Synthesis and structural characterization of three-coordinate Mn II, FeII, and ZnII complexes containing a bulky diamide ligand [DippN(CH2)3NDipp]2- (Dipp = 2,6-iPr2C6H3)

Article abstract of DOI:10.1002/ejic.200400390

The reaction of DippNH(CH₂)₃NHDipp (1) (Dipp = 2,6-iPr₂C₆H₃) with 2 equiv. of MeLi in diethyl ether resulted in the formation of the monomeric dilithium salt [(Dipp)N(CH ₂)₃N(Dipp)][Li(OEt₂)]₂ (2) in high yield. Further reactions of 2 with MnCl₂, FeCl₂, and ZnCl₂, respectively, afforded the complexes [M₂{N(Dipp) (CH₂)₃N(Dipp)}₂] [M = Mn (3), Fe (4), Zn (5)] with three-coordinate metal centers. Complexes 2-5 were characterized by X-ray structural analysis. The complexes contain a nonplanar MNMN central core. The diamide ligand in complexes 3-5 displays a boat conformation and is both chelating and bridging, so that one of the nitrogen atoms is three-coordinate and the other four-coordinate. Complexes 3-5 are the first examples with diamide ligands in such a bonding mode. The magnetic investigations of compounds 3 and 4 reveal an antiferromagnetic exchange between the metal atoms. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

Full text of DOI:10.1002/ejic.200400390

FULL PAPER
Synthesis and Structural Characterization of Three-Coordinate MnII, FeII, and
ZnII Complexes Containing a Bulky Diamide Ligand [DippN(CH2)3NDipp]2؊
(Dipp ؍ 2,6-iPr2C6H3)
Jianfang Chai,[a] Hongping Zhu,[a] Qingjun Ma,[a] Herbert W. Roesky,*[a]
Hans-Georg Schmidt,[a] and Mathias Noltemeyer[a]
Keywords: Iron / Manganese / N ligands / Zinc
The reaction of DippNH(CH2)3NHDipp (1) (Dipp = 2,6-
iPr2C6H3) with 2 equiv. of MeLi in diethyl ether resulted in
the formation of the monomeric dilithium salt
[(Dipp)N(CH2)3N(Dipp)][Li(OEt2)]2 (2) in high yield. Further
reactions of 2 with MnCl2, FeCl2, and ZnCl2, respectively,
afforded the complexes [M2{N(Dipp)(CH2)3N(Dipp)}2] [M =
core. The diamide ligand in complexes 3−5 displays a boat
conformation and is both chelating and bridging, so that one
of the nitrogen atoms is three-coordinate and the other four-
coordinate. Complexes 3−5 are the first examples with di-
amide ligands in such a bonding mode. The magnetic inve-
stigations of compounds 3 and 4 reveal an antiferromagnetic
Mn (3), Fe (4), Zn (5)] with three-coordinate metal centers. exchange between the metal atoms.
Complexes 2−5 were characterized by X-ray structural ana-
lysis. The complexes contain a nonplanar MNMN central
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
group 4 complexes that can catalyze olefin polymerization
under ‘‘living’’ conditions.[5] Cloke and Roesky et al. have
reported lanthanide complexes bearing this ligand.[6]
Transition metal complexes with three-coordinate metal
centers are rare, since it is difficult to reach the preferred
stable configurations with 16 or 18 valence electrons around
the metal center using only three donor ligands.[1] Metal
amide complexes are of wide interest as they show a broad
range of structures and reaction types.[2] Transition metal
amides, for instance, are the first examples with unusually
low coordinate metal centers due to the strong MϪN bonds
and flexible steric properties of the amine ligands.[2b] In ad-
dition, transition metal amides are a useful hydrocarbon-
soluble source of Mnϩ cations and have proved to be good
starting materials to prepare other species.[3] However, re-
ports of saturated hydrocarbon-bridged bidentate diamide
ligands are rare.[2b] Considering the recent success in the
Recently,
we
obtained
the
aluminum
hydride
[DippN(CH2)3NDipp]AlH(NMe3) and its derivatives
{[DippNH(CH2)3NDipp]Al}2(µ-E)2 (E ϭ S, Se and Te) by
hydrogen transfer from chalcogen to nitrogen.[7] Herein we
describe the synthesis and structural analysis of the dilith-
ium salt [N(Dipp)(CH2)3N(Dipp)][Li(OEt2)]2 (2) and the
resulting complexes with three-coordinate MnII, FeII, and
ZnII of composition [M2{N(Dipp)(CH2)3N(Dipp)}2] [M ϭ
Mn (3), Fe (4), Zn (5)].
