO4: m/z (calcd.) =
341.00164 (341.0022) [M - BF4].
[g6-(1-p-Chlorophenyl-4-methoxyphenyl)Mn(CO)3]BF4
Yield: 0.132 g, 93%. H NMR (200 MHz, (CD3)2CO): d = 4.27
19.
g5-(1-o-Chlorophenyl-2-methoxycyclohexadienyl)Mn(CO)3 14.
Yield: 0.023 g, 18%. 1H NMR (200 MHz, CDCl3): d = 3.48 (ddd,
1
4
3
(s, 3 H, MeO), 6.68 (dd, J = 2.2 Hz, J = 7.9 Hz, 2 H, H5,3),
3
4
3J = 5.6 Hz, J = 6.6 Hz, J = 0.9 Hz, 1 H, H5), 3.68 (s, 3 H,
7.66 (m, 4 H, Har, H6,2), 8.00 (d, J = 9.4 Hz, 2 H, HAr) ppm.
3
MeO), 4.08 (d, J = 5.6 Hz, 1 H, H6), 4.22 (td, J = 5.9 Hz, J =
0.7 Hz, 1 H, H4), 5.75 (dd, 3J = 5.3 Hz, 4J = 0.9 Hz, 1 H, H3), 6.75
(dd, 3J = 7.5 Hz, 4J = 1.5 Hz, 2 H, H14), 7.15 (m, 5 H, HAr), 7.35
(ddd, 3J = 7.0 Hz, 3J = 7.7 Hz, 4J = 2.0 Hz, 1 H, HAr), 8.0 (d, 3J =
7.5 Hz, 1 H, HAr) ppm. 13C NMR (100 MHz, CDCl3): d = 52.7
(C6), 54.6 (MeO), 60.5 (C5), 61.5 (C3), 70.7 (C1), 92.3 (C4), 127.2,
136.0 (CAr), 136.6, 136.7, 139.8, 144.6 (C2, C7, C12, C13) ppm. IR
(ATR Diamond): n = 2010, 1919 ((Mn(CO)3) cm-1.
3
3
4
13C NMR (100 MHz, (CD3)2CO): d = 59.9 (MeO), 84.7 (C5,3),
103.5 (C6,2), 130.9, 131.3 (C8,9), 132.0, 138.4, 150.6 (Cq) ppm. IR:
(ATR Diamond): n = 2072, 2020, 1998 ((Mn(CO)3) cm-1. ESI for
C16H11ClMnO4: m/z (calcd.) = 356.97209 (356.9726) [M+ - BF4].
[g6-(1-p-Chlorophenyl-4-methoxyphenyl)Mn(CO)3]BF4
20.
1
0.142 g, 99%. H NMR (200 MHz, (CD3)2CO): d = 4.22 (s, 3 H,
3
3
OMe), 6.60 (d, J = 7.0 Hz, 2 H, H3,5), 7.64 (d, J = 7.0 Hz, 2
H, H6,2), 8.05 (s, 2 H, H8,9), 10.03 (s, 1 H, H11) ppm. IR: (ATR
Diamond): n = 2071, 2008 ((Mn(CO)3), 1666 (CHO) cm-1. ESI for
C15H10MnO5S: m/z (calcd.) = 356.96240 (356.9629) [M+ - BF4].
g5 -(3-p-Methoxyphenyl-2-methoxycyclohexadienyl)Mn(CO)3
15. Yield: 0.090 g, 70%. 1H NMR (200 MHz, CDCl3): d = 3.44
(s, 3 H, MeO), 3.48 (m, 2 H, H5,1), 3.88 (s, 3 H, MeO), 3.96 (t,
3
3J = 6 Hz, 1 H, H6), 5.27 (d, J = 7.3 Hz, 1 H, H4), 7.03 (m, 4
Acknowledgements
3
H, H9,13), 7.25 (m, 3 H, H12,14), 7.69 (d, J = 8.6 Hz, H8) ppm.
