Reinvestigation of arylmanganese chemistry - Synthesis and molecular structures of [(thf)4Mg(μ-Cl)2Mn(Br)Mes], [Mes(thf)Mn(μ-Mes)]2, and (MnPh2)∞ (Ph = C6H5; Mes = mesityl, 2,4,6-Me3C6H2)

Article abstract of DOI:10.1016/j.jorganchem.2008.10.045

The reaction of 2,4,6-trimethylphenylmagnesium bromide (MesMgBr) with manganese(II) chloride in an equimolar ratio yields [(thf)₄Mg(μ-Cl)₂Mn(Br)Mes] (1) with two bridging chloro ligands and a Mn-C bond length of 2.136(5) A??. A molar ratio of 2:1 leads to a metathesis reaction and the formation of [Mes(thf)Mn(μ-Mes)]₂ (2) with two bridging mesityl groups. Whereas THF-free [MnMes₂]₃ crystallizes as a trimer from toluene solution, the reduced bulkiness of the phenyl groups in (MnPh₂)_∞ (3) leads to the formation of a chain-like structure with Mn-C bond lengths of 2.245(3) A??.

Full text of DOI:10.1016/j.jorganchem.2008.10.045

Journal of Organometallic Chemistry 694 (2009) 1107–1111
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Reinvestigation of arylmanganese chemistry – Synthesis and molecular
structures of [(thf)4Mg(
l
-Cl)2Mn(Br)Mes], [Mes(thf)Mn(
l-Mes)]2,
and (MnPh2)1 (Ph = C6H5; Mes = mesityl, 2,4,6-Me3C6H2)
*
Reinald Fischer, Helmar Görls, Manfred Friedrich, Matthias Westerhausen
Institute of Inorganic and Analytical Chemistry, Friedrich-Schiller-Universität Jena, August-Bebel-Street 2, D-07743 Jena, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 25 July 2008
Received in revised form 4 September 2008
Accepted 28 October 2008
Available online 5 November 2008
The reaction of 2,4,6-trimethylphenylmagnesium bromide (MesMgBr) with manganese(II) chloride in an
equimolar ratio yields [(thf)4Mg(
l
-Cl)2Mn(Br)Mes] (1) with two bridging chloro ligands and a Mn–C
bond length of 2.136(5) ÅA. A molar ratio of 2:1 leads to a metathesis reaction and the formation of
[Mes(thf)Mn( -Mes)]2 (2) with two bridging mesityl groups. Whereas THF-free [MnMes2]3 crystallizes
0
l
as a trimer from toluene solution, the reduced bulkiness of the phenyl groups in (MnPh2)1 (3) leads to
0
the formation of a chain-like structure with Mn–C bond lengths of 2.245(3) AÅ.
Dedicated to Professor Ch. Elschenbroich on
the occasion of his 70th birthday.
Ó 2008 Elsevier B.V. All rights reserved.
Keywords:
Manganese
Arylmanganese compounds
Metathesis reactions
Manganates
Diphenylmanganese
1. Introduction
nometylphenyl groups [6]. The synthesis of (thf)2Mn(C6F5)2 and
(dme)Mn(C6F5)2 succeeded via a transmetallation reaction of Mn
Organomanganese compounds are often used in organic syn-
thesis for the preparation of ketones from carbonic acid chlorides.
b-Hydride elimination reactions are less favored for these organo-
metallics than for many other organic transition metal compounds.
It is also well-known that the Mn–Cp bonding in manganocene
exhibits mainly ionic character whereas the metallocenes of the
neighbors chromium and iron represent covalent molecules [1].
These properties together with similar ionic radii lead to compara-
ble chemical behavior of manganese(II) and magnesium(II) in
many aspects. Several organomanganese compounds of the type
(R2Mn)n (n = 1) were characterized by single-crystal X-ray crystal-
lography such as with R as C(Me2)C6H5 (n = 2) and CH2SiMe3 [2].
