Manganese(IV) corroles with σ-aryl ligands

Article abstract of DOI:10.1002/zaac.200700332

Different pathways for the preparation of organometallic manganese(IV) corroles with rj-aryl ligands have been evaluated. The treatment of a manganese(III) corroie with Grignard reagents PhMgX (X = Cl, Br), followed by aerial oxidation yields oxidized halogenido complexes [(cor)Mn^IVX] instead of the anticipated organometallic compounds. Reaction of these halogenido species, especially the bromido compound, with excess Grignard reagents or with lithium aryls results in the formation of the desired σ-aryl compounds via salt metatheses. Three examples of this class of rare complexes have been characterized by means of optical and ¹H NMR spectroscopy, and in two cases single crystal X-ray diffraction studies have been carried out. In the crystal, the molecular structures of the σ-phenyl- and the σ-(p-bromophenyl) derivatives were observed to be very similar, albeit both species pack in different pattern.

Full text of DOI:10.1002/zaac.200700332

DOI: 10.1002/zaac.200700332
Manganese(IV) Corroles with σ-Aryl Ligands
Martin Bröring*, Meike Cordes, and Silke Köhler
Marburg, Fachbereich Chemie der Philipps-Universität
Received June 26th, 2007.
Abstract. Different pathways for the preparation of organometallic
manganese(IV) corroles with σ-aryl ligands have been evaluated.
The treatment of a manganese(III) corrole with Grignard reagents
PhMgX (X ϭ Cl, Br), followed by aerial oxidation yields oxidized
halogenido complexes [(cor)MnIVX] instead of the anticipated
organometallic compounds. Reaction of these halogenido species,
especially the bromido compound, with excess Grignard reagents
or with lithium aryls results in the formation of the desired σ-aryl
compounds via salt metatheses. Three examples of this class of rare
complexes have been characterized by means of optical and 1H
NMR spectroscopy, and in two cases single crystal X-ray diffrac-
tion studies have been carried out. In the crystal, the molecular
structures of the σ-phenyl- and the σ-(p-bromophenyl) derivatives
were observed to be very similar, albeit both species pack in differ-
ent pattern.
Keywords: Manganese; High-spin organometallics; Corroles; X-ray
diffraction; Porphyrinoids
Introduction
Organometallic porphyrinoid transition metal complexes
with σ-bonded alkyl or aryl axial ligands are of interest
as model compounds for understanding the functions and
relationships of several biological macromolecules [1]. From
this viewpoint, a vast amount of data has become available
over recent years, but the majority has concerned com-
pounds with iron, cobalt, or rhodium metal ions. The
chemical reactivity of this family of compounds has also
attracted interest owing to their potential use in the acti-
vation of small molecules.
Although porphyrin complexes with organic co-ligands
are known for 29 metallic and pseudometallic elements,
only one case of a manganese porphyrin with an axial car-
bene ligand has been described, and the corresponding σ-
bonded alkyl complex was postulated only as an intermedi-
ate [2]. This result is in agreement with conclusions from
the reaction of alkyl or fluoroalkyl radicals with manganese
porphyrins [3]. Nonreducing alkyl radicals such as .CH3 ex-
ibit a very low reactivity against manganese(III) porphyrins
and no evidence has been found for the formation of a
[(por)MnR] complex with a lifetime longer than ca. 0.1 ms.
While to the best of our knowledge there is still no defi-
nite evidence for the existence of stable σ-bonded or-
ganometallic manganese(III) porphyrins, one quite well
characterized example of an analogous compound, the σ-
phenyl(corrolato)manganese(IV) (1) exists in the corrole
series (figure 1) [4]. The compound has been thoroughly
Fig. 1 Literature precedent [(oec)MnIV(ph)] (1) [4].
characterized by crystallographic, spectroscopic and elec-
trochemical means, and a high-spin ground state with a S ϭ
3/2 MnIV ion was confirmed for this stable organometallic
complex. In the course of our attempts to prepare func-
tional magnetic [5] and other polynuclear materials [6] by
rational approaches we became interested in novel building
blocks combining kinetic stability and a high-spin electronic
ground state like 1 [7]. In this contribution we wish to re-
port our recent study toward the preparation of such spec-
ies and about the successful preparation and structural
characterization of halogene functionalized σ-arylman-
ganese(IV) corroles.