Results and Discussion
synthesis of complexes of main-group elements, transition Synthesis of Compounds 2؊5
metals and lanthanides of unusual properties with the
The lithiation of DippNH(CH2)3NHDipp (1) with 2
Dippnacnac ligand [HC(CMeNDipp)2]Ϫ (Dipp ϭ 2,6-
iPr2C6H3),[4] we were interested in investigating the be-
havior of the bulky chelating diamide ligand
[DippN(CH2)3NDipp]2Ϫ, which has similar steric proper-
ties to Dippnacnac and is expected to result in interesting
new organometallic chemistry.
equiv. of MeLi in diethyl ether proceeds smoothly to afford
[(Dipp)N(CH2)3N(Dipp)][Li(OEt2)]2 (2) as colorless crys-
tals in high yield (Scheme 1). The existence of the coordi-
The bulky chelating diamide ligand [DippN-
(CH2)3NDipp]2Ϫ was previously used by McConville and
co-workers as a non-cyclopentadienyl ligand to prepare
[a]
Institut für Anorganische Chemie, Universität Göttingen,
Tammannstrasse 4, 37077 Göttingen, Germany
Fax: ϩ 49-551-393-373
E-mail: hroesky@gwdg.de
Scheme 1
Eur. J. Inorg. Chem. 2004, 4807Ϫ4811
DOI: 10.1002/ejic.200400390
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4807

J. Chai, H. Zhu, Q. Ma, H. W. Roesky, H.-G. Schmidt, M. Noltemeyer
FULL PAPER
˚
1
Table 2. Selected bond lengths [A] and bond angles [°] for 3Ϫ5
nated diethyl ether molecules was confirmed by H NMR
spectroscopy, elemental analysis, and an X-ray solid-state
structural analysis. The dilithium salt 2 is soluble in diethyl
ether and stable under an inert gas and is a useful reagent
for metathesis reactions with metal halides.
Compound 3
Mn(1)ϪN(1)
Mn(1)ϪN(2)
Mn(1)ϪN(3)
Mn(1)ϪMn(2)
Mn(2)ϪN(2)
Mn(2)ϪN(3)
Mn(2)ϪN(4)
Compound 4
1.932(2)
2.126(3)
2.078(3)
2.690(2)
2.093(3)
2.128(3)
1.935(2)
N(1)ϪMn(1)ϪN(2)
N(1)ϪMn(1)ϪN(3)
N(2)ϪMn(1)ϪN(3)
N(1)ϪMn(1)ϪMn(2)
N(2)ϪMn(1)ϪMn(2)
N(3)ϪMn(1)ϪMn(2)
Mn(1)ϪN(2)ϪMn(2)
106.79(10)
146.55(9)
96.72(10)
133.93(8)
49.86(8)
The reaction of 2 with 1 equiv. of anhydrous MnCl2,
FeCl2, or ZnCl2, respectively, in diethyl ether at low tem-
perature smoothly provided the corresponding dimeric
compounds [M2{N(Dipp)(CH2)3N(Dipp)}2] [M ϭ Mn (3),
51.07(8)
79.20(9)
Fe (4), Zn (5)] in good yield (Scheme 2). The same products Fe(1)ϪN(1)
1.878(3)
2.085(3)
2.022(3)
2.557(2)
2.022(3)
N(1)ϪFe(1)ϪN(2A)
N(2)ϪFe(1)ϪN(2A)
N(1)ϪFe(1)ϪFe(1A)
N(2)ϪFe(1)ϪFe(1A)
N(2A)ϪFe(1)ϪFe(1A)
Fe(1)ϪN(2)ϪFe(1A)
146.98(12)
97.94(12)
137.06(9)
50.39(9)
52.61(9)
77.00(11)
Fe(1)ϪN(2)
were obtained even when 2 equiv. of MCl2 were employed.
Fe(1)ϪN(2A)
Complexes 3Ϫ5 are soluble in CH2Cl2 and THF and have
Fe(1)ϪFe(1A)
a moderate solubility in diethyl ether and toluene.