The beginning of the arylmanganese chemistry dates back more
than 70 years. A mixture of phenylmanganese iodide and diphenyl-
manganese resulted from the metathesis reaction of phenylmagne-
sium iodide with anhydrous manganous iodide [3]. Pure
diphenylmanganese was prepared from MnI2 and phenyllithium
in diethyl ether [4]. Other diarylmanganese derivatives include
examples with 8-dimethylaminonaphthyl [5] and 2-dimetylami-
metal with Hg(C6F5)2 in tetrahydrofuran (THF) or 1,2-dimethoxy-
ethane (DME) [7]. Excess of aryllithium in the metathesis reaction
with manganese(II) halides yielded lithium triarylmanganates
with aryl groups such as phenyl [8,9], 4-methylphenyl (para-tolyl)
[8], 2,4,6-trimethylphenyl (mesityl) [9,10] and 4-methoxyphenyl
[8]. The molecular structures of these organomanganese com-
pounds are more complex and first crystal structures showed that
dimesitylmanganese crystallized from toluene as trimeric Mes-
Mn(l-Mes)2Mn(l-Mes)2MnMes [11,12]. A trinuclear complex
was also isolated when two mesityl groups were substituted by
an alcoholate derived from glucofuranose [13]. Monomeric diaryl-
manganese derivatives were obtained with 2,4,6-tri(tert-butyl)-
phenyl [14] and 2,6-bis(2,4,6-trimethylphenyl)phenyl groups
[15]. Phenylmanganates also show oligonuclear anions such as
[Mn2Ph6]2ꢀ whereas the bulkier mesityl group leads to the forma-
tion of mononuclear trimesitylmanganate [MnMes3]ꢀ [16]. Fur-
thermore, [Mn2(l
-Ph)2]2+ cations were synthesized and shielded
by the counter ions [BPh4]ꢀ leading to contact ion pairs [12].
Whereas organic manganese(II) compounds were investigated
quite extensively, investigations on organomanganese(III) com-
pounds are far less common. The metathesis reaction of manga-
nese(III) halides with dimesitylmagnesium in the presence of
trimethylphosphane and oxygen yielded [(Mes)MnX2(PMe3)2]
* Corresponding author. Fax: +49 (0) 3641 948102.
E-mail address: m.we@uni-jena.de (M. Westerhausen).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.10.045

1108
R. Fischer et al. / Journal of Organometallic Chemistry 694 (2009) 1107–1111
(X = Cl, Br, I) [17,18]. Bis(2-dimethylaminomethylphenyl)-methyl-
manganese(III) was obtained via addition of methyllithium to
bis(2-dimethylaminomethylphenyl)manganese(II) and
a subse-
quent oxidation with AgBF4 [19]. Manganates(III) were stabl0e with
pentafluorophenyl groups and Mn–C bond lengths of 2.068 ÅA were
observed for [Mg(thf)6][Mn(C6F5)4]2 [20].
Despite the long tradition of the arylmanganese chemistry, the
steps of the metathesis reactions were not investigated in detail,
even though iodine-containing [(Et2O)Li(l-I)2Mn{C6H3-2,6-Aryl}]
has already been investigated [21]. Bulky groups at the aryl sub-
stituents favor the formation of small aggregation degrees leading
to higher solubility in common organic solvents. Whereas diphe-
nylmanganese is known since 70 years [3], its molecular structure
is still unknown and should exhibit a higher nuclearity than dime-
sitylmanganese due to the lower shielding degree.