Results and Discussion
For our study we have chosen the hexaethyldimethylcorrole
ligand (H3hedmc) (5) of which a structurally characterized
square-planar manganese complex [(hedmc)Mn] (6) has
been reported [8]. 5 was prepared in two steps from formyl-
pyrrole 2 and dipyrromethane 3 according to the literature
as depicted in scheme 1. The insertion of a manganese ion
in corroles can in principle be achieved under three different
conditions. In the case of 6 and related octaalkyl derivatives
literature recommends the cyclization of the biladiene 4 in
the presence of excess manganese(II) acetate [9] or the reac-
* Prof. Dr. M. Bröring
Fachbereich Chemie der Philipps-Universität
D-35032 Marburg
Fax: ϩϩ49-(0)6421-2825356
E-mail: martin.Broering@chemie.uni-marburg.de
Z. Anorg. Allg. Chem. 2008, 634, 125Ϫ130
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125

M. Bröring, M. Cordes, S. Köhler
tion of H3hedmc (5) with dimanganesedecacarbonyl, fol-
lowed by aerial oxidation [10]. In our hands the treatment
of the corrole with manganese(II) acetate in hot DMF, pre-
ferred method for triarylcorroles, [11] gave the best results
and produced the desired manganese corrole 6 in 78 % yield
(scheme 1). [(hedmc)Mn] (6) was unambigously identified
sor to a (cor)MX species (X ϭ Cl, Br, I) [4, 11, 12, 17] with
concommitant anion metathesis using (aryl)M reagents as
described before [4, 18].
1
by a comparison of H NMR and UV/Vis spectra as well
as by high-resolution mass spectrometry.
Scheme 2 Attempted preparation of arylmanganese(IV)corroles
9Ϫ11.
The initial attempts to prepare the desired organometall-
ics via the presumably simpler one-pot route failed. Instead,
the treatment of [(hedmc)Mn] (6) with phenyllithium, phe-
nylmagnesium chloride, or phenylmagnesium bromide in
cold dichloromethane yielded the new halogenido com-
plexes [(hedmc)MnCl] (7) and [(hedmc)MnBr] (8), respec-
tively, as the only isolable products. Identical derivatives can
be obtained easier and in better yields upon simple treat-
ment of 6 with industrial grade dichloromethane (for 7) or
a solution of magnesium bromide dietherate in purified di-
chloromethane (for 8). Since no well-formed single crystals
could be obtained from the new complexes, their identity
had to rely on a comparison of 1H NMR and UV/Vis spec-
troscopic data with those of analogous [(cor)MnX] pre-
cedents in the literature. The most characteristic difference
between manganese corroles with the oxidation state ϩ3 (6)
and ϩ4 (7 and 8) is seen in the optical spectra. In the oxid-
ized form the halogenido derivatives display a split soret
band with maxima at 350 and 410 nm (7) and at 342 and
413 nm (8), in addition to markedly less intense Q bands at
586 nm, while the manganese(III) species shows three broad
absorptions at 389, 480 and 588 nm with the band at
480 nm being ascribed to a MLCT transition (figure 2).
Applying the two-step procedure indicated in scheme 2
was immediately successful. The treatment of the bromido
derivate 8 with phenylmagnesium bromide, followed by aer-
ial oxidation resulted in the formation of the anticipated
product [(hedmc)Mn(ph)] (9), albeit a seven-fold excess of
the Grignard reagent had to apply for a complete trans-
formation. The compound was purified by chromato-
graphic filtration over a silica plug and obtained after evap-
oration of all volatiles in 99 % yield. This procedure could,
in a slightly different way, also be applied for the synthesis
Scheme 1 Synthesis of corrole (5) and manganese(III)corrole (6)
on different pathways.
