The reaction of diazocyclopentadienyl compounds with cyclomanganated arenes as a route to ligand-appended cymantrenes

Article abstract of DOI:10.1002/ejic.200300855

The thermolysis of various cyclomanganated arenes in the presence of 5-diazocyclopentadiene, 7-diazoindene or 9-diazofluorene afforded the corresponding arenes tethered with cymantrenyl, benzocymantrenyl or dibenzocymantrenyl groups in fair to good yields. This reaction implies a multi-facetted mechanism that consists of three steps: the insertion of an alkylidene moiety into a C-Mn bond, a C_Ar-C bond formation and several haptotropic ring-slippages. The coupling reaction has proven to be particularly efficient with Mn(CO)₄ chelates derived from acetylarenes and nitrogen-containing heterocycles. In one case of a 2-phenyl-2-oxazoline complex, the coupling with 9-diazofluorene yields a new η¹-dibenzocymantrene complex in which the Mn(CO)₄ moiety is chelated and is part of a six-membered metallacycle. The results of this study are mainly supported by the molecular structures of nine new complexes obtained by X-ray diffraction analyses. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300855

FULL PAPER
The Reaction of Diazocyclopentadienyl Compounds with Cyclomanganated
Arenes as a Route to Ligand-Appended Cymantrenes
Jean-Pierre Djukic,*[a] Christophe Michon,[a] Dirk Heiser,[b] Nathalie Kyritsakas-Gruber,[c]
[c]
[b]
[a]
´
Andre de Cian, Karl Heinz Dötz, and Michel Pfeffer
Keywords: Diazo compounds / Cyclopentadienyl ligands / Insertion / Manganese / Ligand design
The thermolysis of various cyclomanganated arenes in the
presence of 5-diazocyclopentadiene, 7-diazoindene or 9-di-
containing heterocycles. In one case of a 2-phenyl-2-oxazo-
line complex, the coupling with 9-diazofluorene yields a new
azofluorene afforded the corresponding arenes tethered with η1-dibenzocymantrene complex in which the Mn(CO)4 moi-
cymantrenyl, benzocymantrenyl or dibenzocymantrenyl
groups in fair to good yields. This reaction implies a multi-
facetted mechanism that consists of three steps: the insertion
of an alkylidene moiety into a C−Mn bond, a CAr−C bond
formation and several haptotropic ring-slippages. The coup-
ling reaction has proven to be particularly efficient with
Mn(CO)4 chelates derived from acetylarenes and nitrogen-
ety is chelated and is part of a six-membered metallacycle.
The results of this study are mainly supported by the molecu-
lar structures of nine new complexes obtained by X-ray dif-
fraction analyses.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
cently, a series of reactions involving carbonylrhenium com-
plexes were disclosed by Katzenellenbogen and co-work-
ers[3] who were focusing on the synthesis of cyrhetrenes (Re
analogues of cymantrenes) for various applications as con-
trast agents in imaging.[4] Both cymantrenes and their Re
analogues can be used as labels for biomolecules[5,6] and in
radiopharmaceuticals.[7]
We recently reported the thermolytic coupling of cyclo-
manganated compounds with non-cyclic diazoalkanes,
which may efficiently yield new spiralenes.[1] We also
showed that the same experiments carried out with 9-diazo-
fluorene could lead to the corresponding tethered η5-fluor-
enyl complex resulting from the insertion of a fluorenylid-
ene into the CArϪMn bond of the substrate [Equa-
tion (1)].[1a] Such an insertion reaction of an alkylidene li-
gand into
a CArϪMn bond of a cyclomanganated
compound, which leads to an appended dibenzocymantrene
derivative, was unprecedented, although similar insertions
of alkylidenes were already known but never thoroughly ap-
plied to a wide range of substrates. The first reactions of
that kind were between diazocyclopentadiene and
(CO)5MnX (X ϭ Cl, Br, I), and yielded halocymantrenes,
as reported by Shaver and later by Herrmann.[2] More re-
(1)
Our previous results indicated that cymantrenes or
-rhetrenes with either an η5- or an η1-bonding mode [C and
D, Equation (1)] and appended with various internal li-
gands can be easily synthesised from readily available cyclo-
manganated complexes [A, Equation (1)] and 9-diazofluor-
ene [B, Equation (1)]. One potential application of such
complexes could be as chelating ligands for homogeneous
catalysis.[8] Indeed, appended cyclopentadienyl-type ligands
have received a great deal of attention and are widely inves-
tigated for the design of organometallic complexes of both
early and late transition metals, which are expected to be
active catalysts in various transformations such as the
[a]
`
´
CNRS UMR 7513, Laboratoire de Syntheses Metallo-induites,
4 rue Blaise Pascal, 67000 Strasbourg, France
Fax: (internat.) ϩ 33-3-90245001
E-mail: djukic@chimie.u-strasbg.fr
[b]
[c]
´
Kekule Institut für Organische Chemie und Biochemie der
Universität Bonn,
Gerhard-Domagk Straße 1, 53121 Bonn, Germany
Fax: (internat.) ϩ 49-228-73-5813
E-mail: doetz@uni-bonn.de
Service d’Analyse par Diffraction des Rayons X, Institut de
Chimie de Strasbourg,
4 rue Blaise Pascal, 67000 Strasbourg, France
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122
DOI: 10.1002/ejic.200300855
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2107

J.-P. Djukic et al.
FULL PAPER
ZieglerϪNatta polymerisation.[9] These valuable appended
An efficient synthesis of 9-diazofluorene (1c) was
Cp-like ligands can be synthesized by several different achieved by oxidation of the commercially available fluor-
methods. In this article we disclose our recent findings on enone hydrazone by yellow mercury() oxide (or activated
the investigation of the reactivity of a series of cyclomanga- manganese dioxide).[14] This reaction afforded a stable,
nated compounds towards 1-diazocyclopentadiene, 7-diazo- deep-purple crystalline compound that can be stored at
indene and 9-diazofluorene. With the support of various Ϫ10 °C for months. The thermal decomposition of this re-
examples, we show that arenes tethered by cymantrenes can agent in solution in toluene mostly produces the corre-
be efficiently synthesised by a multi-facetted reaction con- sponding azines and alkenes.[15]
sisting of three steps: the insertion of an alkylidene moiety
The synthesis of diazoindene 1b was performed by apply-
into a CϪMn bond, CArϪC bond formation and a series ing the method described by Weil and Cais,[16] and im-
of haptotropic ring-slippages. We further show that the sup- proved by Rewicki and Tuchscherer by the diazo-transfer
posedly temperature-sensitive diazocyclopentadiene and di- reaction of tosyl azide with a large excess of freshly distilled
azoindene react efficiently as alkylidene sources even at indene in the presence of diethylamine at 0 °C.[17] This re-
temperatures as high as 100 °C.
agent can also be obtained from a BamfordϪStevens-type
transformation[18] of the indenone tosylhydrazone[19] pre-
pared in several steps[20] from indanone. This diazoalkane
is quite unstable and decomposes slowly in a non-explosive
manner above 0 °C. When synthesised it can be stored for
weeks if cooled to a temperature lower than Ϫ20 °C. In our
hands, 1b was formed in high yields and had to be extracted
from a crude mixture that mostly contained limited
amounts of insoluble tosylamide and large amounts of un-
changed indene. The extraction and isolation of a highly
enriched sample of diazoindene implied two critical and
crucial steps, as already discussed by Herrmann and co-
workers: (1) the removal of the large amounts of unchanged
indene by distillation under reduced pressure, which had to
be carried out carefully with mild and slow heating of the
crude mixture in an oil-bath, and (2) a low-temperature
(Ϫ10 °C) chromatographic separation on silica gel of the
red-orange diazoindene 1b from the brownish tar formed
during step (1).
The synthesis of diazocyclopentadiene (1a) first reported
by Doering and DePuy in 1953[21] and later improved by
Weil and Cais and by Regitz and Liedhegener,[22] was even
more tricky, although still possible. It was based on the
above-mentioned diazo-transfer reaction between tosyl az-
ide and freshly cracked cyclopentadiene in the presence of
diethylamine in hexane at 0 °C. Because of its sensitive nat-
ure we did not attempt to isolate diazocyclopentadiene (1a)
neat; it was handled instead in solution in an aliphatic sol-
vent. It could be readily extracted from the crude reaction
medium and purified by a low-temperature chromato-
graphic separation on silica gel to remove tosylamide that
was formed during the diazo-transfer reaction. The concen-
tration of 1a was readily assessed, as advocated by Weil and
Cais, by a gravimetric titration of the phosphazine obtained
from reaction of an aliquot of the mother solution with tri-
phenylphosphane.
Results and Discussion
The Preparation of 5-Diazocyclopentadiene (1a), 7-Diazo-
indene (1b), and 9-Diazofluorene (1c)
The poor reputation of diazomethane has thrown a
shadow of suspicion on all the members of this class of
reagents, although recent research has contributed to give a
better and friendlier image, at least, to diazocyclopentadi-
enes. For instance, natural diazofluorenes, such as some ki-
namycins, are active antitumor and antibiotic agents as they
display some capabilities to cleave DNA,[10,11] and diazo-
cyclopentadiene (1a) has been found to regulate ethylene
production in tomatoes.[12]
When we decided to synthesise 1aϪc, most of the prob-
lems we encountered were not related to the putative ex-
plosive and unstable nature of diazoalkanes, which is not
marked for most aryl-substituted diazoalkanes, but rather
to their purification. The chemical stability and the feasibil-
ity of the targeted reagents conditioned our choice of syn-
thetic pathway among all the known methods (Scheme 1).
There are several different ways to introduce the diazo func-
tion that were compiled and detailed in pertinent reviews
or books several years ago; these procedures will therefore
not be detailed here.[13]
The Reaction of Monomanganated Complexes with 1a؊c
It has long been known that cyclomanganated complexes
of formula cis-[(LC)Mn(CO)4] (LC: carbanionic chelating
ligand) can undergo the replacement of one carbonyl ligand
by a σ-donor ligand upon heating (Scheme 2).[23] In every
reported case the incoming ligand occupies the axial posi-
tion formerly occupied by the displaced carbonyl ligand,
although this does not mean that the thermolysis of tetra-
Scheme 1
2108
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122

The Reaction of Diazocyclopentadienyl Compounds with Cyclomanganated Arenes
FULL PAPER
carbonylmanganese chelates proceeds by the selective ex- solved CO to give the [(η1-fluorenyl)Re(CO)4] complex 2e.
pulsion of one of the axial ligands. Although the mecha- To check the validity of this coupling reaction with sub-
nism of this thermolytic decarbonylation is still not known, strates containing various sorts of internal ligands, we de-
a thermodynamic control is probably responsible for the cided to address the reactivity of diazocyclopentadienyl
formation of a fac-tricarbonylmanganese chelate.
compounds such as 1aϪc with complexes 3Ϫ10. Each ther-
molytic coupling reaction was carried out with an excess of
the diazoalkane in order to compensate for the loss of re-
agent caused by a concomitant thermo-promoted conver-
sion into azines and olefins. The course of the reaction
could also be monitored by IR spectroscopy. The reaction
was generally stopped when the characteristic four car-
bonyl-ligand stretching vibration bands generated by the
M(CO)4 group of the substrate completely faded out and
were replaced by the characteristic two CO A1 and E
stretching vibration bands of the final product arising from
the fac-Mn(CO)3 fragment.
Scheme 2
Among all the possible adducts that may arise from the
coordination of a donor ligand to the electron-deficient
MnI centre, only the facial stereoisomer presents three trans
influences that may significantly contribute to the stabilis-
ation of the complex. When the exogenous ligand is a diazo-
alkane, we previously proposed that its coordination to Mn
leads to a zwitterionic transient species — a manganese yl-
ide — that evolves by elimination of N2 to give a metallaal-
kylidene intermediate. A cis migration of the aromatic car-
bon atom bonded to the manganese atom creates a CϪC
bond between the exogenous alkylidene fragment and the
chelate. At this point, we previously showed that the fluor-
enylidene species not only inserts into the carbonϪmetal
bond, but the chelate itself is dismantled by the cleavage of
the MnϪL bond, which is followed by a series of hapto-
tropic shifts. In most cases, the final compounds are the
corresponding [(η5-fluorenyl)Mn(CO)3] complexes 2aϪd
and 2g.
We first focussed our attention on the reactivity of 3 with
1c [Equation (2) and Table 1, Entry 1]. Unfortunately, every
attempted reaction between these two reagents led to the
decomposition of 3 into dark-brown intractable com-
pounds. More promising results were obtained with 4
[Equation (3)] and 5 [Equation (4)], which reacted readily
and cleanly with 1c to yield the corresponding substituted
(η5-fluorenylidene)Mn(CO)3 complexes 4a and 5a (Table 1,
Entries 2 and 3). The treatment of complex 6 with an excess
of 1c yielded a new brownish tetracarbonylmanganese che-
late that was later identified by crystallographic means as
complex 6a, an analogue of 2e [Equation (5) and Table 1,
Entry 4]. The former plausibly arises from the car-
bonylation of the corresponding (η5-fluorenyl)Mn(CO)3
In the case of the rhenium() complex 2d, we showed that precursor, which was not isolated or detected in the crude
it could undergo a haptotropic shift upon reaction with dis- mixture.
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2109