13C NMR (100 MHz, CDCl3): d = 40.9 (C1), 42.8 (C6), 54.8, 55.4
(C5, MeO), 56.8 (MeO), 91.3 (C3), 95.7 (C4), 113.7, 125.5, 127.0,
128.7 (CAr), 132.2 (C8), 127.8, 141.1, 147.5, 159.5 (C2,7,10,11) ppm.
IR (ATR Diamond): n = 2006; 1913 (Mn(CO)3) cm-1.
Financial support by CNRS is kindly acknowledged. We thank
G. Gontard for the X-ray structures, Universite´ P. et M. Curie,
IPCM, UMR CNRS 7201 and the Ministe`re de l’Education
Nationale et de la Recherche for a MENRT grant to D.C.
g5-(3-o-Chlorophenyl-2-methoxycyclohexadienyl)Mn(CO)3 16.
1
Yield: 0.060 g, 46%. H NMR (200 MHz, CDCl3): d = 3.55 (s,
Notes and References
3 H, MeO), 3.43 (m, 1 H, H6), 3.97 (t, 3J = 5.8 Hz, 1 H, H1), 5.00
(td, 4J = 0.7 Hz, 3J = 4.3 Hz, 1 H, H5), 5.73 (d, 3J = 4.3 Hz, 1 H,
H4), 6.97 (d, 3J = 7.4 Hz, 2 H, H14), 7.17–7.52 (m, 7 H, HAr) ppm.
IR (ATR Diamond): n = 2011, 1921 ((Mn(CO)3) cm-1.
1 (a) K. F. McDaniel, in: Comprehensive Organometallic Chemistry II,
Vol. 6 (Eds: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon
Press, Oxford, UK, 1995, pp 93; (b) F. Rose-Munch, V. Gagliardini, C.
Renard and E. Rose, Coord. Chem. Rev., 1998, 178–180, 249; (c) R. D.
Pike and D. A. Sweigart, Coord. Chem. Rev., 1999, 187, 183; (d) A. R.
Pape, K. P. Kaliappan and E. P. Ku¨ndig, Chem. Rev., 2000, 100, 2917;
(e) F. Rose-Munch and E. Rose, Eur. J. Inorg. Chem., 2002, 1269;
(f) E. P. Ku¨ndig, Topics in Organometallic Chemistry, Springer: Berlin,
2004, Vol. 7; (g) D. Astruc, Organometallic Complexes and Catalysis,
Springer, Heidelberg, 2007, pp 243.
2 (a) D. Prim, B. Andrioletti, F. Rose-Munch, E. Rose and F. Couty,
Tetrahedron, 2004, 60, 3325; (b) D. A. Sweigart, J. A. Reingold, S. U.
Son, in: Comprehensive Organometallic Chemistry III, Vol. 5, (Eds:
R. H. Crabtree, D. M. P. Mingos), Elsevier, Oxford, UK, 2006, pp 761.
3 A. J. Pearson and H. Shin, J. Org. Chem., 1994, 59, 2314 and references
therein.
4 See for example: (a) A. J. Pearson and P. R. Bruhn, J. Org. Chem.,
1991, 56, 7092; (b) W. H. Miles and H. R. Brinkman, Tetrahedron Lett.,
1992, 33, 589; (c) W. H. Miles, P. M. Smiley and H. R. Brinkman,
J. Chem. Soc., Chem. Commun., 1989, 1897; (d) A. J. Pearson and H.
Shin, Tetrahedron, 1992, 48, 7527.
5 A. J. Pearson, S. H. Lee and F. Gouzoules, J. Chem. Soc., Perkin Trans.
1, 1990, 2251.
General procedure for the rearomatisation of
g5-(1-aryl-4-methoxycyclohexadienyl)Mn(CO)3 complexes
A round-bottom-flask charged with CPh3BF4 (0.212 g, 0.64 mmol)
and dried CH2Cl2 (3 mL) was transferred to a round-bottom-flask
charged with h -(1-aryl-4-methoxy-cyclohexadienyl)Mn(CO)3
(0.32 mmol) and dried CH2Cl2 (4 mL). After 30 min stirring at
0 ◦C, dried diethyl ether (30 mL) was added. The yellow precipitate
was filtered, washed with diethyl ether and dried in vacuo over
night.