2. Results and discussion
2.1. Synthesis
Fig. 1. Molecular structure of [(Mes)Mn(Br)(
l-Cl)2Mg(thf)4] ꢁ thf (1). Hydrogen
During the attempt to prepare [(Mes)2Mn]3 from manganese(II)
chloride and mesitylmagnesium bromide, two yet unknown mesi-
tylmanganese derivatives were isolated. The addition reaction of
anhydrous MnCl2 with MesMgBr in an equimolar ratio in ether
atoms and intercalated THF are omitted for clarity reasons. Selected bond distances
(Å): Mn–C(1) 2.136(5), Mn–Cl(1) 2.4766(17), Mn–Cl(2) 2.4893(15), Mn–Br
2.5078(12), Mg–O(1) 2.091(4), Mg–O(2) 2.080(4), Mg–O(3) 2.093(4), Mg–O(4)
2.065(4), Mg–Cl(1) 2.526(2), Mg–Cl(2) 2.557(2); selected bond angles (°): Cl(1)–
Mn–Cl(2) 88.97(5), C(1)–Mn–Br 113.43(13), Cl(1)–Mn–Br 102.78(5), Cl(2)–Mn–Br
110.10(5), Cl(1)–Mg–Cl(2) 86.41(6), O(4)–Mg–O(1) 173.79(17), O(2)–Mg–O(3)
94.44(15).
yielded heterobimetallic [(thf)4Mg(l-Cl)2Mn(Br)Mes] 1 which can
be regarded as an intermediate during the synthesis of
[(Mes)2Mn]3. Recrystallization from a toluene solution led to the
formation of [(thf)Mn(Mes)2]2 2 due to traces of THF during the
metathesis reaction, whereas crystals of well-known trinuclear
[Mn(Mes)2]3 were obtained from recrystallization under strict
exclusion of THF.
The metathesis reaction of phenyllithium with manganese(II)
iodide in diethyl ether yielded quantitatively diphenylmanganese
3. Single crystals suitable for X-ray structure determinations were
obtained by diffusion of diethyl ether into a saturated THF solution
of 3.
2.2. Molecular structures
The molecular structures of the organomanganese compounds
1 to 3 are displayed in Figs. 1–3. Similar size of the magnesium(II)
and manganese(II) cations leads to comparable bond lengths in
compound 1. The metal centers Mg(II) and Mn(II) are bridged by
Fig. 2. Molecular structure of [(thf)(Mes)Mn(l–Mes)]2 (2). Hydrogen atoms are
omitted for clarity reasons. Selected bond distances (Å): C(1)–Mn 2.1660(19),
C(10)–Mn 2.2921(19), C(10A)–Mn 2.3008(18), Mn–O(1) 2.2467(14), Mnꢁ ꢁ ꢁMn(A)
2.8628(6). Selected bond angles (°): C(1)–Mn–O(1) 90.83(7), C(1)–Mn–C(10)
122.67(7), C(1)–Mn–C(10A) 126.81(7), C(10)–Mn–C(10A) 102.89(6), O(1)–Mn–
C(10) 105.57, O(1)–Mn–C(10A) 102.75, Mn–C(10)–Mn(A) 77.11(6).
two
l–chloro ligands. The transfer of the bromo and the mesityl
groups from Mg to Mn is already complete and the molecule could
be regarded as a magnesium(II) chloride adduct at mesitylmanga-
nese bromide. The bridging chlorine atoms show average distances
0
of 2.483 and 2.542 ÅA for Mn–Clb and Mg–Clb, respectively. The sub-
scripts b and t distinguish between bridging and terminally bound
atoms. With respect to the different coordination numbers of 4 and
6, rather similar ionic radii can be deduced for Mn(II) and Mg(II)
which are one of the reasons for comparable chemical reactivities
and molecular structures of these elements. Representative exam-
ples include M(C6H2-2,4,6-tBu3)2 (M = Mn, Mg [14]), (MPh2)1
{M = Mn (1, this work), Mg [22]}, and isotypic [(thf)4Li][M(Mes)3]
(M = Mn [16], Mg [23]).
ler than in aryl substituted manganate anions. Higher charge on
the metal center leads to additional repulsion between the carba-
nions and the more electron-rich metal atoms. (III) Aryl-manga-
nese distances depend on the oxidation state of the manganese
atom with smaller Mn–C bond lengths for higher oxidation states.
