Synthesis and Reaction of MnII Iodides Bearing the β-Diketiminate Ligand: The First Divalent Manganese N-Heterocyclic Carbene Complexes [{HC(CMeNAr)2}MnI{C[N(iPr)CMe]2}] and [{HC(CMeNAr)2}MnNHAr{C[N(iPr)CMe]2}] (Ar = 2,6-iPr 2C6H3)

Article abstract of DOI:10.1002/ejic.200300289

The manganese mono-iodide [HC(CMeNAr)₂]MnI(THF) (Ar = 2,6-iPr₂C₆H₃) (3) was prepared in good yield from the reaction of [HC(CMeNAr)₂]K with MnI₂ in THF. Treatment of 3 under reflux in toluene and removing all the volatiles in vacuo afforded the dimeric compound [{HC(CMeNAr)₂}-Mn]₂(μ -I)₂ (4). Displacement of the coordinated THF in 3 by a strong Lewis base C[N(iPr)CMe]₂ or by adding C[N(iPr)CMe]₂ to the toluene solution of 4 readily gave the N-heterocyclic carbene adduct [{HC(CMeNAr)₂}]MnI{C-[N(iPr)CMe]₂} (5). Reduction of 5 with sodium/potassium alloy at room temperature unexpectedly resulted in the formation of the monomeric compound [{HC(CMeNAr) ₂}]MnNHAr{C[N(iPr)CMe]₂} (6). Alternatively 6 was obtained by the salt elimination reaction of 5 with LiNHAr. Compounds 5 and 6 are the first examples of divalent manganese N-heterocyclic carbene adducts and the first manganese non-carbonyl carbene complexes. The single crystal X-ray structural analyses reveal that compounds 3 and 6 are monomeric and compound 4 is dimeric in the solid state. The manganese centers in these compounds exhibit a distorted tetrahedral geometry. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejic.200300289

FULL PAPER
Synthesis and Reaction of MnII Iodides Bearing the β-Diketiminate Ligand:
the First Divalent Manganese N-Heterocyclic Carbene Complexes
[{HC(CMeNAr)2}MnI{C[N(iPr)CMe]2}] and
[{HC(CMeNAr)2}MnNHAr{C[N(iPr)CMe]2}] (Ar ؍ 2,6-iPr2C6H3)
Jianfang Chai,[a] Hongping Zhu,[a] Kerstin Most,[a] Herbert W. Roesky,*[a] Denis Vidovic,[a]
Hans-Georg Schmidt,[a] and Mathias Noltemeyer[a]
Keywords: Manganese / Iodine / N ligands / Heterocycles / Carbene ligands
The manganese mono-iodide [HC(CMeNAr)2]MnI(THF)
(Ar = 2,6-iPr2C6H3) (3) was prepared in good yield from the
reaction of [HC(CMeNAr)2]K with MnI2 in THF. Treatment
of 3 under reflux in toluene and removing all the volatiles in
vacuo afforded the dimeric compound [{HC(CMeNAr)2}-
Mn]2(µ-I)2 (4). Displacement of the coordinated THF in 3 by
[{HC(CMeNAr)2}]MnNHAr{C[N(iPr)CMe]2} (6). Alternat-
ively 6 was obtained by the salt elimination reaction of 5 with
LiNHAr. Compounds 5 and 6 are the first examples of dival-
ent manganese N-heterocyclic carbene adducts and the first
manganese non-carbonyl carbene complexes. The single
crystal X-ray structural analyses reveal that compounds 3
and 6 are monomeric and compound 4 is dimeric in the solid
state. The manganese centers in these compounds exhibit a
distorted tetrahedral geometry.
a
strong Lewis base C[N(iPr)CMe]2 or by adding
C[N(iPr)CMe]2 to the toluene solution of 4 readily gave the
N-heterocyclic carbene adduct [{HC(CMeNAr)2}]MnI{C-
[N(iPr)CMe]2} (5). Reduction of 5 with sodium/potassium
alloy at room temperature unexpectedly resulted in
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
the
formation
of
the
monomeric
compound
Germany, 2003)
Introduction
been reported. Furthermore, no X-ray structural data of
manganese N-heterocyclic carbene complexes are available.