5
[g6-(1-Phenyl-4-methoxyphenyl)Mn(CO)3]BF4
17. Yield:
1
0.118 g, 90%. H NMR (200 MHz, (CD3)2CO): d = 4.27 (s, 3 H,
MeO), 6.68 (d, J = 7.5 Hz, 2 H, H5,3), 7.64 (m, 5 H, H2,6,9,10),
3
7.97 (m, 2 H, H8) ppm. 13C NMR (100 MHz, (CD3)2CO): d =
59.9 (MeO), 84.8 (C3,5), 103.6 (C6,2), 129.1, 131.3, 132.8 (C8,9,10),
150.4 (Cq) ppm. IR: (ATR Diamond): n = 2068, 2021, 1959
((Mn(CO)3) cm-1. ESI for C16H12MnO4: m/z (calcd.) = 323.01106
(323.0116) [M+ - BF4].
6 B. C. Roel, K. F. Mc Daniel, W. S. Waughan and T. S. Macy,
Organometallics, 1993, 12, 224.
7 (a) A. Eloi, F. Rose-Munch and E. Rose, J. Am. Chem. Soc., 2009, 131,
14178; (b) A. Eloi, F. Rose-Munch, E. Rose, A. Pille, P. Lesot and P.
Herson, Organometallics, 2010, 29, 3876.
8 F. Balssa, V. Gagliardini, F. Rose-Munch and E. Rose, Organometallics,
1996, 15, 4373; the first cine,9 tele-meta10 and tele-para11 SNAr in
[g6-(1-p-Fluorophenyl-4-methoxyphenyl)Mn(CO)3]BF4
18.
6
organometallic chemistry have been discovered in the h -Cr complex
Yield: 0.123 g, 90%. 1H NMR (200 MHz, (CD3)2CO): d = 4.21 (s,
3 H, MeO), 6.59 (d, 3J = 7.6 Hz, 2 H, H3,5), 7.37 (tapp, 3J = 8.7 Hz,
4J = 2.1 Hz, 2 H, H9), 7.58 (d, 3J = 7.6 Hz, 2 H, H6,2), 8.01 (m, 2 H,
H8) ppm. 13C NMR (100 MHz, (CD3)2CO): d = 59.0 (MeO), 83.9
(C3,5), 102.5 (C2,6), 106.9 (C1,4,7), 117.3 (2J = 22.3 Hz, C9), 128.6
(C1,4,7), 130.7 (3J = 8.6 Hz, C8), 149.4 (C1,4,7), 165.1 (1J = 248.5 Hz,
series. For ipso substitutions of Cr complexes see references 11d–f.
9 (a) F. Rose-Munch, E. Rose and A. Semra, J. Chem. Soc., Chem.
Commun., 1986, 1551; (b) F. Rose-Munch, E. Rose, A. Semra, Y.
Jeannin and F. Robert, J. Organomet. Chem., 1988, 353, 53; (c) F.
Rose-Munch, E. Rose, A. Semra and C. Bois, J. Organomet. Chem.,
1989, 363, 103; (d) J. P. Djukic, F. Rose-Munch and E. Rose, J. Chem.
Soc., Chem. Commun., 1991, 1634; (e) F. Rose-Munch, O. Bellot, L.
1574 | Dalton Trans., 2011, 40, 1567–1575
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Mignon, A. Semra, F. Robert and Y. Jeannin, J. Organomet. Chem.,
1991, 402, 1.
10 (a) J. C. Boutonnet, F. Rose-Munch and E. Rose, Tetrahedron Lett.,
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Soc., Chem. Commun., 1986, 1108.
and C. Guyard-Duhayon, Organometallics, 2004, 23, 184; (d) S.
Schouteeten, J.-P. Tranchier, F. Rose-Munch, E. Rose, A. Auffrant and
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Munch, D. Jonathan, J.-P. Tranchier and E. Rose, Organometallics,
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11 (a) F. Rose-Munch and E. Rose, J. Chem. Soc., Chem. Commun., 1987,
942; (b) J. C. Boutonnet, F. Rose-Munch, E. Rose and A. Semra, Bull.