Selected structural parameters are compared in Table 1 contain-
ing also the coordination number (C.N.) and oxidation state (O.S.)
of the manganese atoms. A coordination number of 2 can only be
2.3. EPR properties
All organomanganese derivatives are paramagnetic and we
were not in the position to record reliable NMR spectra. The EPR
*
realized for very bulky groups such as C6H2-2,4,6-tBu3 (Mes )
[14] and C6H2-2,6-Mes2 [15]. From this table several characteristics
can be deduced: (I) The Mn–Cb distances to bridging aryl groups
are larger than the Mn–Ct bond lengths to terminally bound aryl li-
gands. This fact can be explained by the formation of M–Cb–M
three-center two-electron bonds leading to low M–C bond orders.
(II) In neutral manganese complexes the Mn–C distances are smal-
spectra of crystalline [(thf)4Mg(
l
-Cl)2Mn(Br)Mes] ꢁ thf (1) show a
strong dependency on the temperature. At 20 °C the characteristic
isotropic signal of a mononuclear Mn(II) compound is obtained
with a characteristic sextet hyperfine coupling A caused by the
55Mn nucleus (S = 5/2, I = 5/2, g = 2.000, A(55Mn) = 8.7 5 mT). In
the solid state at 20 °C we found two lines at g = 2.011 and

R. Fischer et al. / Journal of Organometallic Chemistry 694 (2009) 1107–1111
1109
0
of 2.8134(3) AÅ. Magnetic measurements at crystalline 2 show
an antiferromagnetic coupling of approximately J = ꢀ10 cmꢀ1 so
that spin states with total spin ST = 0, 1,. . ., 5 are populated
according to the Boltzman distribution [25]. These spin states
lead to different contributions to the EPR-spectra of 2 which
were measured in the solid state and in toluene solution at room
temperature and at 77 K. We also found many lines in a large
field range up to 1 T which could not be assigned to the different
spin states.
The EPR spectrum of crystalline (MnPh2)1 (3) displays at room
temperature and at 77 K a broad Mn(II) signal at g = 2.007 with a
half height width
perature-dependent magnetic measurements show
magnetic moment (3.43 B bei 20 °C) in comparison to a spin-only
D
Hpp = 28.0 mT and 48.6 mT, respectively. Tem-
a
reduced
l
value of 5.9 lB for five unpaired electrons of Mn(II) at room tem-
perature. This value decreases with decreasing temperature and
can be explained by an antiferromagnetic coupling of the manga-
nese atoms in the chain. Treatment of (MnPh2)1 (3) with warm
THF and filtration gave a clear solution which showed at room
temperature one broad Mn(II) line (g = 2.001,
77 K we found a signal at g = 2.006 ( Hpp = 24.2 mT) and an addi-
tional band at g = 4 consisting of about sixteen lines
Hpp = 1.5( 0.5) mT, A = 3.9( 0.4) mT). This well-known signal is
DHpp = 24.2 mT). At
D
(D
assigned to a multinuclear manganese cluster in analogy to spectra
described elsewhere [26]. Degradation of the chain-like structure
of (MnPh2)1 (3) with 1,2-dimethoxyethane (DME) led to the for-
mation of mononuclear complexes which showed in the EPR spec-
tra no lines at g = 4 but the common single broad line at g ꢂ 2.00 at
room temperature and at 77 K which can be assigned to a mononu-
clear Mn(II) compound. We interpret these observations in the
sense that smaller THF complexes form in THF solution which
are responsible for the solubility in this solvent. In similarity to
the magnesium chemistry even monomeric molecules such as
[(thf)2MnMes2] (in analogy to [(thf)2MgPh2] [22] and
[(thf)2MgMes2] [27]) seem likely. For di(para-tolyl)magnesium
monomeric [(thf)2Mg(p-Tol)2] and dimeric [(thf)Mg(p-Tol)2]2 were
found at the same time in one crystal [22]. The bidentate chelate
base DME mainly leads to the formation of mononuclear com-
plexes [(dme)MnPh2].