Manganese carbene complexes are important due to their
applications in organic synthesis, synthetic methodology
Organometallic iodide complexes have unique chemical
and theoretical implications and have been studied properties due to their labile MϪI bond compared to the
extensively.[1Ϫ4] N-Heterocyclic carbenes have attracted MϪCl congener.[12] Recent results in our group proved that
great attention in ligand design and homogeneous catalysis aluminum diiodide bearing
a
β-diketiminate ligand
since Arduengo et al. reported the first stable crystalline [AlI2{HC(CMeNAr)2}] (Ar ϭ 2,6-iPr2C6H3) is a good
N-heterocyclic carbene in 1991.[5Ϫ8] A variety of transition starting material for some interesting reactions such as re-
metal N-heterocyclic carbene complexes have been synthe- duction and hydrolysis. For instance, we reported the
sized and isolated and some of them have been successfully monomeric [Al{HC(CMeNAr)2}] as a stable carbene ana-
applied as catalysts in a number of organic reactions such logue by reduction of [AlI2{HC(CMeNAr)2}] with potas-
as iridium-catalyzed transfer hydrogenation,[6] ruthenium- sium.[13a] Furthermore, the aluminum dihydroxide complex
catalyzed olefin metathesis, and especially palladium-cata- [Al(OH)2{HC(CMeNAr)2}], with terminal OH groups, was
lyzed CϪC coupling reactions: the Heck, Suzuki and Kum- obtained by hydrolysis of [AlI2{HC(CMeNAr)2}] using a
ada reactions.[7,9] However, manganese N-heterocyclic car- liquid NH3/toluene two-phase system.[13b] Consequently we
bene complexes are rare and have not attracted much atten- became interested in transition metals and investigated the
tion to date.[9a] To the best of our knowledge, only a few behavior of Mn iodides bearing a β-diketiminate ligand.
monovalent manganese N-heterocyclic carbene complexes However, our efforts to reduce [{HC(CMeNAr)2}Mn(µ-
are known, including [MeC5H4(CO)2MnC(NMeCH2)2],[10] I)2Li(OEt2)2] were unsuccessful with sodium or potassium
[(CO)3MnBr{C(NMeCH2)2}2][10] and [(CO)5MnC{N- due maybe to the existence of the stable lithium salt.[14]
(BH3)CMeCMeNMe}][11] and so far no higher oxidation Herein we report the preparation of manganese iodides
state manganese N-heterocyclic carbene complexes have bearing β-diketiminate ligand free of lithium salt of com-
position [LMnI(THF)] (3), [(LMn)2(µ-I)2] (4) and
[a]
Institut für Anorganische Chemie, Universität Göttingen,
[LMnI{C[N(iPr)CMe]2}] (5) [L ϭ HC(CMeNAr)2, Ar ϭ
2,6-iPr2C6H3] and the derivative [LMnNHAr{C-
[N(iPr)CMe]2}] (6), in which compounds 5 and 6 are the
Tammannstrasse 4, 37077 Göttingen, Germany
Fax: (internat.) ϩ 49-551/393373
E-mail: hroesky@gwdg.de
4332
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200300289
Eur. J. Inorg. Chem. 2003, 4332Ϫ4337

Synthesis and Reaction of MnII Iodides
FULL PAPER
first examples of divalent manganese N-heterocyclic car- Attempts to prepare the di-β-diketiminato complex by
bene adducts and the first manganese non-carbonyl carbene using two equiv. of 2 were unsuccessful.
complexes. Compound 6 is the first structurally charac-
terized manganese N-heterocyclic carbene complex.
Refluxing of 3 in toluene for 0.5 h and removing all the
volatiles in vacuo afforded the dimeric compound
[(LMn)2(µ-I)2] (4). Crystals suitable for X-ray analysis were
obtained by recrystallization from toluene. EI-MS of 4 did
not give the molecular ion peak Mϩ whereas half of the
molecular mass [LMnI]ϩ is observed at m/z ϭ 599 (100%),
which shows that 4 is monomeric in the gas phase, and no
indication of fragments containing a MnϪMn species,
which is consistent with the X-ray structural analysis. Com-
pound 3 can easily be obtained by dissolving 4 in THF
(Scheme 2).
Results and Discussion
Synthesis of Compounds 2؊6
KL (2) was prepared from the reaction of HL (1) with
KN(SiMe3)2 in relatively low yield (27%).[15] Herein we re-
port that this compound can be conveniently obtained as a
crystalline solid in good yield (87%) by the reaction of HL
with KH in diethyl ether at room temperature (Scheme 1).