The data obtained for 6 are indeed identical to those
found in literature [8] and very similar to those of other
manganese(III) corroles, that have been described so far [4,
12]. An interesting subject concerning trivalent manganese
in the corrole environment is the quest for the proper metal
oxidation state. Paolesse, Boschi et al. have reported a
change from ϩ3 to ϩ2 upon the addition of two intermedi-
ately strong axial pyridine ligands, indicated by a change in
the optical spectra [8]. A similar behaviour has been the
topic of many discussions on related manganese porphyrins
before [13]. In general, this behaviour of transition metal
ions to reside in oxidation states lower than the formal oxi-
dation state appears particularly typical for metal corroles
and has been observed in a number of cases [14]. This so-
called non-innocent behaviour [15] of the corrole ligand
has, however, not been observed for 6, and no detailed stud-
ies have so far been attempted.
Preparatively, the metal arylation step is in general
known within the class of metal corroles using one out of
two principal procedures. As detailed in scheme 2 the first
procedure contains only one step and utilizes the formation
of an Ϫate complex from (aryl)MgX or (aryl)Li and
(cor)M, with successive work-up in air [16]. The other path
requires two steps, i.e. the oxidation of the (cor)Mn precur-
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Manganese(IV) Corroles with σ-Aryl Ligands
of functionalized organometallic manganesecorroles. If in-
stead of the Grignard reagent a preformed mixture of equi-
molar n-BuLi and 1,4-dibromobenzene or 1,4-diiodoben-
zene [19] in dry THF is used, the functionalized products
[(hedmc)Mn(4-BrC6H4)] (10) and [(hedmc)Mn(4-IC6H4)]
(11) are isolated in 77 % and 38 % yield, respectively, as
dark violet powders. Since the aryl substituents of 9-11 are
bound in a kinetically inert fashion these three species could
be analyzed by HRMS techniques as the Mϩ ions and with-
out loss of the axial donor ligands. Again, the reaction can
be monitored spectroscopically since optical and nuclear
resonance spectra of the new species show very character-
istic features distinct from the halogenido complexes 7 and
8 as well as from the manganese(III) derivative 6 (figure 2).
Fig. 3 Molecular structure of 9 (side view) and view on the
relative orientation of the phenyl ligand (alkyl groups removed for
˚
clarity). Selected bond lengths /A and -angles /°:
Mn-C34 2.019(5), Mn-N1 1.883(4), Mn-N2 1.905(4), Mn-N3 1.898(4), Mn-
N4 1.878(3); N1-Mn-C34 96.97(16), N2-Mn-C34 100.3(2), N3-Mn-C34
99.39(16), N4-Mn-C34 97.6(2), N1-Mn-N2 90.6(2), N1-Mn-N3 161.43(14),
N1-Mn-N4 78.60(15), N2-Mn-N3 95.07(15), N2-Mn-N4 160.03(15), N3-
Mn-N4 90.53(15).
Fig. 2 Optical spectra (ca. 10Ϫ5 mol/L in CH2Cl2) of [(hedmc)Mn]
(6) (ᎏ), [(hedmc)MnBr] (8) (Ϫ) and [(hedmc)Mn(C6H4Br)] (10)
(···).
Besides the mass spectrometrical analyses and the spec-
troscopic characterization 9 and 10 could be investigated by
single crystal X-ray diffraction studies. Material suitable for
the measurements was obtained in both cases by slow evap-
oration of methanol/dichloromethane solutions. For 9 the
molecules pack with Z ϭ 8 in the monoclinic system, space
group C2/c, while for 10 space group P1bar and the triclinic
system has been found with Z ϭ 2. The molecular struc-
tures and metrical data for the new compounds are pre-
sented in figures 3 (9) and 4 (10).
Fig. 4 Molecular structure of 10 (side view) and view on the rela-
tive orientation of the C6H4Br ligand (alkyl groups removed for
˚
clarity). Selected bond lengths /A and -angles /°:
Mn-C34 2.019(3), Mn-N1 1.891(3), Mn-N2 1.907(2), Mn-N3 1.893(3), Mn-
N4 1.901(2); N1-Mn-C34 95.53(12), N2-Mn-C34 95.29(11), N3-Mn-C34
99.69(12), N4-Mn-C34 99.39(11), N1-Mn-N2 90.29(11), N1-Mn-N3
162.99(11), N1-Mn-N4 79.75(11), N2-Mn-N3 95.79(11), N2-Mn-N4
162.95(11), N3-Mn-N4 90.27(11).