Fe(1A)ϪN(2)
N(1)ϪFe(1)ϪN(2) 108.89(12)
Compound 5
Zn(1)ϪN(1)
Zn(1)ϪN(2)
Zn(1)ϪN(2A)
Zn(1)ϪZn(1A)
Zn(1A)ϪN(2)
1.8537(16) N(1)ϪZn(1)ϪN(2A)
1.9969(16) N(2)ϪZn(1)ϪN(2A)
2.0798(15) N(1)ϪZn(1)ϪZn(1A)
2.6505(5) N(2)ϪZn(1)ϪZn(1A)
2.0798(15) N(2A)ϪZn (1)ϪZn(1A) 48.10(5)
Zn(1)ϪN(2)ϪZn(1A) 81.08(5)
111.45(6)
92.92(6)
136.14(5)
50.82(4)
N(1)ϪZn(1)ϪN(2) 148.69(6)
plexes are given in the Exp. Sect. and selected bond lengths
and angles in Tables 1 and 2.
The X-ray structural analysis of 2 (Figure 1) reveals a
monomer with two three-coordinate lithium atoms. Each of
the lithium atoms is bonded to two nitrogen atoms of the
chelating ligand and one oxygen atom of the coordinated
ether ligand. It is better to describe the coordination sphere
of the Li atoms as trigonal-planar rather than trigonal-pyr-
amidal. Two C3N2Li six-membered rings are formed, one
of which displays a boat conformation while the other is in
a chair conformation. The interplanar angle between the
two central LiN2 planes is 43.8°. The LiϪN distances are
Scheme 2
1
Complexes 2Ϫ5 were characterized by EI-MS, H NMR
and IR spectroscopy and X-ray solid-state structural analy-
sis. The molecular ion peaks of 3Ϫ5 in the EI mass spectra
were all observed. However, the most intense peaks of these
complexes show different fragments: 3: m/z ϭ 705 [M Ϫ
CH2NDipp]ϩ; 4: m/z ϭ 504 [M Ϫ N(Dipp)(CH2)3N-
(Dipp)]ϩ; 5: m/z ϭ 456 [1/2 M]ϩ. In the the monomeric
compounds {such as [N(Dipp)(CH2)3N(Dipp)]AlX·NMe3
(X ϭ H, F)}[7] the four isopropyl methine groups (CHMe2)
are not equivalent and give two resonances in the 1H NMR
spectra, whereas compound 5 gives four isopropyl methine
resonances, which is consistent with restricted rotation
about the NϪCipso bond. The doublets in the range of δ ϭ
0.16Ϫ1.36 ppm correspond to the protons of methyl
groups (CHMe2).
[2b]
˚
in the normal range (1.94Ϫ2.15 A).
In addition, there
are some very close contacts between Li(1), Li(2) and vari-
ous carbon and hydrogen atoms from the chelating ligand
˚
˚
[Li(1)ϪH(26a): 2.29(4) A; Li(2)ϪC(2): 2.36(2) A;
˚
Li(2)ϪH(2a): 2.02(4) A]. Similar contacts have been ob-
served in [Li(Dipp)NCH2CH2N(Dipp)Li]2.[2b]
X-ray Solid-State Structural Analyses
The X-ray solid-state structural analyses for complexes
2Ϫ5 were undertaken. Crystallographic data for these com-
˚
Table 1. Selected bond lengths [A] and bond angles [°] for 2
Li(1)ϪO(1)
Li(1)ϪN(1)
Li(1)ϪN(2)
Li(1)ϪLi(2)
Li(2)ϪN(1)
Li(2)ϪN(2)
Li(2)ϪO(2)
O(1)ϪLi(1)ϪN(1)
1.894(11)
1.999(10)
1.971(10)
2.514(13)
2.028(10)
2.039(10)
1.949(10)
O(1)ϪLi(1)ϪN(2)
N(1)ϪLi(1)ϪN(2)
O(1)ϪLi(1)ϪLi(2)
N(1)ϪLi(1)ϪLi(2)
N(2)ϪLi(1)ϪLi(2)
O(2)ϪLi(2)ϪN(1)
O(2)ϪLi(2)ϪN(2)
N(1)ϪLi(2)ϪN(2)
118.3(5)
96.8(5)
163.6(6)
51.9(3)
52.4(3)
144.0(5)
114.2(5)
93.7(4)
142.8(6)
Figure 1. ORTEP drawing for 2 (50% probability ellipsoids)
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Eur. J. Inorg. Chem. 2004, 4807Ϫ4811

Three-Coordinate MnII, FeII, and ZnII Complexes Containing a Bulky Diamide Ligand
FULL PAPER
The X-ray solid-state structural analysis reveals that com-
plexes 3Ϫ5 are isostructural and dimeric. The dimers are
formed through two bridging nitrogen atoms. Compound
[Mn2{N(Dipp)(CH2)3N(Dipp)}2] (3; Figure 2) crystallizes
¯
in the triclinic space group P1, while compounds
[Fe2{N(Dipp)(CH2)3N(Dipp)}2] (4; Figure 3) and
[Zn2{N(Dipp)(CH2)3N(Dipp)}2] (5; Figure 4) crystallize in
the monoclinic space group C2/c. The central core of these