The 1H NMR spectrum and elemental analysis are identical
with those of the literature.[15] Compound 2 is stable under
an inert atmosphere and can be kept for a long time with-
out obvious decomposition.
Scheme 1
The reaction of MnI2 with one equiv. of [LiL(Et2O)] in
diethyl ether afforded the heterobimetallic complex
[LMn(µ-I)2Li(OEt2)2].[14] Attempts to remove the coordi-
nated lithium salt from the manganese center were unsuc-
cessful. However, the reaction of MnI2 with one equiv. of 2
in THF easily gave the monomeric compound
[LMnI(THF)] (3) in high yield (87%) with a coordinated
THF at the metal center. EI-MS of 3 exhibits [LMnI]ϩ
(m/z ϭ 599, 100%) without the coordinated THF. The for-
mula of 3 was confirmed by the crystal structure (Figure 1).
Scheme 2
Compound 3 can be considered as an adduct of a Lewis
acid LMnI and a weak Lewis base THF. Displacement of
the THF by a strong Lewis base [C{N(iPr)CMe}2] readily
afforded
the
N-heterocyclic
carbene
adduct
[LMnI{C[N(iPr)CMe]2}] (5), which can also be obtained by
adding [C{N(iPr)CMe}2] to a solution of 4 in toluene. On
the other hand we were not able to prepare 4 by removing
the carbene in 5, which shows that the N-heterocyclic car-
bene is a much stronger σ-donor ligand. Compounds 3, 4,
and 5 are all soluble in polar solvents such as THF and
CH2Cl2 and have poor solubility in hydrocarbon solvents.
The chemistry of organometallic dinuclear complexes
containing a metal-metal bond is a burgeoning field.[16] We
are interested in preparing LЈMMLЈ (LЈ ϭ ligands, M ϭ
metal) type compounds by reduction of LЈMX (X ϭ hal-
ide). The first three-coordinate dinuclear manganese()
compound LMnMnL [L ϭ HC(CMeNAr)2, Ar ϭ 2,6-
iPr2C6H3] has been successfully synthesized by reduction of
4 with sodium/potassium alloy.[17] However, further re-
duction of 5 by sodium/potassium alloy at room tempera-
ture, unexpectedly resulted in the formation of the mono-
meric compound [LMnNHAr{C[N(iPr)CMe]2}] (6) in low
yield. The efforts to identify other species were unsuccess-
ful. Given that MnII complexes are used as radical initiators
Figure 1. Molecular structure of 3 (30% probability thermal ellip-
soids); hydrogen atoms are omitted for clarity
Eur. J. Inorg. Chem. 2003, 4332Ϫ4337
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4333

H. W. Roesky et al.
FULL PAPER
for radical polymerisation processes,[18] it is tempting to
propose that the formation of compound 6 is due to the
partial decomposition of the intermediate radical
[LMnC{N(iPr)CMe}2], which cannot aggregate due to the
presence of the bulky N-heterocyclic carbene. In the mass
spectrum, [LMnNHAr]ϩ was observed at m/z ϭ 648 (52%),
followed by [LMn]ϩ (m/z ϭ 472, 100%). The elemental
analyses are consistent with the solid-state structure. Com-
pound 6 can also be prepared in good yield (76%) by the
reaction of 5 with LiNHAr.
X-ray Diffraction Analyses for 3, 4, and 6
The single-crystal X-ray diffraction analyses for com-
pounds 3, 4, and 6 have been undertaken. For 3 and 4, there
are two molecules in the unit cell, one of which is shown in
Figures 1 and 2, respectively. The structure of 6 is presented
in Figure 3. Crystallographic data for 3, 4, and 6 are given
in Table 1 and selected bond lengths and angles in Table 2.