Fig. 3. Molecular structure (at the top) and chain-like structure (at the bottom) of
(MnPh2)1 (3). Hydrogen atoms are neglected for clarity reasons. Selected bond
distances (Å): C(1)–Mn 2.245(3), Mnꢁ ꢁ ꢁMn(A) 2.8134(3). Selected bond angles (°):
C(1)–Mn–C(1D)
112.07(17),
C(1)–Mn–C(1E)
114.16(17),
C(1)–Mn–C(1C)
102.41(11), Mn–Mn(A)–Mn(B) 180.0, Mn–C(1)–Mn(A) 77.59(11).
Table 1
Comparison of selected structural parameters of arylmanganese compounds (average
0
values (AÅ), terminal Mn–Ct and bridging Mn–Cb bonds, Mn–O to bound solvent
molecules) with respect to coordination number (C.N.) and oxidation state (O.S.) of
the manganese atom.
Compound
C.N. O.S. Mn–Ct Mn–Cb Mn–O Lit.
3. Conclusions
Mn(C6H2-2,4,6-tBu3)2
Mn(C6H2–2,6-Mes2)2
[Li(thf)4]+[MnMes3]ꢀ
2
2
3
3
3
4
4
4
4
4
4
4
4
4
5
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
2.108
2.095
2.141
2.066
2.122
–
2.111
–
2.146
2.178
–
–
–
–
–
–
–
-
–
–
–
[14]
[15]
[16]
[12]
[12]
The synthesis of diarylmanganese from the metathesis reac-
tion of mesitylmagnesium bromide with manganese(II) halide
proceeds via several intermediates as shown in Eq. (1). Complex
1 is an addition product, however, the aryl group is already trans-
ferred from the magnesium to the manganese atom. The harder
halogen atoms occupy the bridging positions whereas the soft
bromine atom is bound terminally to the manganese atom. A sol-
vent change from THF to toluene leads to the precipitation of the
magnesium(II) halides which are insoluble in hydrocarbons.
Thorough removal of THF leads to well-known trimeric
[MnMes2]3. Reduced bulkiness of the aryl groups allows higher
aggregation degrees and the formation of polymeric structures
as observed for (MnPh2)1 3.
MesMn(
l
-Ph)2BPh2
Mn3Mes6
2.206
2.331
–
2.199
2.285
2.255
2.245
2.292
–
[(Et2O)3MnMes]+[BPh4]ꢀ
2.133 [12]
[Mn2(
l
-Ph)2(BPh4)2]
–
–
–
–
[12]
[16]
[16]
This work
Li(thf)4]+2[Mn2Ph6]2ꢀ
[{Li(OEt2)2}2Mn2Ph6]
[MnPh2]1 (3)
[Mes(thf)Mn(
l
-Mes)]2(2)
2.166
2.136
2.068
2.089
2.247 This work
(thf)4Mg(
l
-Cl)2Mn(Br)Mes (1)
–
–
–
This work
[20]
[17,18]
[Mg(thf)6]2+ [Mn(C6F5)4]ꢀ2
(Mes)MnBr2(PMe3)2
–
–
g = 4.145. At liquid nitrogen temperature these two signals were
recorded with nearly the same g-factors for the frozen THF solution
as well as for the solid state. In the frozen THF solution we found at
g = 4.15 six hyperfine structure lines from 55Mn nucleus
(A(55Mn) ꢂ 5.3 mT). It is well-known [24] that not only for Fe(III)
but also for Mn(II) in a strong rhombic distorted crystal field in
the presence of a large zero field splitting a signal at a g-factor of
approximately 4 can be estimated.
4. Experimental
All experiments were carried out in an inert gas atmosphere,
using Schlenk techniques. The solvents were dried over Na/benzo-
phenone and distilled under nitrogen prior to use. EPR spectra
were measured on a Bruker spectrometer ESP 300 E. Anhydrous
MnCl2 was prepared from MnCl2(H2O)4 by reaction with thionyl-
chloride. Anhydrous MnI2 was prepared from Mn powder and io-
dine in an ether solution [28].