compounds contains a nonplanar MNMN four-membered
ring, which is in a butterfly configuration, with dihedral
angles of 28.6° in 3, 30.9° in 4, and 35.0° in 5. This arrange-
ment is caused by the strain of the bulky aryl groups. Each
metal atom is surrounded by three nitrogen atoms and al-
ways lies out of the plane formed by these nitrogen atoms
˚
˚
˚
(0.33 A in 3, 0.26 A in 4, and 0.26 A in 5), so that all the
metal atoms are in a trigonal-pyramidal geometry. The two
ligands chelate two metal atoms to fuse two six-membered
MN2C3 rings, which display a boat conformation with the
two metal atoms at the stern and the corresponding op-
posite carbon atoms at the bow. The metal atoms are about
Figure 4. ORTEP drawing for 5 (50% probability ellipsoids)
˚
˚
˚
0.72 A in 3, 0.71 A in 4, and 0.73 A in 5) out of the plane.
The ligand in complexes 3Ϫ5 is both chelating and bridg-
ing, so that one of the nitrogen atoms is three-coordinate
and the other four-coordinate. To the best of our knowl-
edge, complexes 3Ϫ5 are the first examples with the di-
amide ligands in such a bonding mode. The terminal MϪN
˚
˚
˚
˚
0.20 A (av. 0.17 A in 3, 0.22 A in 4, and 0.18 A in 5) out
of the plane formed by the two carbon and two nitrogen
˚
atoms. The opposite carbon atoms are about 0.70 A (av.
˚
distances in these complexes (MnϪN: 1.93 A; FeϪN: 1.88
A; ZnϪN: 1.85 A) are significantly shorter than those of
˚
˚
˚
the corresponding bridging ones (MnϪN: 2.10 A; FeϪN:
˚
˚
2.05 A; ZnϪN: 2.04 A). The MϪN distances decrease in
the order MnϪN Ͼ FeϪN Ͼ ZnϪN, while the NϪMϪN
angles increase in the order NϪMnϪN Ͻ NϪFeϪN Ͻ
NϪZnϪN, which is consistent with the relative sizes of the
cations: Mn2ϩ Ͼ Fe2ϩ Ͼ Zn2ϩ [8]
.
The terminal and bridg-
˚
ing MϪN distances in 3 and 4 are about 0.06 A shorter
than the corresponding distances in the dimeric silylamides
[9]
Mn2[N(SiMe3)2]4
and Fe2[N(SiMe3)2]4.[10] The terminal
MϪN bond lengths in complexes 3 and 4 are even shorter
than those found in amides with two coordinate metal cen-
˚
ters [Mn{N(SiMePh2)2}2] (MnϪN 1.99 A) and
[11]
˚
[Fe{N(SiMe2Ph)2}2] (FeϪN 1.92 A).
This possibly re-
Figure 2. ORTEP drawing for 3 (50% probability ellipsoids)
sults from the strong NǞSi interaction in the silylamide.[10]
The MϪM distances and the MϪNϪM angles in com-
˚
˚
plexes 3 and 4 are 2.69 A and 79.2°, and 2.56 A and 77.0°,
respectively, which indicates that there is some contact be-
tween the metal centers. The MϪM distances are signifi-
cantly shorter than those in the commonly planar MNMN
four-membered rings.[9,10]
Magnetic Susceptibility Measurements
The temperature dependence of the molar magnetic sus-
ceptibility, χm and χmT, for compounds 3 and 4 are dis-
played in Figures 5 and 6, respectively. The plots of χmT(T)
Ϫ T for the two compounds indicate a magnetic behavior
with an antiferromagnetic exchange interaction between the
nearest neighboring spins. The value of χmT at 300 K is
estimated to 6.82 emu·K·molϪ1 for
emu·K·molϪ1 for 4. These values are lower than those of
3
and 5.16
Figure 3. ORTEP drawing for 4 (50% probability ellipsoids)
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J. Chai, H. Zhu, Q. Ma, H. W. Roesky, H.-G. Schmidt, M. Noltemeyer
FULL PAPER
the spin-only value (S ϭ 5/2 for MnII dimer and S ϭ 2 for
FeII dimer). This reveals that there is an antiferromagnetic
exchange interaction between the two metal atoms in both
compounds.