The X-ray structural analyses reveal that the
[LMnI(THF)] (3), [LMnNHAr{C[N(iPr)CMe]2}] (6) are
monomeric and [(LMn)2(µ-I)2] (4) is dimeric in the solid
state (Figures 1Ϫ3). In all three compounds the manganese
centers are four-coordinate and display a distorted tetra-
hedral geometry. The backbone of the chelating ligand is
nearly planar and the manganese atom in all the reported
Figure 3. Molecular structure of 6 (30% probability thermal
ellipsoids); hydrogen atoms are omitted for clarity
˚
˚
˚
compounds is out of the C3N2 plane (0.62 A in 3, 0.43 A
The terminal Mn(1)ϪI(1) distance [2.6272(8) A] in 3 is
˚
in 4, 0.78 A in 6). The N(1)ϪMn(1)ϪN(2) angle in 6 similar to the reported values for the terminal MnϪI bond
˚
[88.94(7)°] is significantly smaller than the corresponding such as those in [MnI(sima)2] [2.6233(6) A] [sima ϭ N(Si-
angles in 3 [93.56(13)°] and 4 [95.57(14)°], while the Me3)C(Ph)N(SiMe3)][19] and [MnI2(PEt3)2] [av. 2.666(2)
[20]
˚
Mn(1)ϪN(1) and Mn(1)ϪN(2) bond lengths in 6 [2.166(2) A],
which is significantly shorter than the bridging
˚
˚
and 2.133(2) A] are obviously longer than those in 3 MnϪI bond length in 4 [2.7688(7) and 2.7484(8) A] and
[2.079(3) and 2.070(3) A] and 4 [2.067(2) and 2.067(2) A], [LMn(µ-I)2Li(OEt2)2] [2.716(9) and 2.733(9) A].[14] The two
which indicates that the metal center in 6 is more weakly manganese atoms are bridged by two iodine atoms in 4 and
˚
˚
˚
˚
bonded to the chelating ligand possibly due to the different the distance between two manganese atoms is 3.615 A,
substituents that cause a stronger trans effect.
which is out of the range of a MnϪMn bond. The Mn2I2
Figure 2. Molecular structure of 4 (30% probability thermal ellipsoids); hydrogen atoms are omitted for clarity
4334 www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2003, 4332Ϫ4337

Synthesis and Reaction of MnII Iodides
FULL PAPER
Table 1. Crystallographic data for compounds 3, 4, and 6
3
1/2 4 incl. toluene
6
Empirical formula
Molecular weight
Temperature (K)
C33H49IMnN2O
671.58
203(2)
C36H49IMnN2
691.61
203(2)
C52H79MnN5
829.14
133(2)
˚
Wavelength (A)
0.71073
0.71073
0.71073
Crystal system
Space group
monoclinic
P21/c
a ϭ 16.752(2)
monoclinic
C2/m
a ϭ 19.188(3)
monoclinic
P21/c
a ϭ 11.694(2)
Unit cell dimensions
˚
(a, b, c ϭ A, α, β, γ ϭ °)
b ϭ 20.290(6)
c ϭ 19.620(3)
α ϭ 90
b ϭ 21.000(4)
c ϭ 16.5839(13)
α ϭ 90
b ϭ 19.388(4)
c ϭ 22.168(4)
α ϭ 90
β ϭ 91.317(14)
γ ϭ 90
6670(1)
β ϭ 100.053(8)
γ ϭ 90
6580.0(16)
8
1.366
3.57 to 25.00°
2856
β ϭ 102.59(3)
γ ϭ 90
4905.3(17)
4
0.307
1.78 to 24.72°
1804
3
˚
Volume (A )
Z
8
Absorption coefficient (mmϪ1
θ range for data collection
F(000)
)
1.348
3.52 to 25.03°
2776
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
R (all data)
14274
7832
34511
11722 (Rint ϭ 0.0616)
11722/0/705
1.053
0.0534, 0.1296
0.0714, 0.1457
0.971 /-1.279
5952 (Rint ϭ 0.0425)
5952/0/374
1.018
0.0349, 0.0900
0.0388, 0.0936
0.977/-0.788
8269 (Rint ϭ 0.0717)
8269/0/543
0.932
0.0422, 0.0983
0.0616, 0.1044
0.431/-0.469
Ϫ3
˚
Largest diff. peak/hole (e·A
)
˚
(R ϭ Me, Et, Bu or CH2SiMe3, TMEDA ϭ tetramethyl-