J.-P. Djukic et al.
FULL PAPER
Table 1. Experimental conditions used for the thermolytic coupling of diazocyclopentadienes 1a؊c with cyclomanganated aromatic
compounds 3Ϫ13
Entry
Substrate
R2CN2
T [°C]
Solvent(s)
Product(s)
Isolated yields (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
3
4
1c
1c
1c
1c
1a
1b
1b
1a
1b
1a
1c
1c
1c
50
100
70
80
100
70
100
100
80
100
100
110
70
pentane/toluene
heptane/toluene
hexane/toluene
cyclohexane/toluene
heptane/hexane
hexane/cyclohexane
heptane/toluene
heptane/cyclohexane
cyclohexane/toluene
heptane/hexane
heptane/toluene
toluene
3a
Ϫ
70
63
74
67
87
76
66
55
71
84
61
Ͼ 90
4a
5
5a
6
6a
7
7a
7
7b
8
8a
9
9a
9
u-9b/l-9b (4:1)
10
11
12
13
10a
11a
12a
13a
hexane/toluene
(2)
Scheme 4
(3)
treated with 1b; complex 7 yielded 7b (Scheme 3 and
Table 1, Entry 6). The latter displayed a surprising dynamic
behaviour when analysed by NMR spectroscopy in CDCl3.
A sample of 7b dissolved in CDCl3 was analysed at various
sub-ambient temperatures until the resolution of the spec-
trum was sufficient to assume that a slow exchange had
been reached. At 243 K we observed two sets of signals be-
longing to two isomers of this tris(aromatic) organometallic
compound in a 1:3 ratio (Figure 1). Figure 1 displays the
two signals of the olefinic protons of the indenyl fragment
and their dependence on temperature. At first we thought
that one of the two species might result from a combination
of reversible coordination of the internal pyridyl group to
the MnI centre and a haptotropic shift — or ring slipp-
age[24] — from an η5 to an η3 mode, which indeed should
cancel out the isochronicity of the three carbonyl ligands of
the Mn(CO)3 moiety.
(4)
(5)
(6)
Scheme 3
Complexes 7 (Scheme 3), 9 (Scheme 4) and 10 [Equa-
A 13C NMR spectrum recorded at Ϫ30 °C displayed only
tion (6)] reacted readily with 1a to give the corresponding one intense signal at δ ϭ 225 ppm, which is rather consist-
substituted (η5-cyclopentadienyl)Mn(CO)3 complexes 7a, ent with a rapidly rotating M(CO)3 group (Figure 2). We
9a and 10a, respectively (Table 1, Entries 5, 8 and 10). Simi- therefore deduced that the observed dynamic effect was
lar results were obtained when the same substrates were probably the consequence of a conformational equilibrium
2110
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122

The Reaction of Diazocyclopentadienyl Compounds with Cyclomanganated Arenes
FULL PAPER
Figure 1. Temperature dependence of the 1H NMR spectrum of 7b in CDCl3; enlargement of the olefinic indenyl protons region; the
temperature dependency plausibly stems from a conformational equilibrium between two unequally populated conformers, whose
Newman-type projections are depicted
or exo with respect to the rest of the molecule (Figure 1).
Strikingly, the 13C NMR signals belonging to the indenyl
group are distinguishable as sharp singlets only when the
temperature drops down to 243 K. They appear as two sets
of five signals between δ ϭ 65 and 110 ppm (Figure 2). At
room temperature, only the signal of the olefinic carbon
atom C-4 (connected to 4-H) is well resolved since the dif-
ference in chemical shift between the two corresponding
signals amounts to only 0.6 ppm at the slow exchange rate
(Figure 2). From the analysis of the cross-peak correlation
1
between the two sets of signals, a two-dimensional H-1H
ROESY experiment carried out at 243 K allowed us to con-
firm that within the timescale of 1H NMR a slow exchange
exists between two unequally populated species (see Sup-
porting Information). Unfortunately, we could not deduce
any clue as to the structure of the major conformer because
of the intricate mixing of the cross-peak correlations gener-
ated by pure nuclear Overhauser effects with those arising
from the chemical exchange.
The reaction of complex 9 with 1b yielded the two dia-
stereomers u-9b and l-9b in a 4:1 ratio (Scheme 4 and
Table 1, Entry 9). The predominance of u-9b, whose struc-
ture was firmly ascertained by X-ray diffraction analyses
(vide infra), can be explained by the intervention of a late
transition state in which the Mn-to-indenyl electronic inter-
action would define the activation barrier of the alkylidene
Figure 2. Temperature dependence of the 13C NMR spectrum of
7b in CDCl3; enlargements of the areas of resonance of the η5-
bonded indenyl 13C atoms (left) and of the Mn(CO)3 fragment
(right)
involving the rotation of the disubstituted pyridyl group. insertion step. This is a proposal somewhat similar to that
Such a conformational equilibrium should likely involve made for the mechanism of formation of ‘‘spiralenes’’.[1b]
two conformers differing only in the orientation of the pyri- Indeed, prior to insertion, the indenylidene ligand may ad-
dyl group, which should place the methyl group either endo opt several conformations, among which only two are rel-
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2111

J.-P. Djukic et al.
FULL PAPER
Scheme 5
evant for the cis-migration step: on the one hand, the benzo
fragment of the indenylidene is placed at an endo position,
and on the other the same fragment is found at an exo posi-
tion with respect to the chelate (Scheme 5).
Upon insertion of the indenylidene, the formation of the
carbonϪcarbon bond is accompanied by the creation of a
vacant coordination site at the manganese centre that can
be filled by an interaction with the π-system of the indenyl
species. The ratio between the two products illustrates the
intracyclic strains, which are putatively lower in the endo
stereoisomer than in the exo isomer.
(8)
(9)
Complex 8 successfully reacted with an excess of 1b to
yield the aromatic ketone 8a in good yield [Equation (7)
and Table 1, Entry 7].
(10)
(7)
This complex displays a pronounced insolubility even in
polar solvents such as tetrahydrofuran, which prevented its
purification by chromatography and its full characterisation
by NMR spectroscopy. Its IR spectrum measured with a
KBr pellet displays the expected stretching bands related to
the Mn(CO)3 group at ν˜ ϭ 2013 and 1926 cmϪ1 and that
The Reaction of Dimanganated Complexes with 1c
Complexes 11 and 12, derived from pyrimidine, were
treated with an excess of 1c and gave the corresponding
dinuclear complexes 11a and 12a in good yields [Equations
(8) and (9), Table 1, Entries 11 and 12]. Both complexes
could be purified by column flash chromatography in spite
of their polarity. The reaction of 13 with 1c under the same
conditions also afforded the corresponding dimetallic prod-
uct 13a, which precipitated immediately [Equation (10),
Table 1, Entry 13].
related to the ketone functions at ν˜ϭ 1694 cmϪ1
.
Structural and Spectroscopic Properties of Complexes
4؊8a, 9b and 10؊12a
Most of the new complexes reported here crystallised re-
adily. In this article, we present the structures obtained by
2112
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122

The Reaction of Diazocyclopentadienyl Compounds with Cyclomanganated Arenes
FULL PAPER
Figure 5. ORTEP diagram of compound 6a, with the atom num-
bering scheme; the molecule of solvent and hydrogen atoms have
been omitted for clarity; the ellipsoids are drawn at the 30% prob-
˚
Figure 3. ORTEP diagram of compound 4a, with the atom num-
bering scheme; hydrogen atoms have been omitted for clarity; the
ellipsoids are drawn at the 30% probability level; selected in-
ability level; selected interatomic distances [A] and angles [°]:
MnϪC14 2.251(2), MnϪC1 1.869(2), MnϪC2 1.868(3), MnϪC3
1.821(3), MnϪN, 2.042(2), NϪC7 1.285(3), O5ϪC7 1.348(3);
NϪMnϪC14 84.36(2), C8ϪC13ϪC12 116.6(2), C15ϪC14ϪC26
102.4(2)
˚
teratomic distances [A]: MnϪC6 2.126(2), MnϪC5 2.189(2),
MnϪC8 2.202(2), MnϪC2 1.803(3), MnϪC1 1.783(3), MnϪC3
1.780(3), C6ϪC17 1.507(3), C6ϪC7 1.439(3), C8ϪC4 1.449(3)
Figure 6. ORTEP diagram of compound 7a, with the atom num-
bering scheme; atoms of hydrogen have been omitted for clarity;
the ellipsoids are drawn at the 30% probability level; selected in-
˚
teratomic distances [A] and angles [°]: MnϪC1 1.787(2), MnϪC2
1.804(3), MnϪC3 1.779(2), MnϪC8 2.154(2), MnϪC4 2.145 (2),
MnϪC5 2.137(2), C8ϪC9 1.488(3); C4ϪC8ϪC7 106.4(2)
Figure 4. ORTEP diagram of compound 5a, with the atom num-
bering scheme; the molecule of solvent and hydrogen atoms have
been omitted for clarity; the ellipsoids are drawn at the 30% prob-
˚
ability level; selected interatomic distances [A] and angles [°]:
MnϪC1 1.789(4), MnϪC2 1.786(3), MnϪC3 1.792(4), MnϪC4
2.181(3), MnϪC5 2.198(3), MnϪC6 2.203(3), MnϪC7 2.191(3),
MnϪC8 2.157(3), FeϪC31 2.060(3), C8ϪC17 1.480(4),
In most structures where the Mn centre is bonded to the
cyclopentadienyl moiety, there are disparities among the
MnϪCAr bond lengths that reveal a sensitivity of the
Mn(CO)3 moiety to steric hindrance (Table 2). In η5-fluor-
centroidFcϪcentroidfluorene
3.792(4);
C1ϪMnϪC2
90.9(1),
C1ϪMnϪC3 93.2(2), C2ϪMnϪC3 91.8(1)
enyl complexes (Figures 3, 4, 10 and 11) the CipsoϪMn dis-
˚
X-ray diffraction analyses for 4a (Figure 3), 5a (Figure 4), tance can vary from 2.126(2) to 2.157(3) A while the other
6a (Figure 5), 7a (Figure 6), 8a (Figure 7), 9a (Figure 8), u-
C
ArϪMn bonds remain unaffected, with an interatomic dis-
5
˚
9b (Figure 9), 11a (Figure 10) and 12a (Figure 11). Main tance of about 2.195 A. In a similar way, with η -indenyl
acquisition and refinement data are collected at the end of complexes, the largest variation of the carbonϪmanganese
the Exp. Sect.; ORTEP diagrams of the relevant structures distances is noticed for the CipsoϪMn and ϽColefinicϪMnϾ
are given in the relevant figure, along with the atom num- distances from 2.139(2) to 2.155(4) A and from 2.126(2) to
bering scheme and selected geometrical information.
˚
˚
2.141(2) A in 8a (Figure 7) and 9b (Figure 9), respectively.
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2113