The bond lengths and angles within the MnN4 coordi-
nation units of 9 and 10 are as expected very similar. All
Mn-N bonds can be found within the narrow range of 1.883
˚
to 1.907 A. The N-Mn-N angles in 9 and 10, that should
found in both cases in an almost coplanar conformation.
The distances between the mean squares planes of the C19
be rectangular for an undistorted square-planar coordi-
nation, are shortened within the bipyrrolic unit to
78.60(15)° and 79.75(11)° and enlarged at the opposite posi-
tion N2-Mn-N4 to 95.07(15)° and 95.79(11)°, respectively,
while the other two angles deviate from 90° by less than
0.6°. The manganese atoms of 9 and 10 are displaced 0.285
˚
ligand backbones and the manganese ions of 0.280 A (9)
˚
and 0.183 A (10) are in fact smaller than the Mn-{mean-
squares plane-N4} distances and indicate a slightly convex
ligand conformation in both cases.
The molecular structures of 9 and 10 differ significantly
with respect to the aryl ligand situations. As the insets in
figure 3 and 4 reveal the planes of the ph and C6H4Br li-
gands are found differently rotated with respect to the
MnN4 coordination unit. This behaviour can be understood
on the basis of the electronic structure of the central ion,
˚
and 0.247 A from the least-squares plane formed by the
pyrrole nitrogen atoms and thus display domed square-pyr-
amidal coordination. This value is about 30-40 % smaller
than that found for halogenidomanganese(IV)corroles [11,
4, 17]. The tetrapyrrolic macrocycle does not react signifi-
cantly to the displacement of the central metal atom and is
3
0
which should be in a dπ dσ configuration and therefore
Z. Anorg. Allg. Chem. 2008, 125Ϫ130
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127

M. Bröring, M. Cordes, S. Köhler
allow a rotation of the axial group with almost no barrier.
Unexpected, however, is the tilted coordination of the
C6H4Br ligand of 10 which bends away from a perpendicu-
lar orientation by 6.39° (9: 1.03°). No obvious electronic or
steric argument could explain this finding. A rational for
this behaviour was found in different intermolecular inter-
actions as revealed by a comparison of the crystal packings
of 9 and 10 (figures 5 and 6).
Fig. 5 Chain-like crystal packing pattern of molecules 9.
For 9, molecules of identical orientation are arranged in
Fig. 6 π-Stacked dimers of 10 (top) and their organization in a
layer (bottom).
˚
chains with a Mn···Mn distance of 8.889 A. One identical
bour dimers and tilt the organometallic ligand from the op-
timum binding position in the sense of a shear.
second chain of molecules 9 displaying a different orien-
tation is located within the van der Waals distance of the
first chain (figure 5), and the crystal is build from the uni-
form association of these double chains with each other. In
the local view the next neighbours within this scenario do
not influence each other significantly. Although the π···π
distance observed between next neighbour molecules of the
In summary we have described a general preparative en-
try for functionalized organometallic manganese(IV) cor-
roles and have characterized the new compounds by spec-
troscopic and X-ray crystallographic means. Future work
will attempt homo- and cross coupling reactions as well as
halide-metal exchange studies on the high spin organomet-
allics in order to produce novel building blocks for mol-
ecule-based functional materials.
˚
same chain is as small as 3.682 A the overlap of the respect-
ive macrocycles is small as realized by the lateral shift of
˚
8.091 A. The contact between the phenyl ligand of one mol-
ecule and the alkyl substituents of the neighbour macrocy-
cle thereby becomes sufficiently weak. This results in the
finding of an almost undistorted binding of the axial C-do-
nor.