The complex [Mes(thf)Mn(l-Mes)2Mn(thf)Mes] (2) contains
two metal centers with a close trans-annular Mnꢁ ꢁ ꢁMn contact

1110
R. Fischer et al. / Journal of Organometallic Chemistry 694 (2009) 1107–1111
Table 2
Crystal data and refinement details for the X-ray structure determinations of the
compounds 1, 2 and 3.
THF
Mg
Br
Mn
THF
THF
+ MnCl2
THF
Cl
Cl
MgBr
Compound
Formula
1
2
3
C25H43BrCl2MgMnO4 ꢁ 1/
2 C4H8O
C
44H60Mn2O2 C12H10Mn
THF
Formula weight
673.71
730.80
209.14
1
(g molꢀ1
)
T (°C)
ꢀ90(2)
ꢀ90(2)
ꢀ90(2)
Orthorhombic
Ibam
9.5195(9)
17.9672(16)
5.6268(5)
90.00
90.00
90.00
962.40(15)
4
1.443
13.15
3901
436
616/0.1069
0.0980
x 2
Mes = 2,4,6-Me3C6H2
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Triclinic
Triclinic
THF + 2 MesMgBr
- MgCl2, -MgBr2
ꢀ
ꢀ
P1
P1
10.444(2)
10.923(2)
16.155(3)
104.57(3)
94.62(3)
100.44(3)
1738.7(6)
2
1.287
17.29
11897
4988
8.2176(3)
10.9440(5)
12.1808(4)
113.983(2)
102.836(2)
97.847(2)
943.71(6)
1
1.286
7.05
6383
3619
Mes
Mn
a
(°)
b (°)
x 3/2
toluene
- 3 THF
Mes
Mes
Mes
Mes
c
(°)
THF
V (Å3)
Z
q
l
Mn
Mn
Mn
Mn
(g cmꢀ3
(cmꢀ1
)
)
THF
Measured data
Data with I > 2
Unique data (Rint
wR2 (all data, on F2)a
r
(I)
)
7897/0.0328
0.2220
0.0709
4183/0.0313
0.1040
0.0393
Mes
R1 (I > 2
r
(I))a
0.0351
1.057
sb
1.030
1.019
2
Residual density
1.448/ꢀ0.809
0.344/
0.475/ꢀ0.571
ð1Þ
(e Åꢀ3
)
ꢀ0.336
Multi-scan
0.8778/
0.9495
Absorption method
Absorption correction
T min/max
Multi-scan
0.7480/0.7976
Multi-scan
0.8480/
0.8976
4.1. [(thf)4Mg(
l
-Cl)2Mn(Br)Mes] ꢁ thf (1)
CCDC no.
696024
696025
696026
a
Definition of the
R
=
indices: R1 = (
2(F2o) + (aP)2.
R
||Fo|-|Fc||)/
R
|Fo| wR2 = {
R
[w(F2o ꢀ F2c)2]/
R
[w(Fo2)2]}1/2 with wꢀ1
r
To a suspension of 6.3 g (50 mmol) MnCl2 in 20 ml diethyl ether
was slowly added a solution of mesitylmagnesium bromide (70 ml,
0.72 M, 50.4 mmol) in diethyl ether. The reaction mixture became
warm and started boiling. After the exothermic reaction finished
the stirring was continued at ambient temperature overnight.
Now the solvent was removed in vacuo and the residue recrystal-
lized from a mixture of THF and toluene. Yield: 25.4 g (71%) of col-
orless crystals of 1. Elemental Anal. Calc. for C29H51BrCl2MgMnO5
(709.8): Br, 11.26; Cl, 9.99. Found: Br, 11.41; Cl, 10.21%. EPR (THF
solution, R.T.): g = 2.000, A(55Mn) = 87( 5) G.
b
s = {
R
[w(Fo2 ꢀ Fc2)2]/(No ꢀ Np)}1/2
.
manganese were obtained by diffusion of diethyl ether into a sat-
urated solution of 3 in THF. Elemental Anal. Calc. for C12H10Mn,
209.1: Mn, 26.27. Found: Mn, 26.09%. leff = 3.43 lB (R.T.). EPR (so-
lid, R.T.): g = 2.0085 (broad, see text). EPR investigations see text.