J.-P. Djukic et al.
FULL PAPER
Figure 9. ORTEP diagram of compound u-9b, with the atom num-
bering scheme; atoms of hydrogen have been omitted for clarity;
the ellipsoids are drawn at the 30% probability level; selected in-
˚
teratomic distances [A]: MnϪC4 2.155(2), MnϪC5 2.138(2),
Figure 7. ORTEP diagram of compound 8a, with the atom num-
bering scheme; atoms of hydrogen have been omitted for clarity;
the ellipsoids are drawn at the 30% probability level; selected in-
MnϪC6 2.144(2), CrϪC16 2.259(2)
˚
teratomic distances [A] and angles [°]:MnϪC12 2.139(2), C12ϪC13
1.484(3), C22ϪC23 1.516(3), C23ϪO4 1.211(2); C4ϪC12ϪC11
106.4(2)
matic distortions are observed in the dinuclear complex 9a,
in which CipsoϪMn is the largest CCpϪMn distance with a
value of 2.167(4) A and C9ϪMn is the smallest distance
with a value of 2.137(4) A (Figure 8). In the (η -aryl)tricar-
bonylchromium fragment the largest CϪCr distance is
CrϪC12, with a value of 2.240(4) A, whereas the remaining
˚
6
˚
˚
˚
C(13Ϫ17)ϪCr distances amount to about 2.216 A.
If we look closely at the reported structures of cymantr-
enes and benzo- and dibenzocymantrenes stored in the
Cambridge Structural Database (CSD), we notice that the
centroidϪMn distance clearly increases from cyclopen-
tadienyl- to fluorenyl-type ligands. As already mentioned,
and revealed previously by Calhorda and Veiros, this rela-
tive increase of the metalϪcyclopentadienyl ligand dis-
tances stems from intrinsically different metal-to-π-system
bonding modes, which is truly η5 in Cp derivatives and
seemingly more η3-η2 in indenyl derivatives.[24,25] The
Figure 8. ORTEP diagram of compound rac-9a, with the atom
numbering scheme; the molecule of solvent and hydrogen atoms
have been omitted for clarity; the ellipsoids are drawn at the 30%
C
ipsoϪMn distances seem much more sensitive to a factor
such as steric hindrance than to changes in the electronic
properties of neighbouring substituents. This can be readily
assessed by the relative dispersion of the CipsoϪMn dis-
tances collected from the CSD for monosubstituted cym-
antrenes.[26] Table 3 lists the statistical data related to
centroidϪMn and CipsoϪMn distances of 20 structures of
monosubstituted cymantrenes deposited with the CSD.[27]
˚
probability level; selected interatomic distances [A]: CrϪC12
2.240(4), CrϪC17 2.215(3), CrϪC15 2.217(4), MnϪC11 2.167(4),
MnϪC9 2.137(4), MnϪC7 2.144(4), C17ϪC18 1.506(5),
C11ϪC12 1.484(5)
Again the CArϪMn bond lengths remain almost unaffected For the benzo and dibenzo analogues, only two and three
˚
and remain at an average value of 2.202 A.
examples, respectively, have been selected based on their
Likewise, within the η5-cyclopentadienyl complexes the substitution pattern and their structural analogy with the
disparity existing between CCpϪMn bond lengths is larger complexes reported herein (Table 4).
and directly related to the presence of bulky groups such as
In complex 6a, the Mn atom sits in an octahedral en-
Cr(CO)3 in the close vicinity of the Mn(CO)3 group. For vironment (Figure 5). The manganese atom is chelated by
instance, in 7a the CipsoϪMn and the C4ϪMn interatomic the pentacyclic ligand and is included in a slightly twisted
distances are the longest, with values of 2.154(2) and six-membered metallacycle consisting of atoms N, C7, C8,
2.145(2) A, respectively, whereas the C(5Ϫ7)ϪMn bond C13, C14 and Mn. The 13C NMR analysis of a solution
˚
˚
lengths are all equal to 2.137(2) A (Figure 6). More dra- of this compound at room temperature reveals a dynamic
2114
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122

The Reaction of Diazocyclopentadienyl Compounds with Cyclomanganated Arenes
FULL PAPER
Figure 10. ORTEP diagram of compound 11a, with the atom numbering scheme; the molecule of solvent and hydrogen atoms have been
˚
omitted for clarity; the ellipsoids are drawn at the 30% probability level; selected interatomic distances [A] and angles [°]: Mn1ϪC1
1.798(4), Mn1ϪC2 1.793(4), Mn1ϪC3 1.793(4), Mn1ϪC7 2.194(3), Mn1ϪC12 2.187(3), Mn1ϪC13 2.197(4), Mn1ϪC18 2.191(4),
Mn1ϪC19 2.155(4); C1ϪMn1ϪC2 94.1(2), C1ϪMn1ϪC3, 91.3(2); C1ϪMn1ϪC7, 90.8(2)
Figure 11. ORTEP diagram of compound 12a, with the atom numbering scheme; atoms of hydrogen have been omitted for clarity; the
˚
ellipsoids are drawn at the 30% probability level; selected interatomic distances [A] and angles [°]: MnϪC1 1.790(3), MnϪC2 1.787(3),
MnϪC3 1.811(3), MnϪC4 2.205(3), MnϪC5 2.210(2), MnϪC10 2.198(2), MnϪC11 2.135(2), MnϪC12 2.191(2); C1ϪMnϪC2 92.2(1),
C1ϪMnϪC3 93.0(1), C2ϪMnϪC3 91.4(1)
Table 2. Structural parameters for the cyclopentadienyl-to-manganese bonding interaction in compounds 4a, 5a, 7aϪ9a, 9b, 11aϪ12a
Coordination mode[a]
Compound
η5-Fl
η5-In
η5-Cp
4a
5a
11a
12a
8a
u-9b
7a
rac-9a
˚
C
ipsoϪMn [A]
2.126(2)
2.195(2)
2.157(3)
2.193(2)
2.155(4)
2.192(4)
2.135(2)
2.201(3)
2.139(2)
2.198(2)
2.126(2)
1.782(2)
2.155(4)
2.207(2)
2.141(2)
1.797(2)
2.154(2)
2.167(4)
˚
ϽCArϪMnϾ [A]
ϽCϪMnϾ [A]
ϽcentroidϪMnϾ [A]
˚
2.139(3)
1.771(3)
2.144(4)
1.778(4)
˚
1.805(2)
1.811(3)
1.807(4)
1.814(3)
[a]
Abbreviations: Fl ϭ fluorenyl; In ϭ indenyl; Cp ϭ cyclopentadienyl.
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2115

J.-P. Djukic et al.
FULL PAPER
Conclusion
Table 3. MnϪcentroid and Mn؊Cipso statistical distances obtained
from 20 structures of monosubstituted cymantrenes deposited with
the Cambridge Structural Database[27]
Cyclomanganated aromatic compounds are generally re-
adily accessible by the thermolysis of (alkyl)pentacar-
bonylmanganese compounds in the presence of an aromatic
ligand. Such complexes have been studied for their reactiv-
ity towards various inorganic and organic reagents. Most
interesting are those reactions that yield new organoman-
ganese compounds and allow further chemical or physical
investigations. We have shown here a valuable synthetic
method for appended cymantrenes that could be of interest
in various domains such as the design of polytopic ligands
for homogeneous catalysts or in the preparation of coordi-
nation polymers from bidentate ligands containing two di-
benzocymantrenyl substituents.[1a] Most coupling reactions
with diazocyclopentadienyl compounds gave excellent
yields of cymantrenes when the manganated substrate con-
tained a pyridyl ring, a parent heterocycle or a ketone as
internal donor ligand. In all other cases, the course of the
reaction was not clear and definitely deserves more atten-
tion. We have shown that dinuclear substrates could also
react even when the steric congestion is important, as in the
case of one di-ortho-manganated 2-phenylpyrimidine.
The release of the cyclopentadienyl ligand, or in other
words the removal of the Mn(CO)3 fragment, is seemingly
readily achievable by applying the method recently sug-
gested by Jaouen and co-workers.[30] In a preliminary
experiment, the photolysis of complex 2b in MeOH ef-
ficiently afforded compound 14 [Equation (11)] as a white
solid in 71% yield.
˚
˚
ϽCentroidϪMnϾ [A]
C
ipsoϪMn [A]
Minimum
Maximum
Points
Mean
Median
Std. deviation
Variance
Std. error
Skewness
1.752
1.784
20
1.767
1.766
0.007
0.00005
0.001
0.04
2.120
2.185
20
2.144
2.147
0.017
0.00031
0.004
0.34
Table 4. MnϪcentroid and MnϪCipso distances in structures of
benzo- and dibenzocymantrenes deposited with the Cambridge
Structural Database[27b,27c]
CSD refcodes
CentroidϪMn
C
ipsoϪMn
R
˚
˚
[A]
[A]
Benzocymantrene:
BINCMN
TURNID
1.791
1.799
2.127
2.155
Br
[(η6-C6H5)Cr-
(CO)3]
Dibenzocymantrene:
BAHFEW
MIYXAT
1.823
1.801
1.813
2.147
2.122
2.154
C6H4
H
Ph
ZUKLOG
behaviour. The four carbonyl ligands give rise to three very
broad and poorly resolved 13C signals at δ ϭ 213.6, 213.0
and 211.8 ppm. Decreasing the temperature to Ϫ50 °C al-
lowed the detection of sharper signals at δ ϭ 213.9, 212.7
and 211.51 ppm, but did not allow us to distinguish separ-
ate signals for the two non-isochronous axial carbonyl li-
gands. This dynamic behaviour possibly stems from the
conformational changes of the six-membered metallacycle
that imply a partial rotation of the organic ligand around
the C14ϪMn axis via a transition state wherein the MnϪN
bond is eclipsed by the C14ϪC13 bond. A similar broaden-
ing was observed in the 1H NMR spectra, although we
could not assign this exactly. To the best of our knowledge
6a is only the second example of a carbonyl(η1-fluorenyl)-
manganese complex that has been characterised by X-ray
(11)
In summary, two synthetic steps are necessary to convert
an aromatic compound into a polycyclic tethered cyman-
trene. Both the cyclomanganation and the coupling steps
involve neutral reagents and are overall relatively efficient.
Experimental Section
diffraction analyses.[28] The MnϪC distance of 2.254(2) A
˚
is in the range reported for similar compounds.[29]
General Remarks: All experiments were carried out under dry ar-
In the crystalline state the homodimetallic complex 11a gon with dry and degassed solvents. The (η6-arene)tricarbonylchro-
mium complexes were synthesised according to published pro-
cedures.[1b] Ligands such as 2-phenylpyrimidine,[31] 4,6-diphenyl-
pyrimidine[32] and 2-ferrocenyl-3-phenylquinoxaline[33] as well
as tetracarbonyl[8-(methyl-κC1Ј)quinoline-κN]manganese() (4)[34]
were synthesised according to published procedures. Other ligands
were purchased from commercial sources and used without further
purification. NMR spectra were acquired with Bruker DRX 500
(1H and 13C nuclei) and AC 300 (1H nucleus) spectrometers at
room temperature unless otherwise stated. Chemical shifts are re-
ported in ppm downfield of SiMe4. IR spectra were measured with
a PerkinϪElmer FT spectrometer. Mass spectra were recorded at
(Figure 10) consists of a pentaaromatic distorted helix of
1,2- and 1,3-disubstituted arenes. The distance between the
˚
two Mn atoms is ca. 1 nm (10.7 A). In this compound the
helical arrangement optimises the electrostatic repulsion
and minimises the steric interactions. The C2-symmetric
compound 12a (Figure 11) is a rare case of a 1,2,3-heterotri-
substituted arene with an encapsulated heterocyclic aro-
matic ligand. In this compound the pyrimidyl ring stands
almost perpendicular to the trisubstituted benzene. The two
metal centres are about 0.9 nm apart.
2116
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122