ethylenediamine).[21] However, it is significantly longer than
the MnϪC (carbene) distance in extensively studied manga-
nese carbonyl carbene complexes [CpMn(CO)2CXY] [X ϭ
Table 2. Selected bond lengths (A) and bond angles (deg) for com-
pounds 3, 4, and 6
Compound 3
[22]
[23]
˚
˚
Y ϭ Me, 1.872(10) A; X ϭ Y ϭ Ph, 1.885(2) A; X ϭ
Mn(1)ϪN(1)
Mn(1)ϪN(2)
Mn(1)ϪO(1)
Mn(1)ϪI(1)
2.079(3) N(2)ϪMn(1)ϪO(1)
2.070(3) N(1)ϪMn(1)ϪO(1)
2.155(3) N(2)ϪMn(1)ϪI(1)
2.6272(8) N(1)ϪMn(1)ϪI(1)
93.56(13) I(1)ϪMn(1)ϪO(1)
104.28(12)
101.90(1)
124.79(9)
124.12(9)
104.96(8)
[24]
˚
F, Y ϭ Ph, 1.830(5) A;
A
X ϭ OEt, Y ϭ Ph, 1.865(14)
[25]]. This could result from two reasons: one is the steric
˚
repulsion between the bulky substituents; the other is the
very weak MnǞC back bonding in 6 due to the relatively
high energy of the formal empty p(π) orbital of the N-het-
erocyclic carbene carbon, which is increased by the NǞC
bond.[9a,26] In this respect N-heterocyclic carbenes are dif-
ferent from the usual carbenes, which have rather strong
MǞC(carbene) back bonding.[25,27] The manganese atom
N(2)ϪMn(1)ϪN(1)
Compound 4
Mn(1)ϪN(1)
Mn(1)ϪN(1C)
Mn(1)ϪI(1)
Mn(1)ϪI(1A)
Mn(1A)ϪI(1)
2.067(2) N(1)ϪMn(1)ϪI(1)
2.067(2) N(1C)ϪMn(1)ϪI(1)
2.7484(8) N(1)ϪMn(1)ϪI(1A)
2.7688(7) I(1)ϪMn(1)ϪI(1A)
119.04(7)
119.04(7)
113.02(7)
98.14(2)
˚
in 6 is out of the carbene plane (0.41 A) and the dihedral
2.7688(7) Mn(1)ϪI(1)ϪMn(1A) 81.86(2)
angle between the carbene plane and the chelating ligand
N(1)ϪMn(1)ϪN(1C) 95.57(14)
plane is 108.8°. The Mn(1)ϪN(3) bond length in 6 is
II
[28]
˚
Compound 6
2.055(2) A, which is close to that reported in Mn amide.
Mn(1)ϪN(1)
Mn(1)ϪN(2)
Mn(1)ϪN(3)
Mn(1)ϪC(42)
N(3)ϪMn(1)ϪN(2)
2.166(2) N(3)ϪMn(1)ϪN(1)
2.133(2) N(2)ϪMn(1)ϪN(1)
2.055(2) N(3)ϪMn(1)ϪC(42)
2.270(2) N(2)ϪMn(1)ϪC(42)
99.25(7)
88.94(7)
117.46(8)
111.68(8)
109.83(7)
Conclusion
As an extension of our previous work, manganese iodides
bearing β-diketiminate ligand free of lithium salt, and
their derivatives, were successfully synthesized and charac-
123.25(7)
N(1)ϪMn(1)ϪC(42)
four-membered ring is exactly planar, bisecting and perpen- terized. Compounds 5 and 6 are the first examples of di-
dicular to the two chelating ligands around them. valent manganese N-heterocyclic carbene adducts and the
[LMnNHAr{C[N(iPr)CMe]2}] (6) is, to the best of our first manganese non-carbonyl carbene complexes. The
knowledge, the first structurally characterized manganese structure of 6 shows that the MnϪC (carbene) bond length
N-heterocyclic carbene complex. The MnϪC(carbene) dis- in 6 is significantly longer than that of a ‘‘real’’ manganese
˚
tance [2.270(2) A] is in the normal range of those in the carbene bond and π-backbonding is considered to be negli-
˚
manganates [Li(TMEDA)]2[MnR4] [2.22(6)Ϫ2.28(1) A] gible in this system.
Eur. J. Inorg. Chem. 2003, 4332Ϫ4337
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4335

H. W. Roesky et al.
FULL PAPER
ν˜ ϭ 3173 cmϪ1 (vw), 1633 (w), 1588 (w), 1543 (w), 1512 (m), 1420
(s), 1406 (m), 1316 (m), 1261 (m), 1169 (m), 1102 (w), 1019 (w),
929 (w), 886 (vw), 841 (w), 794 (m), 758 (w), 737 (m), 722 (m), 600
(vw), 565 (vw), 543(vw).