Universität Göttingen. Mass spectra were recorded with a Finnigan
Mat 8230. IR spectra were measured with a Bio-Rad Digilab FTS-
7
spectrometer as Nujol mulls between KBr plates.
[DippNH(CH2)3NH(Dipp)] (1) was prepared according to a litera-
ture method.[5c]
[N(Dipp)(CH2)3N(Dipp)][Li(OEt2)]2 (2): MeLi (5.5 mL, 1.6  in di-
ethyl ether, 8.8 mmol) was added at Ϫ78 °C to a diethyl ether
(35 mL) solution of 1 (1.58 g, 4 mmol). The mixture was warmed
to room temperature and stirred for an additional 14 h. The pre-
cipitate was removed by filtration. The filtrate was concentrated to
about 10 mL and kept at Ϫ26 °C for 24 h to give colorless crystals.
The crystals were collected by filtration and the mother liquor was
concentrated to about 4 mL and kept at Ϫ26 °C for 24 h to give
1
colorless crystals. Total yield: 2.04 g (92%). M.p. 110 °C (dec). H
NMR (250 MHz, C6D6): δ ϭ 0.95 (t, 12 H, J ϭ 7.1 Hz, MeCH2O),
1.23 (d, 12 H, J ϭ 6.8 Hz, Me2CH), 1.34 (d, 12 H, Me2CH), 1.79
(br., 2 H, NCH2CH2), 3.00Ϫ3.25 (m, 4 H, J ϭ 7.2 Hz, NCH2CH2),
3.12 (t, 8 H, J ϭ 7.0 Hz, MeCH2O), 3.38 (sept, 4 H, J ϭ 6.9 Hz,
CHMe2), 6.91Ϫ7.22 (m, C6H3, 6 H) ppm. 7Li NMR (300 MHz,
C6D6): δ ϭ 1.90 ppm. C35H60Li2N2O2 (554.75): calcd. C 75.78, H
10.90, N 5.05; found C 75.92, H 11.02, N 4.85.
Figure 5. Plots of χm(T) Ϫ T and χmT(T) Ϫ T for compound 3
[Mn2{N(Dipp)(CH2)3N(Dipp)}2] (3): A solution of 2 (1.1 g, 2 mmol)
in diethyl ether (10 mL) was added to a suspension of MnCl2
(0.25 g, 2 mmol) in diethyl ether (30 mL) at Ϫ78 °C. The mixture
was warmed to room temperature and stirred for additional 14 h.
The precipitate was removed by filtration and extracted with di-
chloromethane (10 mL). A yellow-green solid was obtained by re-
moving the solvent in vacuo. The mother liquor was concentrated
to about 10 mL and yellow-green crystals were obtained at room
temperature after 5 d. Total yield: 0.64 g (72%). M.p. 220 °C (dec).
EI-MS: m/z (%) ϭ 894 (49) [M]ϩ, 705 (100) [M Ϫ CH2NDipp]ϩ,
447 (68) [1/2 M]ϩ. C54H80Mn2N4 (895.10): calcd. C 72.39, H 8.94,
N 6.26; found C 72.15, H 8.94, N 6.17. IR (KBr, nujol mull): ν˜ ϭ
1426 (w), 1308 (w), 1260 (w), 1243 (w), 1169 (w), 1092 (w), 1073
(w), 1041(w), 1019 (w), 857 (w), 800 (w), 786 (w), 722 (w) cmϪ1
.