The Reaction of Diazocyclopentadienyl Compounds with Cyclomanganated Arenes
the Service of Mass Spectrometry of University Louis Pasteur (3.41 g, 15.8 mmol) was added. The resulting suspension was
FULL PAPER
(FABϩPEG matrix) or at the Analytical Centre of the Chemical
Institute of the University of Bonn (EI). Elemental analyses were
performed at the Service d’Analyses of the ‘‘Institut de Chimie de
Strasbourg’’ and at the analytical centre of the ‘‘Institut Charles
Sadron’’ in Strasbourg.
stirred for 1 d, filtered and the filtrate dried with MgSO4. The re-
moval of solvents under reduced pressure afforded 1c as a purple-
red stable solid. Yield: 0.948 g, 94%.
General Procedure for the Reaction of 1aϪc with Cyclometalated
Arenes: The cyclometalated substrate was dissolved in a mixture of
n-heptane and toluene and the resulting solution was brought to
reflux. A solution of diazoalkane in toluene was added dropwise
from a syringe and the resulting solution was stirred for an ad-
ditional period of time. The solvents were then evaporated to dry-
ness. The residue was dissolved in dichloromethane and SiO2 was
added. The suspension was stripped of solvent under reduced
pressure and the coated silica gel was loaded on the top of a re-
frigerated SiO2 column packed in n-hexane.
p-Tosyl Azide: p-Toluenesulfonyl chloride (85 g, 0.45 mol) was ad-
ded to a stirred solution of sodium azide (35 g, 0.54 mol) in a mix-
ture of 35 mL of water and 500 mL of absolute ethanol. The re-
sulting mixture was stirred overnight. After this time, 500 mL of
water was added and the resulting slurry was extracted with diethyl
ether. The organic phases were combined and dried with mag-
nesium sulfate and then stripped of solvent under reduced pressure
to afford a pale yellow oil.
5-Diazocyclopentadiene (1a): Freshly cracked cyclopentadiene
(6.6 g, 0.1 mol), p-tosyl azide (19.7 g, 0.1 mol) and diethylamine
(7.3 g, 10.4 mL, 0.1 mol) were dissolved in 50 mL of distilled aceto-
nitrile and stirred under argon at 3 °C for 96 h. The resulting
brownish reaction mixture was extracted with 300 mL of n-hexane
and the organic phase was washed with 200 mL of water. The or-
ganic phase was washed twice with an aqueous solution of KOH
(6% mass) and with water. The combined organic phases were dried
with MgSO4 and concentrated by the removal of half of the sol-
vents under reduced pressure. The resulting solution was then
loaded on the top of a column of SiO2 packed in n-hexane and
cooled to Ϫ10 °C. A large orange band containing the product was
eluted with n-hexane and the corresponding solution was concen-
trated to 30 mL and titrated with triphenylphosphane. Thus, a 2-
mL aliquot of mother solution was added to a solution of tri-
phenylphosphane (1.8 g, 6 mmol) in diethyl ether and stirred under
argon for 15 min. To the resulting mixture, 30 mL of n-hexane was
added and the mixture stirred for an additional 15 min. The re-
sulting orange precipitate was filtered off, washed with 40 mL of
hexane and 30 mL of pentane, and dried under vacuum. The
amount of cyclopentadienonetriphenylphosphazine (0.37 g,
1.04 mmol) recovered from this gravimetric titration gave an ap-
proximate concentration of 0.52  of 5-diazocyclopentadiene.
Yield: 1.44 g, 16%.
8-[1Ј-(Dibenzocymantren-1-yl)methyl]quinoline (4a): From 4 (0.32 g,
1 mmol), a 1:1 mixture of n-heptane (7 mL) and toluene (7 mL),
and a solution of 1c (0.4 g, 2.1 mmol) in toluene (4 mL). Addition
25 min, stirring for an additional 35 min. An initial SiO2 column
chromatography (60 µm, 5 °C) gave a raw sample of 4a contami-
nated with various organic pollutants upon elution with pure di-
chloromethane. A second chromatographic separation (0 °C) with
a different grade of SiO2 (15Ϫ25 µm) gave 4a after elution with
dichloromethane/n-hexane
(1:1).
Yield:
0.35 g
(70%).
C26H16MnNO3 (445.3): calcd. C 70.12, H 3.62, N 3.15; found C
1
69.79; H 3.54, N 3.01. IR (CH2Cl2): ν˜: 2015 vs, 1931 s cmϪ1. H
3
NMR (300 MHz, CDCl3): δ ϭ 9.09 (d, J ϭ 2.9 Hz, 1 H), 8.17 (d,
3
3J ϭ 7.8 Hz, 1 H), 8.11 (m, 2 H), 7.66 (d, J ϭ 8.1 Hz, 4 H), 7.49
3
(m, 1 H), 7.20 (m, 4 H), 7.12 (d, J ϭ 7.0 Hz, 1 H), 5.31 (s, 2 H)
ppm. 13C NMR (125 MHz, CDCl3, 263 K): δ ϭ 225.5 (3 CO),
149.7, 146.4, 138.3, 136.7, 128.3, 127.8, 127.7, 126.6, 126.4, 125.3,
124.6, 123.6, 121.5, 107.2, 93.6, 77.7, 26.4 ppm.
Tetracarbonyl[2-ferrocenyl-3-(phenyl-κC2Ј)-quinoxaline-(κN1)]-
manganese(
I)
(5): 2-Ferrocenyl-3-phenylquinoxaline (0.37 g,
0.95 mmol) and (PhCH2)Mn(CO)5 (0.3 g, 1.1 mmol) were dissolved
in a mixture of cyclohexane (10 mL) and toluene (5 mL). The re-
sulting mixture was brought to reflux for 9 h, the solvents removed
under reduced pressure and the resulting residue redissolved in di-
chloromethane. Silica gel was added to this solution and the sus-
pension was stripped of solvent to afford a coated silica gel residue
that was loaded on the top of a refrigerated (6 °C) SiO2 column
packed in n-hexane. A red band containing the product was eluted
with a 1:1 mixture of n-hexane and dichloromethane. Compound
5 could be recovered as a red powder upon removal of the solvents
under reduced pressure. Yield: 0.34 g, 65%. C28H17FeMnN2O4
(556.2): calcd. C 60.47, H 3.08, N 5.03; found C 60.18, H 3.14, N
Diazoindene (1b): Freshly distilled indene (27.4 g, 0.236 mol) and
p-tosyl azide (44.3 g, 0.224 mol) were dissolved in diethylamine
(50 mL) and stirred at 0 °C under argon for 72 h. The resulting
mixture was extracted with n-hexane and the organic phases
washed with water and brine. The organic phases were combined,
dried with Na2SO4 and concentrated under a reduced pressure of
ca. 20 Torr at 30 °C. The resulting solution was distilled under a
reduced pressure of 9 Torr, using a Vigreux column to improve the
separation of the components of the raw mixture. A large fraction
of indene was distilled at a temperature of 58 Ϯ 4 °C. To avoid any
explosive behaviour, the boiler was heated with an oil bath that was
warmed slowly and whose temperature was homogenised by gentle
stirring. The distillation of indene was stopped as soon as the tem-
perature at the head of the Vigreux column started to fall. The
boiler was then swiftly cooled to room temperature and the remain-
ing residue separated by chromatography on an SiO2 column re-
frigerated at 4 °C and packed in n-hexane. A red band containing
the product was eluted with dry and distilled n-hexane. Removal of
the solvent under reduced pressure afforded a red oil consisting of
92% of diazoindene and 8% of unchanged indene. This oil could
be kept over long periods of time provided it was kept at a tempera-
ture lower than Ϫ20 °C. Yield: 15%.
4.90. IR (CH2Cl2): ν˜: 2075 w, 1993 vs, 1978 s, 1936 m cmϪ1
.
1H
3
NMR (400 MHz, CDCl3): δ ϭ 8.50 (d, J ϭ 7.9 Hz, 1 H), 8.11 (d,
3
3J ϭ 7.1 Hz, 1 H), 8.05 (d, J ϭ 7.3 Hz, 1 H), 7.72 (m, 2 H), 7.55
(d, 3J ϭ 8.2 Hz, 1 H), 7.20 (t, 3J ϭ 7.3 Hz, 1 H), 6.90 (t, 3J ϭ
7.6 Hz, 1 H), 4.98 (t, 3J ϭ 2.0 Hz, 2 H), 4.47 (t, 3J ϭ 1.9 Hz, 2 H),
4.05 (s, 5 H) ppm. 13C NMR (100 MHz, CDCl3): δ ϭ 221.1 (CO),
214.3 (CO), 213.9 (2 CO), 178.9, 162.2, 153.4, 148.6, 141.9, 141.2,
140.7, 131.3, 130.0, 129.9, 129.7, 129.4, 126.7, 122.7, 85.3, 71.6 (2
C), 70.4 (5 C), 69.9 (2 C) ppm.
3-[2Ј-(Dibenzocymantren-1-yl)phenyl]-2-ferrocenylquinoxaline (5a):
From 5 (0.124 g, 0.22 mmol), 10 mL of cyclohexane, 1 mL of tolu-
ene and a solution of 1c (0.09 g, 0.47 mmol) in 2 mL of toluene.
Addition for 20 min, additional stirring for 40 min. Chromatogra-
phy on an SiO2 column (6 °C) gave 5a after elution with a 70:30
mixture of n-hexane/acetone. Deep red powder. Yield: 0.11 g (74%).
C40H25FeMnN2O3·1/2CH2Cl2 (734.8): calcd. C 60.80, H 3.44, N
9-Diazofluorene (1c): 9-Fluorenone hydrazone (1.0 g, 5.3 mmol)
was dissolved in 75 mL of toluene and yellow mercuric oxide
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2117