Method b: A THF (10 mL) solution of LiNHAr (0.18 g, 1 mmol)
was added to a THF (20 mL) solution of 5 (0.78 g, 1 mmol) at Ϫ78
°C. The mixture was allowed to warm to room temperature and
stirred for 14 h. After removal of all volatiles in vacuo, the residue
was extracted with diethyl ether (10 mL). After filtration, the yel-
low filtrate was concentrated to ca. 5 mL and stored at Ϫ26 °C for
3 days to give yellow crystals. Yield: 0.63 g (76%). The spectro-
scopic characterization of the compound is identical to that of the
compound prepared by method a.
Experimental Section
General: All reactions were performed using standard Schlenk and
dry box techniques. Solvents were appropriately dried and distilled
under dinitrogen prior to use. Elemental analyses were performed
by the Analytisches Labor des Instituts für Anorganische Chemie
der Universität Göttingen. Mass spectra were obtained on a Finni-
gan Mat 8230. IR spectra were recorded on a Bio-Rad Digilab
FTS-7 spectrometer as Nujol mulls between KBr plates. HL (1)
[L
ϭ
HC(CMeNAr)2,
Ar
ϭ
2,6-iPr2C6H3][29]
and
[30]
C[N(iPr)CMe]2 were prepared by literature procedures.
KL (2): A suspension of KH (0.18 g, 4.5 mmol) and 1 (1.67 g,
4 mmol) in diethyl ether (50 mL) was stirred at room temperature
for 3 days. After filtration the light yellow filtrate was concentrated
to ca. 10 mL and kept at Ϫ26 °C for 24 h to afford crystalline solid.
Yield: 1.59 g (87%). The 1H NMR spectrum and elemental analyses
are identical with those of the literature.[15]
X-ray Crystallography: Crystallographic data for 3 and 4 were col-
lected on a StoeϪSiemensϪHuber four-circle diffractometer cou-
pled to a Siemens CCD area detector and for 6 on a Stoe IPDS II-
array detector system. In both cases graphite-monochromated Mo-
˚
Kα radiation (λ ϭ 0.71073 A) was used. All structures were solved
by direct methods (SHELXS-97)[31] and refined against F2 using
SHELXL-97.[32] All non-hydrogen atoms were refined aniso-
tropically. The hydrogen atoms were included at geometrically cal-
culated positions and refined using a riding model. Atomic coordi-
nates, thermal parameters, bond lengths and angles. CCDC-207299
(3), -207298 (4), and -207297 (6) contain the supplementary crystal-
lographic 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, Cam-
[LMnI(THF)] (3): A solution of 2 (0.91 g, 2 mmol) in THF (10 mL)
was added to a suspension of MnI2 (0.62 g, 2 mmol) in THF
(35 mL) at Ϫ78 °C. The mixture was allowed to warm to room
temperature and stirred for 14 h. The precipitate was removed by
filtration. The yellow filtrate was concentrated to ca. 5 mL and kept
at Ϫ26 °C for 24 h to give yellow crystals. Yield: 1.17 g (87%). M.p.
379Ϫ381 °C. C33H49IMnN2O (670.84): calcd. C 59.03, H 7.30, N
4.17; found C 58.95, H 7.24, N 4.16. EI-MS: m/z (%) ϭ 599 (100)
[LMnI]ϩ. IR (KBr, Nujol mull): ν˜ ϭ 1624 cmϪ1 (w), 1552 (w),
1520.62 (m), 1314 (m), 1262 (m), 1174 (w), 1100 (w), 1024 (m), 935
(w), 870 (w), 852 (w), 794 (m), 757 (w), 721 (w), 600 (vw), 524 (w),
468 (vw).
bridge CB2 1EZ, UK [Fax: (internat.)
E-mail: deposit@ccdc.cam.ac.uk].
ϩ 44-1223/336-033;
[(LMn)2(µ-I)2] (4): A solution of 3 (1.34 g, 2 mmol) in toluene
(40 mL) was refluxed for 0.5 h. All volatiles were removed in vacuo
and bright yellow micro crystals were obtained. Yield: 1.15 g (96%).
M.p. 271Ϫ273 °C (dec). C58H82I2Mn2N4 (1197.68): calcd. C 58.11,
H 6.84, N 4.67; found C 58.34, H 6.92, N 4.85. EI-MS: m/z (%) ϭ
599 (100) [LMnI]ϩ. IR (KBr, Nujol mull): ν˜ ϭ 1657 cmϪ1 (w), 1625
(w), 1552 (w), 1262 (m), 1097 (m), 1023 (m), 875 (w), 800 (m), 722
(w), 659 (vw), 536 (w), 468 (w).