Experimental Section
Materials and Methods: H3(hedmc) (5) [8] and 1,4-diiodobenzene
[19] were prepared according to published procedures. All other
chemicals were purchased from Aldrich or Merck and used without
further purification. Solvents were dried by standard procedures
and distilled from appropriate drying agents. 1H NMR spectra were
recorded on Bruker AMX 400 spectrometer. δ values are given rela-
tive to residual protio solvent signals. UV/Vis spectra were meas-
ured on a Shimadzu UV-1601 PC in concentrations of about 10Ϫ5
mol LϪ1. Mass spectra were measured on a VG Tribid or a Varian
CH7 (EI), a IonSpec Ultima or a QStar Pulsar i (ESI), or a Bruker
Biflex IV instrument (MALDI-TOF). m/z values are given for the
most abundant isotopes only.
A different situation is present for 10. In the crystal the
bromophenyl derivative forms strongly π-stacked dimers
˚
with a Mn···Mn distance of 5.056 A and a π···π distance of
˚
only 3.389 A, resulting in a largely overlapped structure
˚
with a small lateral shift of 3.752 A. These dimers are than
densely packed in independent layers (figure 6). Within
these layers the manganese atoms of next neighbour dimers
˚
are found in distances of 9.399 A on one side and of
˚
8.564 A on the other. The lateral shift, which is a measure
for the degree of repulsive interaction between the C6H4Br
ligand and the alkyl groups of the neighbour molecule, is
(2,3,8,12,17,18-Hexaethyl-7,13-dimethylcorrolato)manganese(III)
[(hedmc)Mn] (6). A solution of H3(hedmc) (5) (200 mg, 0.4 mmol)
in dry DMF (60 mL) is heated to 80 °C. Manganese(II) acetate
tetrahydrate (490 mg, 2.0 mmol) in DMF (6 mL) are added with
vigorous stirring on air. After 3 min the heating source is removed
˚
˚
found at 8.124 A on the wide side, but at only 7.641 A at
the narrow side. This last distance is insufficient for an un-
distorted arrangement. The packing forces thus arrange the
bromophenyl moieties tightly inbetween two next neigh-
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Manganese(IV) Corroles with σ-Aryl Ligands
and the mixture is stirred for another 45 min. After cooling in ice
the mixture is poored onto diethylether (100 mL) and water
(600 mL), and the layers are separated. The aqueous layer is ex-
tracted three times with ether (3 ϫ 100 mL), and the combined
organic layers are washed once with water (100 mL) and dried with
sodium sulfate. Chromatographic purification on basic alumina III
with toluene/ether (2:1) and removal of the solvent in vacuo yields
the title compound as a blueish-black, fibrous solid. Yield: 170 mg
perature for 140 min. A suspension of [(hedmc)MnBr] (8) (60 mg,
0.096 mmol) in dry THF (50 mL) is treated at 0 °C with 0.35 mL
of this solution and stirred for 3 min, before the next aliquot is
added. This operation is repeated 7 times, before the mixture is
quenched with water (5 mL), extracted with dichloromethane
(25 mL) and filtered over silica. Removal of all volatiles from the
eluat yields the title compound as a brownish-red powder. Yield:
1
52 mg (0.074 mmol, 77 %). Ϫ H NMR (400 MHz, CD2Cl2): δ ϭ
1
(0.31 mmol, 78 %). Ϫ H NMR (400 MHz, toluene-d8): δ ϭ 70.8,
76.6, 52.5, 47.7, 28.9, 26.6, 11.5, 5.0, 3.9, 3.8, Ϫ26.1. Ϫ UV/Vis
(CH2Cl2): λ /nm ϭ 376, 528, 619. Ϫ HRMS (ESI): m/z 701.2034;
calcd. for [C39H43BrN4Mn]ϩ: 701.2052.
39.6, 18.8, 15.5. Ϫ UV/Vis (toluene): λ /nm ϭ 389, 480, 588. Ϫ
HRMS (EI): m/z 546.2572; calcd. for [C33H39N4Mn]ϩ: 546.2555.