J.-P. Djukic et al.
FULL PAPER
3.42; found C 60.81, H 3.40, N 3.53. IR (CH2Cl2): ν˜: 2016 s, 1934
211.6 (2 MnCO), 169.1 (OCϭN), 157.4, 157.4 (2 C), 150.0, 133.3,
s cmϪ1 1H NMR (500 MHz, CDCl3, 263 K): δ ϭ 8.18 (d, 3J ϭ 133.3 (2 C), 133.2, 130.2, 126.6, 126.1, 126.1, 125.1, 122.7, 122.6,
.
4.5 Hz, 1 H), 8.01 (d, 3J ϭ 8.4 Hz, 1 H), 7.96 (t, 3J ϭ 4.6 Hz, 1
122.6, 120.8, 120.8, 120.0, 120.0 (2 C), 67.4 (NCH2), 61.0 (OCH2),
3
3
H), 7.86 (d, J ϭ 8.6 Hz, 1 H), 7.78 (m, 3 H), 7.64 (t, J ϭ 8.4 Hz,
51.9 (C-9) ppm. EI-MS: m/z ϭ 449 [Mϩ Ϫ CO], 421 [Mϩ Ϫ 2 CO],
2 H), 7.58 (t, J ϭ 7.6 Hz, 1 H), 7.01 (m, 2 H), 6.95 (m, 1 H), 6.79 393 [Mϩ Ϫ 3 CO], 369 [Mϩ Ϫ 4 CO].
3
(t, 3J ϭ 7.6 Hz, 1 H), 6.66 (d, 3J ϭ 8.8 Hz, 1 H), 6.24 (t, 3J ϭ
2-[2Ј-(Cymantren-1ЈЈ-yl)phenyl]-3-methylpyridine (7a): From
7
(0.205 g, 0.61 mmol), n-heptane (10 mL) and a solution of 1a in n-
hexane (2 mL, 1.04 mmol, 0.52 ). Addition 5 min and stirring for
an additional 25 min. Chromatography on hydrated SiO2 (5 °C)
gave 7a upon elution with a mixture of n-hexane and acetone (4:1).
Canary-yellow powder. Yield: 0.149 g (66%). C20H14MnNO3
(275.2): calcd. C 64.70, H 3.80, N 3.77; found C 64.51, H 3.68, N,
7.6 Hz, 1 H), 4.24 (s, 1 H), 3.91 (s, 1 H), 3.83 (s, 1 H), 3.74 (s, 5
H), 3.44 (s,1 H) ppm. 13C NMR (125 MHz, CDCl3, 263 K): δ ϭ
225.3 (3 CO), 154.1, 152.1, 141.3, 141.1, 139.7, 135.0, 131.9, 130.1,
129.8, 129.7, 129.1, 128.7, 128.6, 127.9, 127.1, 125.2, 125.1, 124.8,
124.6, 124.3, 124.1, 123.2, 107.4, 103.2, 95.5, 90.9, 82.1, 81.5, 71.2,
70.1, 69.7, 69.6 (5 C), 68.2 ppm.
1
3.70. IR (CH2Cl2): ν˜ ϭ 2020 s, 1934 s cmϪ1. H NMR (300 MHz,
Tetracarbonyl[2-(phenyl-κC2)-2-oxazoline-κN]manganese(
I) (6): 2-
CDCl3): δ ϭ 8.51 (d, 3J ϭ 4.8 Hz, 1 H), 7.54 (d, 3J ϭ 7.7 Hz, 1
Phenyl-2-oxazoline and (PhCH2)Mn(CO)5 were dissolved in n-hep-
tane and the resulting mixture was boiled for 9 h. The resulting
suspension was stripped of solvent and the residue loaded on the
top of an SiO2 column packed in n-hexane. A pale yellow band was
eluted with a 1:1 mixture of n-hexane/CH2Cl2, and the resulting
solution stripped of solvents to afford a yellow powder. Yield:
1.61 g, 71%. M.p.: 106 °C. C13H8MnNO5 (313.1): calcd. C 49.86,
H 2.58, N 4.47; found C 49.70, H 2.61, N 4.45. HRMS: calcd. for
C13H8MnNO5 312.9782; found 312.9782. IR (n-hexane): ν˜ ϭ 2077
3
3
H), 7.50 (d, J ϭ 7.5 Hz, 1 H), 7.41 (t, J ϭ 7.1 Hz, 1 H), 7.35 (t,
3J ϭ 7.0 Hz, 1 H), 7.23 (m, 2 H), 4.53 (m, 4 H), 2.02 (s, 3 H) ppm.
13C NMR (125 MHz, CDCl3, 263 K): δ ϭ 224.9 (3 CO), 158.8,
146.9, 139.2, 138.1, 132.0, 131.2, 129.9, 129.5, 128.4, 128.0, 122.9,
103.1, 84.6, 84.3, 82.0, 80.7, 19.2 ppm.
[1-(Acetyl-κO)naphthyl-κC2]tetracarbonylmanganese(
I
)
(8):
(PhCH2)Mn(CO)5 (1.43 g, 5 mmol) and 1-acetylnaphthalene
(1.02 g, 6 mmol) were dissolved in n-heptane (20 mL) and refluxed
for 15 h. The resulting mixture was stripped of solvents and the
residue subjected to flash chromatography on SiO2. Compound 8
was eluted with a 1:1 mixture of dichloromethane/n-hexane. Yellow
solid. Yield: 0.93 g (56%). C16H9MnO5·1/2CH2Cl2 (378.7): calcd. C
54.62, H 2.66; found C 54.65, H 2.71. HR-MS: calcd. for
C16H9MnO5 335.9830; found 335.9831. IR (n-hexane): ν˜ ϭ 2082
w, 1991 vs, 1982 m, 1943 s cmϪ1
δ ϭ 7.96 (ddd, JH,H ϭ 7.4, JH,H ϭ 1.0, JH,H ϭ 0.6 Hz, 1 H),
.
1H NMR (500 MHz, CDCl3):
3
4
5
3
4
5
7.52 (ddd, JH,H ϭ 7.6, JH,H ϭ 1.5, JH,H ϭ 0.6 Hz, 1 H), 7.35
3
4
3
(td, JH,H ϭ 7.4, JH,H ϭ 1.5 Hz, 1 H), 7.14 (ddd, JH,H ϭ 7.6,
3JH,H ϭ 7.4, JH,H ϭ 1.0 Hz, 1 H), 4.75 (t, JH,H ϭ 9.4 Hz, 2 H,
4
2
2
2
N-CH2), 3.82 (dd, JH,H ϭ 9.6, JH,H ϭ 9.3 Hz, 2 H, OCH2) ppm.
13C NMR (125 MHz, CDCl3): δ ϭ 219.6 (MnCO), 215.3 (MnCO),
213.3 (2 MnCO), 179.0, 175.3, 141.8, 133.6, 131.8, 126.7, 123.7,
71.3 (NCH2), 54.1 (OCH2) ppm. EI-MS: m/z ϭ 313 [Mϩ], 285 [Mϩ
Ϫ CO], 257 [Mϩ Ϫ 2 CO], 229 [Mϩ Ϫ 3 CO], 157 [Mϩ Ϫ 4 CO Ϫ
C3H4NO Ϫ H], 147 [Mϩ Ϫ Mn(CO)4 ϩ H].
m, 1997 vs, 1946 s, 1562 w cmϪ1
.
1H NMR (300 MHz, CDCl3):
3
δ ϭ 8.31 (d, 3J ϭ 8.8 Hz, 1 H), 8.27 (d, J ϭ 8.3 Hz, 1 H), 7.93 (d,
3
3J ϭ 8.1 Hz, 1 H), 7.81 (d, J ϭ 8.0 Hz, 1 H), 7.60 (t, 3J ϭ 7.7 Hz,
1 H), 7.47 (t, 3J ϭ 7.5 Hz, 1 H), 3.03 (s, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ ϭ 220.6 (CO), 215.1 (CO), 213.2 (CO), 210.9
(CO), 210.2 (CO), 140.7, 138.3, 134.2, 133.4, 132.4, 130.5, 128.1,
124.7, 121.7, 32.2 ppm. EI-MS: m/z ϭ 336 [M], 280 [M Ϫ 2 CO],
252 [M Ϫ 3 CO], 224 [M Ϫ 4 CO], 196 [M Ϫ 5 CO], 170 [M Ϫ
Mn Ϫ 4 CO].
Tetracarbonyl{9-[2Ј-(2ЈЈ-oxazolin-2ЈЈ-yl-κN3Ј Ј)phenyl]-
fluorenyl-κC9}manganese(
I) (6a): From 6 (782 mg, 2.5 mmol), n-
hexane (10 mL) and a solution of 1c (5 mmol) in toluene (17.5 mL).
Addition 60 min, stirring for an additional 60 min. Chromatogra-
phy on SiO2 (5 °C) gave a brownish mixture containing mainly 6a
after elution with n-hexane/dichloromethane (1:1). A second chro-
matographic separation gave a brown-yellow solution of 6a. Yield:
0.76 mg (63%). The air sensitivity of 6a prevented its complete
characterisation by elemental analysis. HRMS: calcd. for
C25H16MnNO4 [M Ϫ CO] 449.0459; found 449.0453. IR (n-hex-
1-Acetyl-2-(benzocymantren-1Ј-yl)naphthalene (8a): From 8 (0.2 g,
0.6 mmol), n-heptane (5 mL), toluene (5 mL) and 1b (0.2 g,
1.4 mmol) in toluene (3 mL). Addition 30 min and stirring for an
additional 30 min. Chromatography on a hydrated SiO2 column
(5 °C), elution with pure dichloromethane. Canary-yellow powder.
Yield: 0.19 g (76%). C24H15MnO4 (422.3): calcd. C 68.26, H 3.58:
found C 68.12, H 3.40. IR (KBr): ν˜ ϭ 2017 vs, 1942 s, 1925 s, 1694
ane): ν˜ ϭ 2071 w, 1993 vs, 1986 s, 1940 s cmϪ1
.
1H NMR
3
(300 MHz, CD2Cl2): δ ϭ 7.96 (d, JH,H ϭ 7.6 Hz, 2 H, Hfluorene),
1
3
m cmϪ1. H NMR (400 MHz, CDCl3): δ ϭ 8.02 (d, J ϭ 8.5 Hz,
2 H), 7.96 (m, 1 H), 7.76 (m, 1 H), 7.57 (m, 3 H), 7.49 (d, 3J ϭ
8.7 Hz, 1 H), 7.23 (t, 3J ϭ 7.4 Hz, 1 H), 7.16 (t, 3J ϭ 7.4 Hz, 1 H),
4
3
7.89 (dd, 3JH,H ϭ 7.6, JH,H ϭ 1.2 Hz, 1 H, HPh), 7.45 (d, JH,H ϭ
7.6 Hz, 2 H, Hfluorene), 7.25 (m, 7 H), 4.75 (dd, 2JH,H ϭ 9.8, 3JH,H ϭ
2
3
9.5 Hz, 2 H, NCH2), 4.01 (dd, JH,H ϭ 9.8, JH,H ϭ 9.5 Hz, 2 H,
5.36 (d, 3J ϭ 2.7 Hz, 1 H), 5.25 (d, J ϭ 2.8 Hz, 1 H), 2.08 (s, 3
3
1
O-CH2) ppm. H NMR (500 MHz, CDCl3, Ϫ50 °C): δ ϭ 8.04 (d,
H) ppm. 13C NMR (100 MHz, CDCl3): δ ϭ 224.6 (3 CO), 206.9
(CO), 141.0, 133.1, 130.4, 129.8, 128.7, 128.6, 128.0, 127.9, 127.0,
126.6, 126.2, 124.6, 122.9, 105.9, 100.4, 92.8, 90.7, 77.4, 72.1,
32.8 ppm.
3
3JH,H ϭ 7.6 Hz, 2 H), 7.86 (d, JH,H ϭ 7.6 Hz, 1 H), 7.50 (br. s, 2
3
H), 7.36 (m, 3 H), 7.30 (m, 3 H), 7.21 (t, JH,H ϭ 7.6 Hz, 1 H),
4.83 (t, JH,H ϭ 9.6 Hz, 2 H, NCH2), 4.01 (t, JH,H ϭ 9.6 Hz, 2
H, OCH2) ppm. 13C NMR (125 MHz, CDCl3, 293 K): δ ϭ 213.7
(MnCO), 213.1 (MnCO), 211.7 (2 MnCO), 169.4 (OCϭN), 157.6, 2-[2Ј-(Benzocymantren-1ЈЈ-yl)phenyl]-3-methylpyridine (7b): From 7
157.6 (2 C), 150.4, 133.5, 133.5 (2 C), 133.2, 130.2, 126.8, 126.1, (0.22 g, 0.79 mmol) cyclohexane (15 mL), 1b (0.24 g, 1.7 mmol) and
126.1, 125.0, 122.9, 122.8, 122.8, 120.8, 120.8, 120.1, 120.1, 67.5
n-hexane (3 mL). Addition 10 min, stirring for an additional
(NCH2), 61.1 (OCH2), 52.2 ppm. 13C NMR (125 MHz, CDCl3, 50 min. Chromatography on SiO2 (5 °C), elution with n-hexane/
263 K): δ ϭ 213.9 (MnCO), 212.7 (MnCO), 211.5 (2 MnCO), 168.8 acetone (70:30). Red waxy solid. Yield: 0.24 g (87%).
(O-CϭN), 157.3, 157.3 (2C), 149.4, 133.0, 133.0 (2 C), 132.9, 130.1, C24H16MnNO3·1/2CH2Cl2 (463.7): calcd. C 63.45, H 3.69, N 3.02;
126.5, 126.0, 126.0, 125.1, 122.4, 122.3, 122.3, 120.7, 120.7, 119.9,
found C 63.92, H 3.86, N 3.05. HRMS (FABϩ): calcd. for
119.9 (2 C), 67.4 (NCH2), 61.0 (OCH2), 51.5 (C-9) ppm. 13C NMR C24H17NMnO3 [Mϩ] 422.058888; found 422.058890. IR (CH2Cl2):
(125 MHz, CDCl3, 223 K): δ ϭ 213.7 (MnCO), 212.9 (MnCO), ν˜ ϭ 2018 vs, 1934 s cmϪ1
.
1H NMR (300 MHz, CDCl3, 298 K):
2118  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122