4.4. X-ray structure determinations
4.2. [Mes(thf)Mn(l-Mes)2Mn(thf)Mes] (2)
Intensity data were collected on a Nonius Kappa CCD diffrac-
tometer using graphite-monochromated Mo K
a radiation. Data
Sixty milliliters (60.0 mmol) of mesitylmagnesium bromide
(1.0 M in THF) were added to a suspension of 3.75 g (29.8 mmol)
of MnCl2 in 10 ml of THF at ꢀ78 °C. The brown suspension was
warmed to room temperature and stirred overnight. Then the reac-
tion mixture was refluxed for 5 h and 50 ml of dioxane were added.
The resulting suspension was stirred overnight and allowed to set-
tle for 2 h. The precipitate was separated and the filtrate evapo-
rated to dryness to give a green solid. The residue was dissolved
in warm toluene (40 ml) and all solid materials were carefully re-
moved. Then 5 ml of THF were added. At ꢀ20 °C slightly yellow
crystals precipitated which also contained a very small amount
of brown needles. Yield: 5.7 g (52%) of crystalline 2. Elemental
Anal. Calc. for C22H30MnO, 730.8: Mn, 15.04. Found: Mn, 15.31%.
EPR investigations see text.
were corrected for Lorentz polarization and for absorption effects
[29–31]. Crystallographic data as well as structure solution and
refinement details are summarized in Table 2. The structures were
solved by direct methods (SHELXS [32]) and refined by full-matrix
least squares techniques against F20 (SHELXL-97 [33]). The hydrogen
atoms were included at calculated positions with fixed thermal
parameters. All non-hydrogen atoms were refined anisotropically
[33]. XP (SIEMENS Analytical X-ray Instruments, Inc.) and POVRAY
were used for structure representations.
Supplementary material
CCDC 696024, 696025 and 696026 contain the supplementary
crystallographic data for 1, 2 and 3. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
4.3. (MnPh2)1 (3)
9.1 g (29.47 mmol) of solid MnI2 were added to a solution of
phenyl lithium in diethyl ether (60 ml, 1.0 M, 60.0 mmol) at 0 °C.
The color of the reaction mixture changed over yellow to brown.
The cooling bath was removed and stirring was continued over-
night. The precipitate was removed, washed intensively with
diethyl ether and dried in vacuo. Yield: 5.99 g (97%) of pyrophoric
brownish yellow powder of Ph2Mn. Single crystals of diphenyl-
Acknowledgement
We thank the German Research Foundation (DFG, Bonn, Ger-
many) and the Fonds der Chemischen Industrie (Frankfurt, Ger-
many) for generous financial support. We gratefully acknowledge
the support of Prof. W. Plass.

R. Fischer et al. / Journal of Organometallic Chemistry 694 (2009) 1107–1111
[18] R.J. Morris, G.S. Girolami, Organometallics 10 (1991) 799–804.
1111
References
[19] J.L. Latten, R.S. Dickson, G.B. Deacon, B.O. West, E.R.T. Tiekink, J. Organomet.
Chem. 435 (1992) 101–108.
[20] J. Forniers, A. Martin, L.F. Martin, B. Menjon, H. Zhen, A. Bell, L.F. Rhodes,
Organometallics 24 (2005) 3266–3271.
[21] A.D. Sutton, T. Ngyuen, J.C. Fettinger, M.M. Olmstead, G.J. Long, P.P. Power,
Inorg. Chem. 46 (2007) 4809–4814.
[22] P.R. Markies, G. Schat, O.S. Akkerman, F. Bickelhaupt, W.J.J. Smeets, P. van der
Sluis, A.L. Spek, J. Organomet. Chem. 393 (1990) 315–331.
[23] S. Krieck, H. Görls, M. Westerhausen, unpublished results (see: S. Krieck, Ph.D.