Chlorido-(2,3,8,12,17,18-hexaethyl-7,13-dimethyl-
corrolato)manganese(IV)
4-Iodophenyl-(2,3,8,12,17,18-hexaethyl-7,13-
dimethylcorrolato)manganese(IV)
[(hedmc)MnCl] (7). A solution of [(hedmc)Mn] (6) (100 mg,
0.18 mmol) in CH2Cl2 (50 mL) is stirred in air for 5 min and fil-
tered on silica with dichloromethane/ether (2:1). After removal of
the solvent a dark residue remains. Yield: 103 mg (98 %). The com-
pound is identical to the one formed upon treatment of (6) with
phenylmagnesium chloride in ether. Ϫ 1H NMR (400 MHz,
CD2Cl2): δ ϭ 29.8, 19.4, 16.1, 9.2, Ϫ2.5, Ϫ10.9. Ϫ UV/Vis
(CH2Cl2): λ /nm ϭ 350, 410, 586.
[(hedmc)Mn(4-IC6H4)] (11). 1,4-Diiodobenzene (330 mg, 1.0 mmol)
in dry THF (3 mL) is cooled to Ϫ78 °C under a blanket of argon
and treated with 1 eq. of n-BuLi (0.58 mL of a 1.65 mol LϪ1 solu-
tion in n-hexane), and the solution is stirred at this temperature for
210 min. A suspension of [(hedmc)MnBr] (8) (60 mg, 0.096 mmol)
in dry THF (50 mL) is treated at 0 °C with 0.35 mL of this solution
and stirred for 3 min, before the next aliquot is added. This oper-
ation is repeated 7 times, before the mixture is quenched with water
(5 mL), extracted with dichloromethane (25 mL) and filtered over
silica. Removal of all volatiles from the eluat yields the title com-
pound as a brownish-red solid. Yield: 27 mg (0.036 mmol, 38 %).
Bromido-(2,3,8,12,17,18-hexaethyl-7,13-dimethyl-
corrolato)manganese(IV)
1
Ϫ H NMR (400 MHz, CD2Cl2): δ ϭ 52.6, 47.8, 29.0, 26.6, 11.5,
5.0, 4.0, 3.9, Ϫ30.5. Ϫ UV/Vis (CH2Cl2): λ /nm ϭ 376, 525, 618. Ϫ
[(hedmc)MnBr] (8). A solution of [(hedmc)Mn] (6) (100 mg,
0.18 mmol) in CH2Cl2 (50 mL) is stirred in air for 5 min. After
addition of MgBr2 ϫ Et2O (253 mg, 1.1 mmol) and further stirring
for 5 min the mixture is extracted with water and filtered over silica
with dichloromethane/ether (2:1). Removal of the solvent yields a
black microcrystalline material. Yield: 110 mg (98 %). The com-
pound is identical to the one formed upon treatment of (6) with
phenylmagnesium bromide in ether. Ϫ 1H NMR (400 MHz,
CD2Cl2): δ ϭ 30.1, 21.5, 16.3, 11.8, Ϫ0.2, Ϫ8.6. Ϫ UV/Vis
(CH2Cl2): λ /nm ϭ 342, 413, 586.
HRMS (ESI): m/z 749.1908; calcd. for [C39H43IN4Mn]ϩ: 749.1913.
Collection and Reduction of X-ray Data. Intensity data for 9 and
10 were collected from single crystals at 193(2) K, using a Stoe
IPDS-1 X-ray diffractometer. Graphite monochromated Mo KͰ
˚
radiation (0.71073 A) was used. The structures were solved by the
Patterson method (9) or by direct methods (10) with SHELXS-
97 [20]. Refinements were carried out by full-matrix least-squares
techniques against F2 using SHELXL-97 [21]. All non-hydrogen
atoms were refined anisotropically. Hydrogen atoms were assigned
to idealized positions. Crystallographic data (excluding structure
factors) for the structures reported in this paper has been deposited
with the Cambridge Crystallographic Data Centre as supplemen-
tary publication no. CCDC-651948 and -651949. Copies of the data
can be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK [Fax: ϩ44(1223) 336-033;
E-mail: deposit@cam.ac.uk].