The Reaction of Diazocyclopentadienyl Compounds with Cyclomanganated Arenes
δ ϭ 8.38 (m, 1 H), 8.02 (d, 3J ϭ 7.5 Hz, 1 H), 7.57 (t, 3J ϭ 7.6 Hz, Complex 10a: From 10 (0.2 g, 0.44 mmol), heptane (10 mL) and a
FULL PAPER
3
3
1 H), 7.48 (t, J ϭ 7.5 Hz, 1 H), 7.41 (d, J ϭ 8.5 Hz, 1 H), 7.36
solution of 1a (1.9 mL, 1.0 mmol, 0.52 ) in n-hexane, added in 3
(m, 2 H), 7.29 (d, J ϭ 7.7 Hz, 1 H), 7.03 (m, 3 H), 4.96 (d, J ϭ fractions: 1 mL was added over 7 min, followed by an additional
2.9 Hz, 1 H), 4.65 (m, 1 H), 1.74 (s, 3 H) ppm. 13C NMR
0.45 mL after 1 h of reaction, and finally 0.45 mL after 2 h of
3
3
(125 MHz, CDCl3, 293 K): δ ϭ 225.0, 158.8, 146.7 (C-3), 141.2, reaction. The reaction mixture was then stirred for an additional
137.7 (C-1), 132.8, 131.8 (2 C), 129.8, 128.6, 128.3, 126.9 (broad), hour. Chromatography on SiO2 (5 °C), elution of 10a with n-hex-
125.9 (2 C), 123.0 (broad), 122.4, 105.0 (broad), 100.0 (broad), 93.7
(broad), 90.4 (C5), 71.0 (broad), 19.1 (CH3, broad) ppm. Major
ane/acetone (9:1). Yellow powder. Yield: 0.112 g, 71%.
C23H14CrNO6Re (638.6): calcd. C 43.26, H 2.21, N 2.19; found C
conformer: 1H NMR (500 MHz, CDCl3, 243 K): δ ϭ 8.45 (d, 3J ϭ 43.05, H 2.45, N 2.02. IR (CH2Cl2): ν˜ ϭ 2026 s, 1972 vs, 1928 s,
4.0 Hz, Hpyridyl), 8.04 (d, 3J ϭ 7.5 Hz, Hphenyl), 7.58 (t, 3J ϭ 7.3 Hz, 1901 m cmϪ1
.
1H NMR (300 MHz, CDCl3): δ ϭ 8.53 (d, 3J ϭ
3
3
3
Hphenyl), 7.52 (d, J ϭ 8.8 Hz, H6), 7.49 (t, J ϭ 7.5 Hz, Hphenyl), 4.2 Hz, 1 H), 7.55 (t, J ϭ 7.6 Hz, 1 H), 7.28 (m, 1 H), 5.65 (m, 1
3
3
3
3
7.41 (d, J ϭ 8.6 Hz, 9-H), 7.37 (d, J ϭ 7.2 Hz, Hphenyl), 7.32 (d, H), 5.49 (t, J ϭ 5.6 Hz, 1 H), 5.41 (d, J ϭ 6.6 Hz, 1 H), 5.38 (d,
3J ϭ 10.8 Hz, Hpyridyl), 7.16 (t, 3J ϭ 7.5 Hz, H7), 7.12 (t, 3J ϭ
3J ϭ 6.2 Hz, 1 H), 5.32 (t, J ϭ 5.8 Hz, 1 H), 5.20 (m, 1 H), 4.98
7.1 Hz, Hpyridyl), 7.06 (t, J ϭ 7.7 Hz, 8-H), 4.95 (d, J ϭ 2.5 Hz, (m, 1 H), 4.84 (m, 1 H), 2.19 (s, 3 H) ppm. 13C NMR (125 MHz,
5-H), 4.51 (d, 3J ϭ 2.6 Hz, 4-H), 1.55 (s, 3 H, CH3) ppm. 13C NMR
CDCl3, 263 K): δ ϭ 232.4 [Cr(CO)3], 193.5 [Re(CO)3], 152.9, 147.3,
(125 MHz, CDCl3, 243 K): δ ϭ 224.9 (3 CO), 158.5, 146.6 (C-3), 138.4, 132.6, 124.0, 102.0, 93.9, 92.1 (2 C), 91.9, 89.8 (2 C), 88.1,
3
3
3
140.8, 137.8 (C-1), 132.3, 131.8, 131.5, 129.5, 128.5, 128.2, 127.5,
126.2, 125.8, 122.5, 122.2, 105.2, 98.8, 92.6, 90.1 (C-5), 71.4 (C-4),
18.9 ppm. FAB-MSϩ: m/z ϭ 422 [Mϩ], 337 [M Ϫ 3 CO], 282 [M
Ϫ Mn Ϫ 3 CO]. Minor conformer: 13C NMR (125 MHz, CDCl3,
243 K): δ ϭ 224.9 (3 CO), 158.2, 146.7, 140.5, 137.8, 132.9, 131.7,
131.6, 129.9, 128.6, 128.2, 125.8, 125.7, 124.8, 124.2, 122.4, 103.8,
101.7, 93.8, 90.8, 69.3, 19.5 ppm.
87.8, 83.9, 82.6, 19.8 ppm.
[4,6-(Diphenyl-κC2Ј,κC2ЈЈ)pyrimidine-(κN1,κN2)]bis(tetracarbonyl-
manganese(I)] (11): 4,6-Diphenylpyrimidine (0.4 g, 1.7 mmol) and
(PhCH2)Mn(CO)5 (1.48 g, 5.2 mmol) were dissolved in a mixture
of n-heptane (10 mL) and toluene (10 mL) and the resulting mix-
ture heated to reflux for 11 h. The mixture was then stripped of its
solvents, the residue was dissolved in dichloromethane and SiO2
was added to this solution. After removal of the solvent under re-
duced pressure, the coated silica gel was loaded on the top of an
SiO2 column packed in n-hexane and refrigerated at 6 °C. A large
band containing pure compound 11 was eluted with dichlorometh-
ane/n-hexane (3:2). Yellow powder. Yield: 0.71 g, 73%.
C24H10Mn2N2O8 (564.2): calcd. C 51.09, H 1.79, N 4.96; found C
50.97, H 1.46, N 5.03. IR (CH2Cl2): ν˜ ϭ 2082 w, 2000 vs, 1985 s,
1937 m cmϪ1. 1H NMR (300 MHz, [D6]acetone): δ ϭ 9.70 (s, 1 H),
Complex 9a: From 9 (0.2 g, 0.44 mmol), heptane (10 mL) and 1a
(2.1 mL, 1.1 mmol, 0.52 ). Addition 7 min, additional stirring for
30 min. Chromatography on hydrated SiO2 (5 °C), elution with n-
hexane/acetone (4:1). Canary yellow solid. Yield: 0.145 g (67%).
C22H12CrMnNO6 (493.3): calcd. C 53.57, H 2.45, N 2.84; found C
53.84, H 2.78, N 2.69. IR (CH2Cl2): ν˜ ϭ 2025 s, 1971 vs, 1939 s,
1899 m cmϪ1 1H NMR (300 MHz, CDCl3): δ ϭ 8.62 (d, 3J ϭ
.
4.2 Hz, 1 H), 7.68 (t, 3J ϭ 7.8 Hz, 1 H), 7.35 (d, 3J ϭ 7.9 Hz, 1
3
H), 7.30 (m, 1 H), 5.75 (d, J ϭ 6.1 Hz, 1 H), 5.52 (m, 2 H), 5.45
3
8.79 (s, 1 H), 8.44 (d, J ϭ 7.3 Hz, 2 H), 8.01 (d, 3J ϭ 7.4 Hz, 2
3
(t, J ϭ 5.7 Hz, 1 H), 5.29(m, 1 H), 4.64 (m, 1 H), 4.52 (m, 1 H),
3
3
H), 7.42 (t, J ϭ 7.3 Hz, 2 H), 7.29 (t, J ϭ 7.5 Hz, 2 H) ppm. 13C
NMR (100 MHz, CDCl3): δ ϭ 221.1 (CO), 214.7 (CO), 214.0 (2
CO), 180.2, 173.0, 166.4, 145.4, 142.2, 133.2, 128.3, 125.4,
109.2 ppm.
4.26 (m, 1 H) ppm. 13C NMR (125 MHz, CDCl3, 263 K): δ ϭ
232.4 [3CO (Cr)], 224.0 [3 CO (Mn)], 154.5, 149.3, 136.4, 126.7,
123.6, 110.4, 104.0, 99.2, 94.8, 94.3, 92.2, 91.6, 88.0, 86.4, 82.4,
79.8 ppm.
Complexes u-9b and (rel)-l-9b: From 9 (0.2 g, 0.4 mmol), cyclohex-
ane (10 mL), toluene (1 mL) and a solution of 1b (0.12 g, 0.9 mmol)
in toluene (3 mL). Addition 20 min, stirring for an additional
25 min. Chromatography on SiO2 (Ϫ5 °C), u- and (rel)-l-9b were
4,6-Bis[2Ј-(dibenzocymantren-1ЈЈ-yl)phenyl]pyrimidine (11a): From
11 (0.2 g, 0.35 mmol), n-heptane (5 mL), toluene (5 mL) and a solu-
tion of 1c (0.27 g, 1.42 mmol) in toluene (3 mL). Addition 25 min,
stirring for an additional 35 min. Chromatography on SiO2 (6 °C),
11a was eluted with pure acetone. Yellow powder. Yield: 0.25 g,
84%. C42H22N2Mn2O6·1/3CH2Cl2 (788.8): calcd. C 64.48, H 2.90,
N 3.55; found C 64.38, H 2.97, N 3.61. IR (CH2Cl2): ν˜ ϭ 2016 s,
1
eluted with n-hexane/acetone (70:30). H NMR spectroscopy indi-
cated that the two diastereomers are in a 78:22 ratio. Conversion:
0.13 g (55%). C26H14CrMnNO6 (543.3): calcd. C 57.48, H 2.60, N
2.58; found C 57.67, H 2.42, N 2.65. IR (CH2Cl2): ν˜ ϭ 2023 s, 1970
vs, 1937m, 1899 m cmϪ1. u-9b: 1H NMR (300 MHz, CDCl3,
1935 s cmϪ1 1H NMR (300 MHz, CDCl3): δ ϭ 8.23 (d, 3J ϭ
.
7.7 Hz, 2 H), 8.08 (s, 1 H), 8.06 (d, 3J ϭ 8.2 Hz, 4 H), 7.67 (t, 3J ϭ
7.6 Hz, 2 H), 7.43 (t, 3J ϭ 7.6 Hz, 2 H), 7.17 (t, 3J ϭ 7.3 Hz, 4 H),
3
298 K): δ ϭ 8.42 (d, J ϭ 4.8 Hz, 1 H), 7.36 (d, 3J ϭ 8.7 Hz, 1 H),
7.25 (m,1 H), 7.19 (t, 3J ϭ 6.5 Hz, 1 H), 7.00 (m, 3 H), 6.85 (t,
3
7.04 (m, 8 H), 6.71 (d, J ϭ 7.8 Hz, 2 H), 6.29 (s, 1 H) ppm. 13C
3J ϭ 7.6 Hz, 1 H), 6.02 (d, 3J ϭ 6.4 Hz, 1 H), 5.90 (d, 3J ϭ 6.4 Hz,
NMR (125 MHz, CDCl3, 263 K): δ ϭ 224.9 (3 CO), 165.2, 157.3,
139.4, 136.3, 130.6, 130.5, 129.5, 128.8, 128.2, 125.1, 124.8, 123.0,
120.6, 107.2, 92.9, 83.3 ppm.
3
3
1 H), 5.65 (t, J ϭ 6.3 Hz, 1 H), 5.59 (t, J ϭ 6.4 Hz, 1 H), 5.54
(d, J ϭ 3.0 Hz, 1 H), 5.14 (d, J ϭ 3.0 Hz, 1 H) ppm. 13C NMR
(125 MHz, CDCl3, 263 K): δ ϭ 232.5 [Cr(CO)3], 224.0 [Mn(CO)3],
154.2, 149.1, 135.7, 126.8, 126.7, 125.6, 125.1, 123.2, 122.7, 112.5,
3
3
[2-(Phenyl-κC2Ј,κC2ЈЈ)pyrimidine-(κN1,κN2)]bis(tetracarbonylman-
105.0, 103.2, 101.9, 99.0, 93.6, 93.5, 92.8, 91.1, 90.5, 69.5 ppm. ganese(
(rel)-l-9: 1H NMR (300 MHz, CDCl3, 298 K): δ ϭ 8.55 (d, 3J ϭ (PhCH2)Mn(CO)5 (3.46 g, 1.21 mmol) were dissolved in a mixture
5.4 Hz, 1 H), 7.97 (d, 3J ϭ 8.9 Hz, 1 H), 7.49 (m, 2 H), 7.30 (t,
of n-heptane (5 mL) and toluene (10 mL). The mixture was re-
3J ϭ 7.8 Hz, 1 H), 7.13 (m, 1 H), 6.91 (m, 2 H), 6.10 (d, 3J ϭ fluxed for 10 h and the solution was cooled to Ϫ20 °C overnight.
6.4 Hz, 1 H), 5.96 (d, 3J ϭ 6.2 Hz, 1 H), 5.65 (t, 3J ϭ 6.3 Hz, 1
Then the supernatant was removed and the solid residue was
H), 5.59 (t, J ϭ 6.4 Hz, 1 H), 5.04 (d, J ϭ 3.4 Hz, 1 H), 4.49 (d, washed three times with 20 mL of diethyl ether and twice with
I)] (12): 2-Phenylpyrimidine (0.79 g, 5.06 mmol) and
3
3
3J ϭ 3.1 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3, 263 K): δ ϭ
232.6 [Cr(CO)3], 224.1 [Mn(CO)3], 154.5, 149.4, 136.0, 128.0 (2 C),
126.4, 126.3, 123.5, 123.4, 109.7, 105.5, 105.4, 99.0, 93.6, 93.5, 92.8,
91.1, 90.5, 69.5 ppm.
20 mL of pentane and dried under vacuum. Yield: 2.0 g (81%).
C18H6Mn2N2O8 (488.1): calcd. C 44.29, H 1.24, N 5.74; found C
44.49, H 1.15, N 5.60. IR (CH2Cl2): ν˜ ϭ 2072 w, 1997 vs, 1981 s,
1938 m cmϪ1. 1H NMR (400 MHz, [D6]acetone): δ ϭ 8.98 (d, 3J ϭ
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2119