Thesis, Jena/Germany, presumingly 2010).
[24] M.T. Caudle, C.K. Mobley, L.M. Bafaro, R. LoBrutto, G.T. Yee, T.L. Groy, Inorg.
Chem. 43 (2004) 506–514.
[25] V.V. Pavlishuk, M. Prushan, A. Addison, Theor. Exp. Chem. 41 (2005)
229–234.
[26] D.H. Kim, R.D. Britt, M.P. Klein, K. Sauer, J. Am. Chem. Soc. 112 (1990) 9389–
9391.
[27] K.M. Waggoner, P.P. Power, Organometallics 11 (1992) 3209–3214.
[28] B. Heyn, B. Hipler, G. Kreisel, H. Schreer, D. Walther, Anorganische
Synthesechemie: Ein integriertes Praktikum, Springer, Berlin, 1986.
[29] B.V. Nonius, COLLECT, Data Collection Software, Netherlands, 1998.
[30] Z. Otwinowski, W. Minor, in: C.W. Carter, R.M. Sweet (Eds.), Methods in
enzymology, Macromolecular Crystallography, Part A, vol. 276, Academic
Press, 1997, pp. 307–326.
[31] SORTAV R.H. Blessing, Acta Crystallogr., Sect. A 51 (1995) 33–38.
[32] G.M. Sheldrick, Acta Crystallogr., Sect. A 46 (1990) 467–473.
[33] G.M. Sheldrick, SHELXL-97 (Release 97-2), University of Göttingen, Germany,
1997.
[1] (a) G.A. Razuvaev, V.N. Latyaeva, Russ. Chem. Rev. 34 (1965) 251–267;
(b) K. Oshima, Sci. Synth. 2 (2003) 13–89;
(c) R.A. Layfield, Chem. Soc. Rev. 37 (2008) 1098–1107.
[2] R.A. Andersen, E. Carmona-Guzman, J.F. Gibson, G. Wilkinson, J. Chem. Soc.,
Dalton Trans. (1976) 2204–2211.
[3] H. Gilman, J.C. Bailie, J. Org. Chem. 2 (1938) 84–94.
[4] C. Beermann, K. Clauss, Angew. Chem. 71 (1959) 627.
[5] H. Drevs, J. Organomet. Chem. 433 (1992) C1–C3.
[6] L.E. Manzer, L.J. Guggenberger, J. Organomet. Chem. 139 (1977) C34–C38.
[7] G.B. Deacon, R.S. Dickson, J.L. Latten, B.O. West, Polyhedron 12 (1993) 497–500.
[8] R. Riemenschneider, H.G. Kassahn, Z. Naturforsch. 15b (1960) 547–551.
[9] G. Fiour, G. Cahiez, A. Alexakis, J.F. Normant, Bull. Soc. Chim. Fr. (1979) 515–
517.
[10] W. Seidel, I. Bürger, Z. Chem. 17 (1977) 31.
[11] S. Gambarotta, C. Floriani, A. Chiesi-Villa, C. Guastini, J. Chem. Soc., Chem.
Commun. (1983) 1128–1129.
[12] E. Solari, F. Musso, E. Gallo, C. Floriani, N. Re, A. Chiesi-Villa, C. Rozzoli,
Organometallics 14 (1995) 2265–2276 (Erratum: Organometallics 14 (1995)
4030).
[13] U. Piarulli, C. Floriani, N. Re, G. Gervasio, D. Viterbo, Inorg. Chem. 37 (1998)
5142–5148.
[14] R.J. Wehmschulte, P.P. Power, Organometallics 14 (1995) 3264–3267.
[15] D.L. Kays, A.R. Cowley, Chem. Commun. (2007) 1053–1055.
[16] R.A. Bartlett, M.M. Olmstead, P.P. Power, S.C. Shoner, Organometallics 7 (1988)
1801–1806.
[17] R.J. Morris, G.S. Girolami, Organometallics 6 (1987) 1815–1816.