[Fe2{N(Dipp)(CH2)3N(Dipp)}2] (4): A solution of 2 (1.1 g, 2 mmol)
in diethyl ether (10 mL) was added to a suspension of FeCl2 (0.25 g,
2 mmol) in diethyl ether (30 mL) at Ϫ78 °C. The mixture was
warmed to room temperature and stirred for additional 14 h. The
precipitate was removed by filtration. The dark-blue filtrate was
Figure 6. Plots of χm(T) Ϫ T and χmT(T) Ϫ T for compound 4
In summary, we have successfully synthesized and
characterized novel dimeric MnII, FeII, and ZnII complexes,
which contain three-coordinate metal centers by using the concentrated to about 10 mL and crystals of 4 were obtained at
room temperature after 5 d. Yield: 0.67 g (75%). M.p. 228 °C (dec).
EI-MS: m/z (%)
bulky diamide ligand DippNH(CH2)3NHDipp. In com-
plexes 3Ϫ5 the ligand is both chelating and bridging, so
that one of the nitrogen atoms is three-coordinate and the
other four-coordinate. Complexes 3Ϫ5 are the first ex-
amples with diamide ligands in such a bonding mode.
ϭ
896 (68) [M]ϩ, 504 (100) [M
Ϫ
N(Dipp)(CH2)3N(Dipp)]ϩ, 448 (13) [1/2 M]ϩ. C54H80Fe2N4
(896.92): calcd. C 72.25, H 8.92, N 6.24; found C 72.08, H 8.63, N
6.13. IR (KBr, nujol mull): ν˜ ϭ 1403 (w), 1308 (w), 1262 (w), 1201
(w), 1155 (w), 1094 (m), 1030 (m), 973 (w), 933 (w), 918 (w), 890
(w), 801 (m), 750 (w), 722 (m), 658 (w), 597 (w), 564 (w), 540 (w),
465 (w) cmϪ1
.
Experimental Section
[Zn2{N(Dipp)(CH2)3N(Dipp)}2] (5): The procedure is the same like
that described for 3. Yield: 0.72 g (79%). M.p. 223 °C (dec). EI-
MS: m/z (%) ϭ 916 (7) [M]ϩ, 456 (100) [1/2 M]ϩ. 1H NMR
(500 MHz, CDCl3): δ ϭ 0.16 (d, 6 H, J ϭ 6.8 Hz, Me2CH), 0.43
(d, 6 H, Me2CH), 0.99 (d, 6 H, Me2CH), 1.21Ϫ1.28 (m, 24 H,
Me2CH), 1.36 (d, 6 H, Me2CH), 2.20Ϫ2.34 (m, 4 H, J ϭ 9.7 Hz,
NCH2CH2), 2.71(t, 2 H, J ϭ 7.1 Hz, NCH2CH2), 2.81 (m, 2 H,
J ϭ 6.9 Hz, CHMe2), 3.02 (t, 2 H, NCH2CH2), 3.12 (m, 4 H,
NCH2CH2), 3.27 (m, 2 H, CHMe2), 3.72 (m, 2 H, NCH2CH2),
3.97 (t, 2 H, NCH2CH2), 4.04 (m, 2 H, CHMe2), 3.72 (m, 2 H,
General: All reactions were performed using standard Schlenk and
dry-box techniques. Solvents were appropriately dried and distilled
under dinitrogen prior to use. 1H and 7Li NMR spectra were re-
corded with Bruker AM-250, AM-300 and AM-500 instruments.
The chemical shifts are reported in ppm with reference to external
standards: SiMe4 for H and LiCl/D2O for Li. The magnetic sus-
ceptibility measurements were carried out with a Quantum-Design-
MPMS-5S SQUID magnetometer in the range from 300 K to 2 K.