J.-P. Djukic et al.
FULL PAPER
5.4 Hz, 2 H), 7.53 (d, 3J ϭ 4.9 Hz, 2 H), 7.34 (t, 3J ϭ 5.5 Hz, 1
H), 7.21 (t, J ϭ 7.3 Hz, 1 H) ppm.
and methanol (10 mL). The sealed Schlenk tube containing the
solution was then irradiated with the aid of a medium-pressure
Hg lamp. A slight precipitation of brownish air-sensitive solid was
noticed shortly after the beginning of the UV irradiation. The or-
ganic product 14 was purified by chromatography on SiO2 and re-
covered as an off-white solid. Yield: 0.1 g (71%). HRMS (FABϩ):
calcd. for C25H20N [MHϩ] 334.159565; found 334.159575. 1H
NMR (300 MHz, CDCl3): δ ϭ 8.59 (m, 1 H), 7.85 (d, 3J ϭ 7.5 Hz,
2 H), 7.77 (d, 3J ϭ 7.5 Hz, 1 H), 7.45 (m, 1 H), 7.34 (m, 6 H), 7.24
(t, 3J ϭ 7.4 Hz, 2 H), 7.14 (t, 3J ϭ 7.4 Hz, 1 H), 6.42 (d, 3J ϭ
6.7 Hz, 1 H), 4.88 (s, 1 H), 2.41 (s, 3 H) ppm. 13C NMR (75 MHz,
[D6]acetone): δ ϭ 160.1, 149.7, 147.7, 142.4, 141.1, 138.9, 132.6,
129.9, 129.1, 128.7, 128.2, 128.1, 127.2, 126.5 (2 C), 123.5, 120.6,
51.2, 19.8 ppm.
3
2-[2Ј,6Ј-Bis(dibenzocymantren-1ЈЈ-yl)phenyl]pyrimidine (12a): From
12 (0.3 g, 0.62 mmol), toluene (10 mL) and a solution of 1c (0.47 g,
2.46 mmol) in toluene (3 mL). Addition 25 min, stirring for an ad-
ditional 35 min. Chromatography on SiO2 (5 °C), 12a was eluted
with dichloromethane/n-hexane (80:20). Yellow powder. Yield:
0.28 g (61%). C42H22Mn2N2O6·1/3CH2Cl2 (516.4): calcd. C 64.48,
H 2.90, N 3.55; found C 64.38, H 2.97, N 3.61. IR (CH2Cl2): ν˜ ϭ
2018 s, 1934 s cmϪ1. 1H NMR (500 MHz, CDCl3, 263 K): δ ϭ 8.52
(d, 3J ϭ 7.8 Hz, 2 H), 8.03 (t, 3J ϭ 7.7 Hz, 1 H), 7.98 (d, 3J ϭ
8.6 Hz, 4 H), 7.56 (d, 3J ϭ 4.9 Hz, 2 H), 7.29 (d, 3J ϭ 8.7 Hz, 4
3
3
H), 7.10 (t, J ϭ 7.6 Hz, 4 H), 7.05 (t, J ϭ 7.6 Hz, 4 H), 6.15 (t,
3J ϭ 4.9 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3, 263 K): δ ϭ
225.3 (3 CO), 166.0, 155.3, 142.4, 136.2, 132.2, 130.1, 127.6, 124.6,
124.5, 123.9, 117.5, 107.3, 92.6, 84.6 ppm.
Experimental Procedure for the X-ray Diffraction Analysis of Com-
pounds 4a, 5a, 6a, 7a, 8a, 9a, 9b, 11a and 12a: Acquisition and
processing parameters are displayed in Tables 5 and 6. Reflections
were collected with a Nonius KappaCCD diffractometer using Mo-
1,4-Diacetyl-2,5-bis(dibenzocymantren-1Ј-yl)benzene (13a): From 13
(0.22 mmol), n-hexane (7 mL) and a solution of 1c (0.88 mmol) in
toluene (5 mL). Addition 30 min, stirring for an additional 60 min.
Compound 13a precipitated as a yellow solid. Due to its insolu-
bility in most polar solvents (THF, DMSO) it could not be further
purified. This precipitate was washed several times with n-hexane
and acetone and dried under reduced pressure. M.p. 233Ϫ240 °C.
IR (KBr): ν˜ ϭ 2013 vs, 1926 s, 1694 w cmϪ1. FAB-MSϩ: m/z ϭ
767 [M ϩ H]ϩ, 682 [M Ϫ 3 CO ϩ H]ϩ, 613 [4 matrix ϩ H]ϩ, 599
[M Ϫ Mn(CO)3 Ϫ 3 CO ϩ H]ϩ, 488 [M Ϫ 2 Mn(CO)3]ϩ, 460 [3
matrix ϩ H]ϩ.
˚
Kα graphite-monochromated radiation (λ ϭ 0.71073 A). The struc-
tures were solved by direct methods and were refined against |F|
with the Nonius OpenMoleN package.[35] Hydrogen atoms were
introduced as fixed contributors. Flack’s x parameter for 9a was
determined to be x ϭ 0.36(2). CCDC-220450 to -220458 contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html [or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: (internat.)
ϩ 44-1223-336-033; E-mail: deposit@ccdc.cam.ac.uk].
2-{2Ј-(9-Fluorenyl)phenyl}-3-methylpyridine (14): Compound 2b Supporting Information: One- and two-dimensional (1H-1H COSY,
1
(0.2 g, 0.5 mmol) was dissolved in a mixture of diethyl ether (5 mL)
ROESY and H-13C HETCORR) NMR spectra for compound 7b
Table 5. Acquisition and refinement parameters for the X-ray diffraction analyses of complexes 4a؊7a
4a
5a
6a
7a
Empirical formula
M
C26H16MnNO3
445.36
C40H25FeMnN2O3·CH2Cl2
777.38
monoclinic
P21/c
16.3945(3)
13.8198(3)
14.9630(4)
90
94.573(5)
90
3379.4(1)
4
C26H16MnNO5·CH2Cl2
562.29
C20H14MnNO3
371.28
orthorhombic
Pbca
12.4955(2)
13.1900(2)
20.4495(4)
90
90
90
3370.4(1)
8
Crystal system
Space group
triclinic
triclinic
¯
¯
P1
P1
˚
a [A]
8.3364(2)
11.6063(4)
12.1151(4)
101.778(5)
106.174(5)
108.494(5)
1011.11(5)
2
10.1810(3)
11.1509(4)
11.5676(4)
75.737(5)
84.768(5)
70.853(5)
1202.27(7)
2
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
3
˚
V [A ]
Z
Crystal dim. [mm]
0.10 ϫ 0.06 ϫ 0.06
1.46
456
0.14 ϫ 0.14 ϫ 0.10
1.53
1584
1.005
0.20 ϫ 0.16 ϫ 0.16
1.55
572
0.16 ϫ 0.14 ϫ 0.08
1.46
1520
0.801
Dc [g·cmϪ3
F000
]
µ [mmϪ1
]
0.682
0.812
Trans. min./max.
hkl limits
θ limits [°]
Data measd.
Data with I Ͼ 3σ(I)
Number of var.
R
0.9107/1.0000
Ϫ11, 11/Ϫ16, 14/Ϫ17, 15
2.5/30.11
6862
3392
280
0.040
0.049
1.008
0.351
0.865/0.904
Ϫ21, 21/Ϫ19, 17/Ϫ23, 23
2.5/30.02
16735
4404
0.9479/1.0000
Ϫ13, 13/Ϫ10, 15/Ϫ13, 15
2.5/29.13
8501
3850
325
0.037
0.047
1.048
0.410
0.9596/1.1284
Ϫ17, 17/Ϫ18, 18/Ϫ28, 28
2.5/30.03
9815
2613
451
226
0.037
0.044
1.039
0.787
0.030
0.039
1.049
0.266
Rw
GOF
Largest peak in final
Ϫ3
˚
diff. [e·A
]
2120
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122

The Reaction of Diazocyclopentadienyl Compounds with Cyclomanganated Arenes
Table 6. Acquisition and refinement parameters for the X-ray diffraction analyses of complexes 8a, 9a, 9b, 11a and 12a
FULL PAPER
8a
rac-9a
(rel)-u-9b
11a
12a
Empirical formula
M
C24H15MnO4
422.32
C22H12CrMnNO6·CH2Cl2 C26H14CrMnNO6 C48H26Mn2N2O6·2CH2Cl2 C42H22Mn2N2O6
578.21
orthorhombic
P212121
9.1959(2)
13.6927(3)
18.1864(5)
90
543.34
orthorhombic
Pbcn
38.2715(1)
7.6620(2)
15.1092(5)
90
1006.49
monoclinic
P21/n
8.0794(1)
18.4324(2)
30.1912(4)
90
760.53
orthorhombic
Pbcn
8.2243(2)
15.4115(4)
26.9270(7)
90
Crystal system
Space group
triclinic
¯
P1
˚
a [A]
8.5271(2)
10.4016(2)
11.2111(3)
103.243(5)
99.995(5)
93.117(5)
948.63(4)
2
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
90
90
90
90
93.110(5)
90
90
90
3
˚
V [A ]
2289.97(9)
4
4430.6(2)
8
4489.53(9)
4
3413.0(2)
4
Z
Crystal dim. [mm]
0.10 ϫ 0.08 ϫ 0.06 0.20 ϫ 0.10 ϫ 0.08
0.16 ϫ 0.12 ϫ 0.08 0.12 ϫ 0.12 ϫ 0.10
0.12 ϫ 0.10 ϫ 0.08
1.48
1544
Dc [g·cmϪ3
F000
]
1.48
432
1.68
1160
1.63
2192
1.49
2040
µ [mmϪ1
]
0.724
1.300
1.105
0.854
0.794
Trans. min./max.
hkl limits
0.9678/1.0000
Ϫ12, 12/Ϫ14,
14/Ϫ15, 15
2.5/30.06
8741
0.768/0.901
Ϫ12, 12/Ϫ19,
19/Ϫ25, 25
2.5/30.01
6365
0.835/0.925
Ϫ10, 10/Ϫ20,
20/Ϫ52, 52
2.5/29.11
11275
0.9482/1.0000
Ϫ10, 10/Ϫ24,
22/Ϫ39, 39
2.5/27.85
19403
0.907/0.938
0, 10/0, 20/0, 34
θ limits [°]
Data measd.
2.5/27.48
4424
Data with I Ͼ 3σ(I) 3557
2661
307
3535
316
6102
577
2360
237
Number of var.
262
R
Rw
GOF
0.034
0.042
1.075
0.035
0.043
1.041
0.470
0.032
0.044
1.058
0.366
0.049
0.072
1.277
1.301
0.035
0.049
1.052
0.580
Largest peak in final 0.312
diff. [e·A
Ϫ3
˚
]
[5]
M. Salmain, M. Grunn, A. Gorfis, S. Top, G. Jaouen, Bioconj.
Chem. 1993, 4, 425Ϫ433.
Z. Wang, B. A. Roe, K. M. Nicholas, R. L. White, J. Am.
Chem. Soc. 1993, 115, 4399Ϫ4400.
in CDCl3 at 243 K (see also footnote on the first page of this arti-
cle).
[6]
[7]
Acknowledgments
`
G. Jaouen, S. Top, A. Veyssieres, P. Pigeon, G. Leclercq, I.
Laios, Chem. Commun. 2001, 383Ϫ384.
The authors would like to thank the Centre National de la Recher-
che Scientifique and the Deutsche Forschungs Gemeinshaft for
their financial contribution. One of us (J. P. D.) acknowledges also
the financial support provided by the Alexander von Humboldt
foundation. We thank Drs. Rolland Graff and Lionel Allouche
(CNRS, Institut de Chimie de Strasbourg) for carrying out the mul-
tidimensional and low-temperature NMR experiments.
[8] [8a]
S. Kudis, G. Helmchen, Angew. Chem. 1998, 110,
[8b]
3210Ϫ3212; Angew. Chem. Int. Ed. 1998, 37, 3047Ϫ3050.
C. Bolm, M. Kesselgruber, N. Hermanns, J. P. Hildebrand, G.
[8c]
Raabe, Angew. Chem. Int. Ed. 2003, 40, 1488Ϫ1490.
T. D.
Weiß, G. Helmchen, U. Kazmaier, Chem. Commun. 2002,
[8d]
1270Ϫ1271.
C. Bolm, L. Xiao, M. Kesselgruber, Org. Bi-
omol. Chem. 2003, 1, 145Ϫ152. [8e] O. Delacroix, J. A. Gladysz,
Chem. Commun. 2003, 665Ϫ675.
[9] [9a]
[1]
M. Enders, R. Rudolph, H. Pritzkow, J. Organomet. Chem.
[1a] C. Michon, J. P. Djukic, Z. Ratkovic, J. P. Collin, M. Pfeffer,
A. de Cian, J. Fischer, D. Heiser, K. H. Dötz, M. Nieger, Or-
ganometallics 2002, 21, 3519Ϫ3535. [1b] J. P. Djukic, A. Maisse-
Franc¸ois, M. Pfeffer, K. H. Dötz, A. de Cian, J. Fischer, Or-
ganometallics 2000, 19, 5484Ϫ5499.
[9b]
1997, 549, 251Ϫ256.
K. Theopold, Eur. J. Inorg. Chem.
[9c]
1998, 15Ϫ24.
C. Müller, D. Vos, P. Jutzi, J. Organomet.
Chem. 2000, 600, 127Ϫ143. [9d] U. Siemeling, Chem. Rev. 2000,
[9e]
100, 1495Ϫ1526.
M. Enders, G. Kohl, H. Pritzkow, J. Or-
[9f]
[2] [2a]
ganomet. Chem. 2001, 622, 66Ϫ73.
K. Kunz, G. Erker, S.
K. J. Reimer, A. Shaver, J. Organomet. Chem. 1975, 93,
[2b]
Döring, R. Fröhlich, G. Kehr, J. Am. Chem. Soc. 2001, 123,
239Ϫ252.
ganomet. Chem. 1977, 139, C4ϪC8.
Chem. Ber. 1978, 111, 2458Ϫ2460.
W. A. Herrmann, B. Reiter, M. Huber, J. Or-
[2c]
6181Ϫ6182. [9g] M. Enders, P. Fernandez, G. Ludwig, H. Pritz-
W. A. Herrmann,
[9h]
kow, Organometallics 2001, 20, 5005Ϫ5007.
Fröhlich, G. Erker, J. Organomet. Chem. 2001, 621, 197Ϫ206.
T. Dreier, R.
[3] [3a]
T. W. Spradau, J. A. Katzenellenbogen, Organometallics
[10] [10a]
1998, 17, 2009Ϫ2017. [3b] F. Minutolo, J. A. Katzenellenbogen,
J. Am. Chem. Soc. 1998, 120, 4514Ϫ4515. [3c] F. Minutolo, J. A.
Katzenellenbogen, Organometallics 1999, 18, 2519Ϫ2530. [3d] F.
Minutolo, J. A. Katzenellenbogen, Angew. Chem. 1999, 111,
S. J. Gould, N. Tamayo, C. R. Melville, M. C. Cone, J.
[10b]
Am. Chem. Soc. 1994, 116, 2207Ϫ2208.
S. Mithani, G.
Weeratunga, N. J. Taylor, G. I. Dmitrienko, J. Am. Chem. Soc.
[10c]
1994, 116, 2209Ϫ2210.
D. P. Arya, D. J. Jebaratnam, J.
Org. Chem. 1995, 60, 3268Ϫ3269. [10d] W. Williams, X. Sun, D.
[3e]
1730Ϫ1732; Angew. Chem. Int. Ed. 1999, 38, 1617Ϫ1620.
[10e]
Jebaratnam, J. Org. Chem. 1997, 62, 4364Ϫ4369.
S. J.
R. R. Cesati, J. A. Katzenellenbogen, J. Am. Chem. Soc. 2001,
[10f]
Gould, Chem. Rev. 1997, 97, 2499Ϫ2509.
R. S. Laufer, G.
123, 4093Ϫ4094.
[4] [4a]
I. Dmitrienko, J. Am. Chem. Soc. 2002, 124, 1854Ϫ1855.
J. R. Dilworth, S. J. Parrott, Chem. Soc. Rev. 1998, 27,
43Ϫ55. [4b] J. Bernard, K. Ortner, B. Spingler, H.-J. Pietzch, R.
Alberto, Inorg. Chem. 2003, 42, 1014Ϫ1022.
[11]
H. J. Eppley, S. M. lato, A. D. Ellington, J. M. Zaleski, Chem.
Commun. 1999, 2405Ϫ2406.
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2121