Acknowledgments
This work was supported by the Deutsche Forschungsgemeinschaft
and Ciba company. We thank Dr. Frauendorf (Institut für organis-
che Chemie, Universität Göttingen) for MS(DCI) and helpful dis-
cussions.
[1]
[LMnI{C[N(iPr)CMe]2}] (5): A solution of C[N(iPr)CMe]2 (0.18 g,
1 mmol) in THF (10 mL) was added to a THF (20 mL) solution
of 3 (0.67 g, 1 mmol) at room temperature. The resulting mixture
was stirred for 1 h. After removal of all volatiles in vacuo, a yellow
solid was obtained. Yield: 0.76 g (98%). M.p. 271 °C (dec).
C40H61IMnN4 (778.8): calcd. C 61.63, H 7.83, N 7.19; found C
61.78, H 8.02, N 7.20. EI-MS: m/z (%) ϭ 599 (100) [LMnI]ϩ. IR
(KBr, Nujol mull): ν˜ ϭ 1625 cmϪ1 (m), 1552 (s), 1505 (m), 1318
(m), 1261 (s), 1232 (w), 1218 (vw), 1190 (vw), 1171 (m), 1105 (m),
1071 (vw), 1020 (m), 936 (w), 929 (w), 793 (s), 763 (m), 758 (m),
722 (m).
K. H. Dötz, H. Fischer, P. Hoffmann, F. R. Kreissl, U. Schub-
ert, K. Weiss, Transition Metal Carbene Complexes, Verlag
Chemie, Weinheim, 1983.
[2]
´
N. M. Kostic, R. F. Fenske, J. Am. Chem. Soc. 1982, 104,
3879Ϫ3884.
[3]
[4]
[5]
[6]
[7]
[8]
[9]
N. Lugan, C. Kelley, M. R. Terry, G. L. Geoffroy, A. L. Rhein-
gold, J. Am. Chem. Soc. 1990, 112, 3220Ϫ3221.
T. R. Hoye, G. M. Rehberg, Organometallics 1990, 9,
3014Ϫ3015.
C. D. Abernethy, G. M. Codd, M. D. Spicer, M. K. Taylor, J.
Am. Chem. Soc. 2003, 125, 1128Ϫ1129.
M. Albrecht, J. R. Miecznikowski, A. Samuel, J. W. Faller, R.
H. Crabtree, Organometallics 2002, 21, 3596Ϫ3604.
[LMnNHAr{C[N(iPr)CMe]2}] (6). Method a: A solution of 5
(0.78 g, 1 mmol) in THF (20 mL) was added to a suspension of
sodium/potassium alloy (Na, 0.01 g, 0.5 mmol; K 0.04 g, 1 mmol)
in THF (10 mL). The mixture was stirred for 6 days at room tem-
perature. All volatiles were removed in vacuo and the residue was
extracted with n-hexane (10 mL). Yellow crystals were obtained
after cooling for one week at 4 °C. The crystals were collected by
filtration and the mother liquor was concentrated to ca. 4 mL and
kept at 4 °C for 4 days to give yellow crystals. Total yield: 0.19 g
(23%). M.p. 170Ϫ172 °C. C52H79MnN5 (829.14): calcd. C 75.26, H
9.53, N 8.44; found C 74.84, H 9.92, N 8.85. EI-MS: m/z (%) ϭ
472 (100) [LMn]ϩ, 648 (52) [LMnNHAr]ϩ. IR (KBr, Nujol mull):
´
V. C e sar, S. Bellemin-Laponnaz, L. H. Gade, Organometallics
2002, 21, 5204Ϫ5208.
A. J. Arduengo, III, R. L. Harlow, M. Kline, J. Am. Chem.
Soc. 1991, 113, 361Ϫ363.
[9a] D. Bourissou, O. Guerret, F. P. Gabba¨ı, G. Bertrand, Chem.
[9b]
Rev. 2000, 100, 39Ϫ91.
L. Jafarpour, S. P. Nolan, Adv. Or-
[9c]
ganomet. Chem. 2000, 46, 181Ϫ222.