The powdered samples were placed in a gel bucket and fixed in a
1
7
nonmagnetic sample holder. Elemental analyses were performed by CHMe2), 6.78Ϫ7.45 (m, 12 H, C6H3) ppm. C54H80N4Zn2 (915.96):
the Analytisches Labor des Instituts für Anorganische Chemie der calcd. C 70.75, H 8.73, N 6.11; found C 70.34, H 8.68, N 5.85. IR
4810
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Three-Coordinate MnII, FeII, and ZnII Complexes Containing a Bulky Diamide Ligand
FULL PAPER
Table 3. Crystallographic data for compounds 2Ϫ5
2
3
4
1/2 5
Empirical formula
Formula mass
C35H60Li2N2O2
554.73
200(2)
C54H80Mn2N4
895.10
203(2)
C54H80Fe2N4
896.92
203(2)
C27H40N2Zn
457.98
133(2)
Temperature [K]
˚
Wavelength [A]
0.71073
0.71073
0.71073
1.54178
Crystal system
Space group
Unit cell dimensions [A]
monoclinic
P21/n
triclinic
P1
monoclinic
C2/c
monoclinic
C2/c
¯
˚
a ϭ 11.224(2)
b ϭ 9.6466(19)
c ϭ 32.070(6)
α ϭ 90°
β ϭ 92.19(3)°
γ ϭ 90°
3469.7(12)
1.00 ϫ 0.70 ϫ 0.60
4
a ϭ 11.545(9)
b ϭ 13.642(10)
c ϭ 18.014(15)
α ϭ 105.26(8)°
β ϭ 94.01(3)°
γ ϭ 111.954(18)°
2490(1)
1.00 ϫ 0.50 ϫ 0.30
2
0.545
a ϭ 25.14(2)
b ϭ 11.472(12)
c ϭ 18.121(9)
α ϭ 90°
β ϭ 108.12(6)°
γ ϭ 90°
4970(1)
1.30 ϫ 0.40 ϫ 0.40
4
0.623
3.55 to 22.51°
1936
a ϭ 25.057(2)
b ϭ 11.447(2)
c ϭ 17.881(2)
α ϭ 90°
β ϭ 108.00(2)°
γ ϭ 90°
4877.7(11)
0.10 ϫ 0.10 ϫ 0.10
8
3
˚
Volume [A ]
Crystal size [mm]
Z
Absorption coefficient [mmϪ1
θ range for data collection
F(000)
]
0.063
3.60 to 22.53°
1224
1.491
3.71 to 60.69°
1968
3.54 to 25.04°
964
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
R (all data)
7629
11007
8774 (Rint ϭ 0.0616)
8774/0/557
3256
11348
4515 (Rint ϭ 0.0710)
4515/0/393
1.115
0.0979, 0.2922
0.1357, 0.3219
0.527/Ϫ0.427
3219 (Rint ϭ 0.0799)
3219/0/279
1.044
0.0591, 0.1561
0.0661, 0.1665
0.491/Ϫ1.112
3661 (Rint ϭ 0.0383)
3661/0/279
1.032
0.0295, 0.0736
0.0328, 0.0754
0.032/Ϫ0.460
1.023
0.0461, 0.1150
0.0601, 0.1258
0.533/Ϫ0.638
Ϫ3
˚
Largest difference peak/hole [e·A
]
(KBr, nujol mull): ν˜ ϭ 1587 (w), 1320 (w), 1309 (m), 1273 (w), 1262
(w), 1245 (w), 1167 (m), 1100 (m), 1073 (w), 1043 (w), 967 (w), 931
(w), 888 (w), 861 (w), 801 (w), 788 (m), 759 (w), 746 (w), 722 (m),
[1]
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610 (w), 556 (w), 479 (w) cmϪ1
.
X-ray Crystallography: Crystallographic data for 2Ϫ4 (Table 3)
were collected with StoeϪSiemensϪHuber four-circle dif-
fractometer coupled to
a
[3]
[4]
a
Siemens CCD area-detector with
˚
graphite-monochromated Mo-Kα radiation (λ ϭ 0.71073 A) and
for 5 with a Bruker three-circle diffractometer equipped with a
SMART 6000 CCD area-detector using Cu-Kα radiation (λ ϭ
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˚
1.54178 A). All structures were solved by direct methods
[5c]
(SHELXS-97)[12] and refined against F2 using SHELXL-97.[13] All
non-hydrogen atoms were refined anisotropically. The central car-
bon atom C(2) in 2 is disordered over two positions C(2) and C(2Ј),
which were isotropically refined with site-occupation factors of 0.34
and 0.66, respectively. CCDC-233452 (2), -233453 (3), -233454 (4),
and -233455 (5) 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: ϩ 44-1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk].
McConville, J. Am. Chem. Soc. 1996, 118, 10008Ϫ10009.
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D. Scollard, D. H. McConville, J. J. Vittal, Organometallics
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[10]
[11]
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Received May 12, 2004
[12]
[13]
Acknowledgments
The work was supported by the Deutsche Forschungsgemeinschaft,
the Göttinger Akademie der Wissenshaften and Ciba company. We
are thankful to Dr. Xiaoming Ren and Mr. Björn Sass for per-
forming the magnetic measurements.
Early View Article
Published Online November 10, 2004
Eur. J. Inorg. Chem. 2004, 4807Ϫ4811
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4811