J.-P. Djukic et al.
FULL PAPER
[12]
F. M. Mathooko, Y. Kubo, A. Inaba, R. Nakamura, Posthar-
skov, N. V. Podberezskaya, V. E. Zavodnik, I. V. Bragina, L. K.
Kedrova, E. D. Korniets, V. K. Bel’skii, V. V. Bakakin, S. P.
Gubin, Koord. Khim. 1986, 12, 1132Ϫ1140; HIGRIY: T. Bit-
terwolf, A. L. Rheingold, M. B. Allen, private communication,
1996; LASLOG: S. Pitter, G. Huttner, O. Walter, L. Zsolnai, J.
Organomet. Chem. 1993, 454, 183Ϫ198; MIRSOV: J. C. Roder,
F. Meyer, R. F. Winter, E. Kaifer, J. Organomet. Chem. 2002,
641, 113Ϫ120; NEZSUG: T. E. Bitterwolf, S. C. Everly, A. L.
Rheingold, G. Yapp, J. Organomet. Chem. 1997, 531, 1Ϫ7;
QIFBEM: M. A. O. Volland, S. Kudis, G. Helmchen, I. Hyla-
Kryspin, F. Rominger, R. Gleiter, Organometallics 2001, 20,
227Ϫ230.; QODVEK: M. Enders, G. Kohl, H. Pritzkow, J. Or-
ganomet. Chem. 2001, 622, 66Ϫ73; SENSOT: M. D. Raush, W.
C. Spink, B. G. Conway, R. D. Rogers, J. L. Atwood, J. Or-
ganomet. Chem. 1990, 383, 227Ϫ252; VAVHIJ: P. Harter, G.
Boguth, E. Herdtweck, J. Riede, Angew. Chem. 1989, 101,
1058Ϫ1059; VIPGEG: S. Fortier, M. C. Baird, K. F. Preston,
J. R. Morton, T. Ziegler, T. J. Jaeger, W. C. Watkins, J. H.
McNeil, K. A. Watson, K. Hensel, Y. Le Page, J. P. Charland,
A. J. Williams, J. Am. Chem. Soc. 1991, 113, 542Ϫ551;
YIHMOR: V. D. Makhaev, M. Kh. Dzhafarov, N. K. Baranet-
skaya, V. D. Vil’chevskaya, A. S. Batsanov, A. I. Yanovsky,
Yu. T. Struchkov, Koord. Khim. 1994, 20, 838Ϫ841; YUNGAP,
YUNGET: K. Onotsuka, N. Hosokawa, T. Adachi, T. Yosh-
ida, K. Sonogashira, Chem. Lett. 1994, 2067Ϫ2070. [27b] Mono-
benzocymantrenes: BINCMN: N. B. Honan, J. L. Atwood, I.
Bernal, W. A. Herrmann, J. Organomet. Chem. 1979, 179,
vest Biol. Technol. 1995, 5, 221Ϫ233.
[13] [13a]
M. Regitz, G. Maas, in Diazo Compounds, Properties and
[13b]
Synthesis, Academic Press, Orlando, USA, 1986.
The
Chemistry of Diazonium and Diazo groups, part I (Ed.: S. Patai),
[13c]
Wiley, Chichester, U.K., 1978.
B. Eistert, M. Regitz, G.
Heck, H. Schwall, in Methoden der Organischen Chemie, 4th
ed. (Ed.: E. U. Miller), Georg Thieme Verlag, Stuttgart, 1968,
[13d]
vol. X/4, p. 473Ϫ893.
M. Bösch, J. Fink, H. Heydt, O.
Wagner, M. Regitz, in Methoden der Organischen Chemie, 6th
ed. (Eds.: D. Klaman, H. Hagemann), Georg Thieme Verlag,
New York, 1990, vol. E14B, p. 996Ϫ1010. [13e]A. Albini, H.
Kirsch, Top. Curr. Chem. 1976, 65, 105Ϫ145.
[14] [14a] H. Staudinger, O. Kupfer, Ber. Dtsch. Chem. Ges. 1911, 44,
[14b]
2197Ϫ2212.
P. S. R. Anjaneyulu, A. K. Lala, FEBS Lett.
1982, 146, 165Ϫ167.
[15] [15a]
J. Pfeiffer, M. Nieger, K. H. Dötz, Chem. Eur. J. 1998, 4,
[15b]
1843Ϫ1851.
L. J. McDowell, M. M. Khodaei, D. Bethell,
Org. Biomol. Chem. 2003, 1, 995Ϫ1003.
[16]
T. Weil, M. Cais, J. Org. Chem. 1963, 28, 2472Ϫ2473.
[17] [17a]
D. Rewicki, C. Tuchscherer, Angew. Chem. 1972, 84,
[17b]
31Ϫ32.
R. O. Duthaler, H. G. Förster, J. D. Roberts, J.
[17c]
Am. Chem. Soc. 1978, 100, 4974Ϫ4979.
A. Black, J. Am. Chem. Soc. 1984, 106, 1029Ϫ1040.
J. E. Baldwin, K.
[18]
[19]
W. R. Bamford, T. S. Stevens, J. Chem. Soc. 1952, 4735Ϫ4740.
C. S. Marvel, C. W. Hinman, J. Am. Chem. Soc. 1954, 76,
5435Ϫ5437.
[20] [20a]
S. Kapur, N. C. Mathur, K. McManus, A. L. Pincock, J.
403Ϫ410; TURNID: C. Qian, J. Guo, J. Sun, J. Chen, P. Zheng,
[20b]
[27c]
A. Pincock, Can. J. Chem. 1988, 66, 2888Ϫ2893.
A. Mar-
Inorg. Chem. 1997, 36, 1286Ϫ1295.
Dibenzocymantrene:
rochi, L. Minuti, A. Tatichi, H. W. Scheeren, Tetrahedron 2001,
BAHFEW: A. de Cian, J. P. Djukic, J. Fischer, M. Pfeffer, K.
H. Dötz, Chem. Commun. 2002, 638Ϫ639; MIYXAT: A.
Decken, A. J. Mackay, M. J. Brown, F. Bottomley, Organomet-
allics 2002, 21, 2006Ϫ2009; ZUKLOG: A. I. Yarmolenko, S.
V. Kukharenko, L. N. Novikova, N. A. Ustinyuk, F. M. Dlogu-
shin, A. I. Yanovsky, Yu. T. Struchkov, T. G. Kaftaeva, Yu. F.
Oprunenko, V. V. Strelets, Izv. Akad. Nauk. SSSR, Ser. Khim.
1996, 199Ϫ203.
57, 4959Ϫ4965.
[21]
[22]
W. E. von Doering, C. H. DePuy, J. Am. Chem. Soc. 1953,
75, 5955Ϫ5957.
M. Regitz, A. Liedhegener, Tetrahedron 1967, 23, 2701Ϫ2708.
[23] [23a]
M. I. Bruce, M. Z. Iqbal, F. G. A. Stone, J. Chem. Soc. A
[23b]
1970, 3204Ϫ3209.
R. J. Doedens, R. G. Little, J. T. Veal, J. Organomet. Chem.
R. L. Bennet, M. I. Bruce, I. Matsuda,
[23c]
[28]
[29]
1974, 67, C72ϪC74.
G. J. Depree, N. D. Chiderhouse, B.
The structures of η1-fluorenyl complexes of Mn(CO)5 and
Re(CO)5, respectively, are referenced by the CSDB as:
MIYXEX: A. Decken, A. J. MacKay, M. J. Brown, F. Bot-
tomley, Organometallics 2002, 21, 2006Ϫ2009; WENQOV: A.
L. Mejdrich, T. W. Hanks, Synth. React. Inorg. Met.-Org.
Chem. 1998, 28, 953Ϫ973.
CSDB refcode ROMQIT: A. Decken, S. S. Rigby, L. Girard,
A. D. Bain, M. J. McGlinchey, Organometallics 1997, 16,
1308Ϫ1315.
S. Top, E. B. Kaloun, S. Toppi, A. Herrbach, M. J. McGlin-
chey, G. Jaouen, Organometallics 2001, 20, 4554Ϫ4561.
T. Wang, I. S. Cloudsdale, Synth. Commun. 1997, 27,
2521Ϫ2526.
K. Nicholson, J. Organomet. Chem. 1997, 533, 143Ϫ159.
[24] [24a] L. F. Veiros, J. Organomet. Chem. 1999, 587, 221Ϫ232. [24b]
[24c]
L. F. Veiros, Organometallics 2000, 19, 3127Ϫ3136.
L. F.
[24d]
Veiros, Organometallics 2000, 19, 5549Ϫ5558.
M. Stradi-
otto, M. J. McGlinchey, Coord. Chem. Rev. 2001, 219Ϫ221,
311Ϫ378.
[25]
[26]
[27]
M. J. Calhorda, L. F. Veiros, Coord. Chem. Rev. 1999,
185Ϫ186, 37Ϫ51.
[30]
[31]
[32]
A. G. Orpen, L. Brammer, F. H. Allen, O. Kennard, D. G.
Watson, R. Taylor, J. Chem. Soc., Dalton Trans. 1989, S1ϪS83.
CSDB refcodes for: [27a] Cymantrenes: BEHGAW: V. G. Andri-
anov, Yu. T. Struchkov, P. V. Petrovskii, E. I. Fedin, D. N. Kur-
sanov, S. P. Dolgova, V. N. Setkina, J. Organomet. Chem. 1981,
221, 183Ϫ191; BUWDEC: V. B. Ribakov, L. A. Aslanov, V.
M. Ionov, S. A. Eremin, Zh. Strukt. Khim. 1983, 24, 74Ϫ82;
CPMNCO01: P. J. Fitzpatrick, Y. Le Page, J. Sedman, I. S.
Butler, Inorg. Chem. 1981, 20, 2852Ϫ2861; CPMNCO02: J. Co-
wie, E. J. M. Hamilton, J. C. V. Laurie, A. J. Welch, J. Or-
ganomet. Chem. 1990, 394, 1Ϫ13; CUMGUM: V. A. Milyukov,
A. V. Zverev, S. M. Podlesnov, D. B. Krivolapov, I. A. Litvinov,
A. T. Gubaidullin, O. N. Kataena, A. G. Ginzburg, O. G. Siny-
ashin, Eur. J. Inorg. Chem. 2000, 225Ϫ228; DAJSOW: A.
Tuozzi, C. L. Sterzo, A. Sperandio, G. Bocelli, Tetrahedron
1999, 55, 461Ϫ474; ETCYMT: N. M. Loim, Z. N. Parnes, V.
G. Andrianov, Yu. T. Struchkov, D. N. Kursanov, J. Or-
ganomet. Chem. 1980, 201, 301Ϫ310; FAZXAF: V. A. Mak-
H. Bredereck, R. Gompper, G. Morlock, Chem. Ber. 1957,
90, 942Ϫ952.
[33] [33a]
C. Glidewell, S. Z. Ahmed, M. Gottfried, P. Lightfoot, B.
J. L. Royles, J. P. Scott, J. Wonnemann, J. Organomet. Chem.
1997, 530, 177Ϫ185. [33b] P. Zanello, M. Fontani, S. Z. Ahmed,
C. Glidewell, Polyhedron 1998, 17, 4155Ϫ4162.
M. Pfeffer, E. Urriolabeitia, J. Fischer, Inorg. Chem. 1995, 34,
643Ϫ650.
C. K. Fair in MolEN. An Interactive Intelligent System for
Crystal Structure Analysis, Nonius, Delft, The Netherlands,
1990.
[34]
[35]
Received November 19, 2003
Early View Article
Published Online April 6, 2004
2122
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2107Ϫ2122