Phenyl-(2,3,8,12,17,18-hexaethyl-7,13-dimethyl-
corrolato)manganese(IV)
[(hedmc)Mn(ph)] (9). A solution of [(hedmc)MnBr] (8) (30 mg,
0.048 mmol) in dry CH2Cl2 (25 mL) is treated under an atmosphere
of argon dropwise with 6 eq. of PhMgBr in diethylether
(0.29 mmol, 0.58 mL of a 0.5 mol LϪ1 solution). After 3 min the
mixture is quenched with water (5 mL), extracted with dichloro-
methane (50 mL) and filtered on silica. Removal of all volatiles
from the eluat yields the title compound as a brownish-red powder.
Yield: 34 mg (99 %). Ϫ 1H NMR (400 MHz, CD2Cl2): δ ϭ 76.2,
51.2, 46.5, 27.7, 25.8, 11.1, 4.9, 3.8, 2.8, Ϫ50.9. Ϫ UV/Vis (CH2Cl2):
λ /nm ϭ 376, 526, 614. Ϫ HRMS (ESI): m/z 623.2946; calcd. for
[C39H44N4Mn]ϩ: 623.2933.
Crystal data for 9: C39H44MnN4, 623.37, brown needle, crystal
size /mm 0.36 ϫ 0.08 ϫ 0.04, monoclinic, space group C2/c, a ϭ
˚
32.001(11), b ϭ 8.8888(18), c ϭ 27.391(8) A, β ϭ 124.24(2)°, V ϭ
3
6441(4) A , Z ϭ 8, ρcalc ϭ 1.286 g cmϪ3, μ(Mo-Kα) ϭ 0.444 cmϪ1
,
˚
θmin ϭ 1.80°, θmax ϭ 26.00°, 30703 reflections measured, 6273 inde-
pendent, 2149 observed with I > 2σ(I), 404 parameters, 0 restraints,
R1 [I > 2σ(I)] ϭ 0.0461, R1 (all data) ϭ 0.1667, wR2 (all data) ϭ
Ϫ3
˚
0.0822, max./min. peak ϭ 0.328/Ϫ0.282 eA
.
Crystal data for 10: C39H43BrMnN4, 702.62, brown block, crystal
4-Bromophenyl-(2,3,8,12,17,18-hexaethyl-7,13-
dimethylcorrolato)manganese(IV)
¯
size /mm 0.34 ϫ 0.23 ϫ 0.13, triclinic, space group P1, a ϭ
˚
11.2309(13), b ϭ 12.6237(15), c ϭ 13.1136(16) A, Ͱ ϭ 71.843(14)°,
3
˚
[(hedmc)Mn(4-BrC6H4)] (10). 1,4-Dibromobenzene (236 mg,
1.0 mmol) in dry THF (3 mL) is cooled to Ϫ78 °C under a blanket
of argon and treated with 1 eq. of n-BuLi (0.58 mL of a 1.65 mol
LϪ1 solution in n-hexane), and the solution is stirred at this tem-
β ϭ 84.285(15)°, γ ϭ 85.048(14)°, V ϭ 1754.8(4) A , Z ϭ 2, ρcalc ϭ
1.330 g cmϪ3, μ(Mo-Kα) ϭ 1.547 cmϪ1, θmin ϭ 2.36°, θmax
ϭ
26.06°, 17583 reflections measured, 6425 independent, 4387 ob-
served with I > 2σ(I), 414 parameters, 0 restraints, R1 [I > 2σ(I)] ϭ
Z. Anorg. Allg. Chem. 2008, 125Ϫ130
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
129

M. Bröring, M. Cordes, S. Köhler
´
0.0429, R1 (all data) ϭ 0.0667, wR2 (all data) ϭ 0.1112, max./min.
Köhler, E. Consul Tejero, Z. Anorg. Allg. Chem. 2004, 630,
817Ϫ820; (j) M. Bröring, A. Pfister, K. Ilg, Chem. Commun.
2000, 1407Ϫ1408.
Ϫ3
˚
peak ϭ 0.509/Ϫ0.500 eA
.
[7] K. Venkatesan, O. Blacque, H. Berke, Dalton Trans. 2007,
Acknowledgements. We gratefully acknowledge financial support
for this work by the Deutsche Akademische Austauschdienst
(DAAD).
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Z. Anorg. Allg. Chem. 2008, 125Ϫ130