SHORT COMMUNICATION

DOI: 10.1002/ejic.200701320

Carbamates of Polyamines – Versatile Building Blocks for the Construction of

Polynuclear Metal Complexes[‡]

Christian Neis,[a] Thomas Weyhermüller,[b] Eckhard Bill,[b] Stefan Stucky,[a] and

Kaspar Hegetschweiler*[a]

Keywords: Carbon dioxide / Chelates / Iron / Mössbauer spectroscopy / N ligands / O ligands

A new concept for the design of polynuclear metal com- aerobic conditions. After partial conversion of L into its di-
plexes is described: Partial aeration of a polyamine solution carbamate derivative H–2L(CO2)22–, the components sponta-
with CO2 generates a system where both, a chelating agent neously assemble to the tetranuclear complex [(µ-O)2(FeIIIL)4-
(the unreacted polyamine) and a bridging agent (the poly- {µ-H–2L(CO2)2}2]4+ (14+). 1(ClO4)4 was characterized by sin-
carbamate) are present. Together with a metal cation, these gle-crystal X-ray analysis, Mössbauer spectroscopy, and
components constitute an ideal set of building blocks for the magnetic susceptibility measurements.
construction of extended molecular architectures. These con-
siderations are exemplified in the reaction of the well-known (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
triamine 6-methyl-1,4-diazepan-6-amine (L) with FeII under Germany, 2008)

Introduction N–C–C–N–C–O substructure in a mononuclear complex

would enforce the formation of unfavorable seven- or even
Polyamines such as 1,2-diaminoethane (en), 1,4,7-triaza-
nine-membered chelate rings. Consequently, a bridging co-
heptane (den), 1,4,7,10-tetraazadecane (trien) or corre-
ordination mode would be expected to be more suitable. In
sponding cyclic derivatives constitute one of the best
this communication, we will demonstrate that polycarbam-
studied class of ligands for di- or trivalent transition metal
ates are indeed promising synthons for the construction of
cations.[1,2] These amines are classical chelating agents,
extended metal-organic architectures.
forming usually mononuclear species with the nitrogen do-
nors incorporated in five- or six-membered chelate rings. It
is well known that solutions of free amines readily absorb
CO2 to yield the corresponding carbamates,[3] and a variety Results and Discussion
of metal complexes with carbamates of monoamines have
Under aerobic conditions, the addition of iron(II) per-
been described in the literature.[3–5] However, the synthetic
chlorate and 6-methyl-1,4-diazepan-6-amine (= L) to a
procedures used, such as CO2 insertion into the metal–ni-
solution of L, which has been aerated previously with CO2,
trogen bond of the corresponding metal amide, was often
resulted in the spontaneous formation of the tetranuclear
rather demanding.[4] The motivation of this research was
complex [(µ-O)2(FeL)4{µ-H–2L(CO2)2}2]4+ (14+). It could
primarily to study one-carbon sources[5] in synthetic appli-
be crystallized as a perchlorate salt of composition 1(ClO4)4·
cations and modeling of CO2 fixation[6] in biological sys-
6MeOH·H2O, and the structure could be elucidated by X-
tems. However, the possibility to use carbamates of the
ray diffraction analysis (Figure 1). The complex contains
above-mentioned polyamines[6c,6e,7,8] as particularly suitable
four FeIIIL units, with the triamine L adopting a facial ori-
building blocks for the construction of polynuclear struc-
entation in the distorted FeN3O3 octahedron. In 14+, each
tures has, to the best of our knowledge, not widely been
two FeIIIL units are connected through a µ-oxido bridge to
considered. This is surprising since coordination of a mono-
two LFeIII–O–FeIIIL fragments which in turn are further
carbamate derivative with its O–C–N–C–C–N substructure
fused by two bis(carbamate) derivatives H–2L(CO2)22– to
and in particular the dicarbamate derivative with its O–C–
the tetranuclear cation. Only CO2 addition at the two sec-
[‡] Facially Coordinating Cyclic Triamines, 4. Part 3: Ref.[2c] ondary amino groups is observed; the primary amino
[a] Universität des Saarlandes, Anorganische Chemie, groups are not affected. The entire complex closely adopts
Postfach 151150, 66041 Saarbrücken, Germany C2v symmetry; however, in the crystal structure, the two
Fax: +49-681-302-2663
E-mail: [email protected] mirror planes are destroyed by an asymmetric conformation
[b] Max-Planck-Institut für Bioanorganische Chemie, of the two central seven-membered diazepane rings. The
Stiftstr. 34–36, 45470 Mülheim, Germany
Supporting information for this article is available on the true crystallographic symmetry is therefore C2. The Vis
WWW under http://www.eurjic.org or from the author. spectrum of this complex is in agreement with the charac-

Eur. J. Inorg. Chem. 2008, 1019–1021 © 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1019
SHORT COMMUNICATION C. Neis, T. Weyhermüller, E. Bill, S. Stucky, K. Hegetschweiler