Soc. Chim. Fr., 1987, 640; (c) J. P. Djukic, F. Rose-Munch and E. Rose,
Organometallics, 1995, 14, 2027; (d) For ipso SNAr in Cr complexes, see
for example: F. Rose-Munch, E. Rose, A. Semra, J. Garcia-Oricain and
C. Knobler, J. Organomet. Chem., 1989, 363, 297; (e) F. Rose-Munch,
K. Aniss and E. Rose, J. Organomet. Chem., 1990, 385, C1; (f) F. Rose-
Munch, K. Aniss, E. Rose and J. Vaisserman, J. Organomet. Chem.,
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12 (a) B. Jacques, M. Chavarot, F. Rose-Munch and E. Rose, Angew.
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M. Chavarot-Kerlidou, F. Rose-Munch, E. Rose and H. Ge´rard,
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Kerlidou, F. Rose-Munch, E. Rose, H. Ge´rard and P. Herson,
Organometallics, 2008, 27, 2505; (d) D. Cetiner, B. Jacques, E. Payet,
M. Chavarot-Kerlidou, F. Rose-Munch, E. Rose, J. P. Tranchier and P.
Herson, Dalton Trans., 2009, 27; (e) A. Eloi, F. Rose-Munch, E. Rose,
M. Chavarot-Kerlidou and H. Ge´rard, Organometallics, 2009, 28, 925.
13 A. Eloi, F. Rose-Munch, E. Rose and P. Lennartz, Organometallics,
2009, 28, 5757.
15 (a) M. Li, N. Riache, J. P. Tranchier, F. Rose-Munch, E. Rose, P.
Herson, A. Bossi, C. Rigamonti and E. Licandro, Synthesis, 2007,
2, 277; (b) M. Ethe`ve-Quelquejeu, J. P. Tranchier, F. Rose-Munch, E.
Rose, L. Naesens and E. De Clercq, Organometallics, 2007, 26, 5727;
(c) D. Cetiner, L. Norel, J. P. Tranchier, F. Rose-Munch, E. Rose and P.
Herson, Organometallics, 2010, 29, 1778.
16 P. L. Pauson and J. A. Segal, J. Chem. Soc., Dalton Trans., 1975, 1677.
17 D. Jackson, S. J. Villa, D. S. Bacon, R. D. Pike and G. B. Carpenter,
Organometallics, 1994, 13, 3972.
18 F. Carpentier, Y. Castanet, J. Brocard, A. Mortreux, F. Rose-Munch,
C. Susanne and E. Rose, J. Organomet. Chem., 1995, 493, C22.
19 (a) D. Prim, A. Auffrant, F. Rose-Munch, E. Rose and J. Vaissermann,
Organometallics, 2001, 20, 1901; (b) D. Cetiner, J. P. Tranchier, F. Rose-
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20 See for example: D. Prim, J.-P. Tranchier, F. Rose-Munch, E. Rose and
J. Vaissermann, Eur. J. Inorg. Chem., 2000, 901.
21 See for example: M. Jakt, L. Johannissen, H. S. Rzepa and D. A.
Widdowson, J. Chem. Soc., Perkin Trans. 2, 2002, 576.
22 See for example: Y. Tanaka, T. Sakamoto, K. Kamikawa and M.
Uemura, Synlett., 2003, 519.
14 (a) A. Auffrant, D. Prim, F. Rose-Munch, E. Rose and J. Vaissermann,
Organometallics, 2001, 20, 3214; (b) A. Auffrant, D. Prim, F. Rose-
Munch, E. Rose and J. Vaissermann, Organometallics, 2003, 22, 1898;
(c) B. Jacques, J.-P. Tranchier, F. Rose-Munch, E. Rose, R. Stephenson
23 V. Farina, B. Krishnan, D. R. Marshall and G. P. Ross, J. Org. Chem.,
1993, 58, 5434.
24 J. P. Djukic, F. Rose-Munch, E. Rose and J. Vaissermann, Eur. J. Inorg.
Chem., 2000, 1295.
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