Weskamp, V. P. W. Böhm, Adv. Organomet. Chem. 2002, 48,
W. A. Herrmann, T.
1Ϫ69.
[10]
[11]
M. F. Lappert, P. L. Pye, J. Chem. Soc., Dalton Trans. 1977,
2172Ϫ2180.
A. Wacker, H. Pritzkow, W. Siebert, Eur. J. Inorg. Chem.
1998, 843Ϫ849.
4336
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 4332Ϫ4337

Synthesis and Reaction of MnII Iodides
FULL PAPER
P. Friedrich, G. Besl, E. O. Fischer, G. Huttner, J. Organomet.
Chem. 1977, 139, C68ϪC72.
W. A. Herrmann, J. L. Hubbard, I. Bernal, J. D. Korp, B. L.
Haymore, G. L. Hillhouse, Inorg. Chem. 1984, 23, 2978Ϫ2983.
E. O. Fischer, W. Kleine, W. Schambeck, U. Schubert, Z. Na-
turforsch., Teil B 1981, 36, 1575Ϫ1579.
U. Schubert, Organometallics 1982, 1, 1085Ϫ1088.
D. S. McGuinness, B. F. Yates, K. J. Cavell, Organometallics
2002, 21, 5408Ϫ5414 and references cited therein.
B. L. Balzer, M. Cazanoue, M. Sabat, M. G. Finn, Organo-
metallics 1992, 11, 1759Ϫ1761.
H. Chen, R. A. Bartlett, H. V. R. Dias, M. M. Olmstead, P. P.
Power, Inorg. Chem. 1991, 30, 2487Ϫ2494 and references
cited therein.
J. Feldman, S. J. McLain, A. Parthasarathy, W. J. Marshall, J.
C. Calabrese, S. D. Arthur, Organometallics 1997, 16,
1514Ϫ1516.
[12]
[22]
[23]
[24]
G. B. Nikiforov, H. W. Roesky, T. Labahn, D. Vidovic, D. Nico-
lei, Eur. J. Inorg. Chem. 2003, 433Ϫ436.
[13] [13a]
C. Cui, H. W. Roesky, H.-G. Schmidt, M. Noltemeyer, H.
Hao, F. Cimpoesu, Angew. Chem. 2000, 112, 4444Ϫ4446; An-
gew. Chem. Int. Ed. 2000, 39, 4274Ϫ4276. [13b] G. Bai, Y. Peng,
H. W. Roesky, J. Li, H.-G. Schmidt, M. Noltemeyer, Angew.
Chem. 2003, 115, 1164Ϫ1167; Angew. Chem. Int. Ed. 2003,
[25]
[26]
42, 1126Ϫ1132.
J. Prust, K. Most, I. Müller, A. Stasch, H. W. Roesky, I. Uson,
[14]
´
[27]
[28]
Eur. J. Inorg. Chem. 2001, 1613Ϫ1616.
W. Clegg, E. K. Cope, A. J. Edwards, F. S. Mair, Inorg. Chem.
1998, 37, 2317Ϫ2319.
S. K. Hurst, T. Ren, J. Organomet. Chem. 2003, 670, 188Ϫ197.
J. Chai, H. W. Roesky, unpublished results.
D. Reardon, G. Aharonian, S. Gambarotta, G. P. A. Yap, Or-
ganometallics 2002, 21, 786Ϫ788 and references cited therein.
D. Walther, P. Gebhardt, R. Fischer, U. Kreher, H. Görls, In-
org. Chim. Acta 1998, 281, 181Ϫ189.
N. Hebendanz, F. H. Köhler, G. Müller, Inorg. Chem. 1984,
23, 3043Ϫ3044.
C. Eaborn, P. B. Hitchcock, J. D. Smith, S. Zhang, W. Clegg,
K. Izod, P. O’Shaughnessy, Organometallics 2000, 19,
1190Ϫ1193 and references cited therein.
[15]
[16]
[17]
[18]
[29]
[19]
[20]
[21]
[30]
[31]
[32]
N. Kuhn, T. Kratz, Synthesis 1993, 561Ϫ562.
G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467Ϫ473.
G. M. Sheldrick, SHELXL-97, Program for Crystal Structure
Refinement, Universität Göttingen, 1997.
Received May 15, 2003
Early View Article
Published Online October 10, 2003
Eur. J. Inorg. Chem. 2003, 4332Ϫ4337
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4337