teristics reported previously for the bis(µ-carboxylato)(µ- metal complexes by using simple solutions of a metal salt
oxido)diiron(III) unit (Supporting Information).[9] The and a polyamine ligand which was partially converted into
compound is paramagnetic, and the dependence of χ on T a polycarbamate derivative.
in the range of 2–290 K can simply be interpreted by adopt- (i) We have demonstrated that the dicarbamate unit with
ing two independent, antiferromagnetically coupled FeIII– its O–C–N–C–C–N–C–O substructure has a low tendency
O–FeIII dimers with high-spin configuration for the ferric to bind both donor atoms to the same metal cation. This
ions (S1 = S2 = 5/2, Figure S1 in the Supporting Infor- generates an easy route to obtain a bridging agent
mation). The resulting exchange coupling constant J of H–2L(CO2)22– from the chelating agent L. The ability of the
–108.4 cm–1 (H = –2JS1·S2) lies at the low end of the range H–2L(CO2)22– anion for bridging interactions gains further
known for (µ-RCO2)2(µ-O)(FeIII)2 systems.[9–11] Additional support by the well-known tendency of the carbamate
interactions between the two diiron centers within the tetra- group for M–O–C(NRR⬘)–O–M interactions.[5]
nuclear unit are obviously not significant. The zero-field (ii) Controlled dosage of CO2 to the amine allows a spe-
Mössbauer spectrum (Figure S2 in the Supporting Infor- cific fine tuning of the amount of free amino groups and
mation) is also in agreement with literature values.[9,11] The carbamate groups, i.e. a fine tuning of the chelating vs.
data measured at 80 K could be fitted by two symmetric bridging properties of this system. It is hoped that such
quadrupole doublets, each having a relative intensity of considerations will allow a specific control of the amount
50 %. The observation of two slightly different quadrupole of aggregation in framework architectures.
doublets with isomer shifts of 0.47 und 0.48 mm/s and qua-
drupole splittings of 1.50 und 1.72 mm/s is obviously due
to the different configuration of the two FeIII centers in the Experimental Section
diiron unit: with regard to the free amino groups of the two
H–2L(CO2)22– bridges, one of the Fe centers adopts a cisoid, Synthesis: 6-Methyl-1,4-diazepan-6-amine[12] (50 mg, 0.39 mmol)
was dissolved in MeOH (3 mL) and aerated with CO2 for a period
the other a transoid arrangement.
of 30 min. To this solution was added Fe(ClO4)2 (99 mg,
0.39 mmol) dissolved in acetonitrile (2.5 mL). An additional por-
tion of free 6-methyl-1,4-diazepan-6-amin (50 mg, 0.39 mmol) was
directly added to the reaction mixture. The resulting clear, yellow-
brownish solution was placed in an open beaker and was allowed
to stand in a desiccator which contained an additional beaker with
ethyl acetate. Within a period of 24 h, yellow-brownish crystals de-
posited. They were separated by filtration and dried at reduced
pressure (yield: 120 mg, 0.07 mmol, 70 % in reference to Fe). C,H,N
analysis (see Supporting Information) is in agreement with
the composition [(µ-O)2(FeL)4{µ-H–2L(CO2)2}2](ClO4)4·3MeOH·
3H2O; the crystals of composition [(µ-O)2(FeL)4{µ-H–2L-
(CO2)2}2](ClO4)4·6MeOH·H2O disintegrate rapidly; they were
Figure 1. Ball-and-stick representation of the tetranuclear cation therefore directly moved from the mother liquor to the goniometer
14+ (yellow: Fe, red: O, blue: N); the C backbone is shown as a head without further characterization.
stick model in black; H atoms were omitted for clarity.
Instrumentation: A description of the equipment used for spec-
The bis(µ-carboxylato)(µ-oxido)diiron(III) unit has been troscopy (UV/Vis and Mössbauer) and the magnetic susceptibility
observed in a variety of biological compounds. A particu- measurements is provided in the Supporting Information. The iso-
larly prominent example is hemerythrin.[11] Several model mer shift in the Mössbauer spectra refers to α-iron at room tem-
complexes have been prepared,[9–11] and a few specific perature. The molar magnetic susceptibility (χ ⫻ T) was simulated
by using a spin Hamiltonian for a symmetric dimer with two cou-
bridging agents have been designed and prepared to fuse
pled spins of 5/2 (see the Supporting Information).
two such diiron units to a tetranuclear system.[10] However,
the synthesis of such bridging agents often enforces exten- Crystal-Structure Analysis: Bruker-Nonius Kappa-CCD dif-
sive synthetic procedures. The L/CO2 concept presented fractometer, graphite monochromator, Mo-Kα radiation (λ =
here obviously offers ideal prerequisites for the spontaneous 0.71073 Å), crystal size: 0.05 ⫻ 0.10 ⫻ 0.26 mm, monoclinic, space
group C2/c, a = 17.4978(5), b = 27.9355(7), c = 19.1930(6) Å, β =
formation and isolation of such polynuclear species. The
108.277(3)°, V = 8908.4(5) Å3, Z = 4 for C46H112Cl4Fe4N18O33 (Mr
particular advantage of our approach is the possibility to
= 1810.74 g mol–1), ρcalcd. = 1.350 g cm–3, µ = 0.839 mm–1,
use the triamine unit at the same time not only as a chelat- 2.96° ⬍ θ ⬍ 26.00°, T = 100(2) K. Intensities: 81435 measured, 8748
ing agent, stabilizing the cation and preventing further hy- unique, 6928 observed [I ⬎ 2σ(I)], empirical absorption correction
drolysis, but also as the bridging agent in its dicarbamate (Tmin/Tmax = 0.8345/0.9492). The structure was solved by direct
form. methods (SHELXS-97), and refined on F2 (512 parameters) using
full-matrix least-squares calculations (SHELXL-97). The position
of the water oxygen atom O100 was refined isotropically with an
Conclusions and Outlook occupancy of 0.5; all other non-hydrogen atom positions were re-
fined by using anisotropic displacement parameters. Treatment of
In this communication, we present a promising and easily hydrogen atom positions: H45A and H45B (free primary amino
applicable concept for the construction of polynuclear group) were located in a difference Fourier map and refined iso-

1020 www.eurjic.org © 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Eur. J. Inorg. Chem. 2008, 1019–1021
Carbamates of Polyamines

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