Insertion reactions of organic anhydrides and the Cu(I) alkoxide [CuO tBu]

Article abstract of DOI:10.1016/j.ica.2005.06.061

The synthesis and structural characterization of the copper salts [Cu ₈(benzoate)₈(THF)₆] (1), [Cu ₂{(CO₂)₂C₆H₂(Boc) ₂}dppm₂]₂ (2) and

Full text of DOI:10.1016/j.ica.2005.06.061

Inorganica Chimica Acta 358 (2005) 3967–3973
www.elsevier.com/locate/ica
Insertion reactions of organic anhydrides
and the Cu(I) alkoxide [CuOtBu]
*
Christopher E. Anson, Robert Langer, Lukasz Ponikiewski, Alexander Rothenberger
Institut fu¨r Anorganische Chemie, Universita¨t Karlsruhe, Engesser Straße 15, Geb. 30.45, D-76131 Karlsruhe, Germany
Institut fu¨r Nanotechnologie, Forschungszentrum Karlsruhe GmbH, Postfach 3640, 76021 Karlsruhe, Germany
Received 23 May 2005; accepted 13 June 2005
Available online 9 August 2005
Abstract
The synthesis and structural characterization of the copper salts [Cu8(benzoate)8(THF)6] (1), [Cu2{(CO2)2C6H2(Boc)2}dppm2]2
(2) and [Cu2{(CO2)2C10H4(Boc)2}dppm2]2 (3) [Boc = tert-butoxycarbonyl, dppm = 1,2-bis(diphenylphosphino)methane] prove that
cyclic organic anhydrides and dianhydrides readily insert into the Cu–O bond of [CuOtBu] forming carboxylate ligands with ester
functionalities in the ligand periphery. [Mn3(o-Boc-benzoate)6(DME)2] (4) (DME = 1,2-dimethoxyethane) was synthesized by the
metathesis reaction of [Cu(I)(o-Boc-benzoate)] with MnCl2.
Ó 2005 Elsevier B.V. All rights reserved.
Keywords: Metal alkoxide; Anhydride; Insertion reactions
1. Introduction
been applied by Bergman and coworkers [3,4] to late tran-
sition metal alkoxide complexes and we have recently ex-
tended those investigations to copper alkoxides.
Reactions of organic anhydrides with [CuOtBu] produce
Cu(I) and Cu(II) carboxylate complexes and complement
well-established synthetic procedures to these species
[5–7]. Challenges in this area now include the application
of the alkoxide–anhydride insertion reaction to a range of
organic anhydrides and to develop synthetic methods
allowing the incorporation of a variety of metal atoms
before the properties of the metal organic frameworks
can be investigated. As a contribution to this area, we wish
to report here the recent progress made, including the syn-
thesis and structure of unusually solvated Cu(I)benzoate,
reactions of [CuOtBu] with organic dianhydrides and a
metathesis reaction which should be widely applicable
in future.
The interest in the synthesis of inorganic/organic hy-
brid materials is driven by possible applications as storage
devices for gases, as matrices for catalytic transforma-
tions and for a variety of other purposes [1,2]. It is desir-
able to develop synthetic routes for molecular
complexes suitable for any of these applications that al-
low to incorporate specific metal atoms into organic
frameworks with functional groups, e.g., carboxylates,
sulfonates, and phosphonates, and at the same time gen-
erate a variety of organic ligands. A contribution to this
field is the exploration of insertion reactions of organic
anhydrides into the metal–O bond of late transition metal
alkoxides. This reaction allows a range of transition met-
als to be incorporated and at the same time to modify the
organic ligand by selecting different alkoxy groups and or-
ganic anhydrides. This type of reaction has successfully
2. Experimental
*
Corresponding author. Tel.: +49 0 721 6082849; fax: +49 0 721
6088440.
General remarks. All operations were carried out in
E-mail address: rothenberger@chemie.uni-karlsruhe.de(A. Rothen-
berger).
an atmosphere of purified argon. Solvents were dried
0020-1693/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.06.061

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C.E. Anson et al. / Inorganica Chimica Acta 358 (2005) 3967–3973
over sodium/benzophenone. Organic anhydrides were
recrystallized from diethylether. Chemicals were pur-
chased from Aldrich. [CuOtBu] was prepared according
to a published procedure [8]. Yields given were opti-
mized by repeated crystallization and concentration of
the mother liquor. The uniform composition of isolated
products was confirmed by unit-cell determination of
different batches of crystals.
C6H2(Boc)2}dppm2]2 2 (11 molecules of THF as lat-
tice-bound solvent), which slowly decomposed at room
temperature upon the loss of lattice-bound solvent.
Yield 0.58 g, 68%; m.p. 232 °C; Anal. Calc. for
C
136H128Cu4O16P8 (excluding lattice-bound THF): C,
~
64.8; H, 5.1. Found: C, 65.3; H, 5.4%. IR (KBr) m ¼
1718, 1591, (COO), 1433 (P–Ph), 735, 692 (C–H ar.)
cmꢀ1 31P{1H} NMR (CDCl3, 25 °C, 161.975 MHz,
;
1. To a solution of 0.14 g of (1.00 mmol) [CuOtBu] in
10 mL THF was added a solution of 0.27 g (1.00 mmol)
benzoic acid anhydride in 5 mL of THF. The yellow
solution was heated to reflux for 5 min. A colour change
to pale green occurred. Storage of the reaction mixture
at ꢀ40 °C for 4 days produced pale yellow crystals of
[Cu8(benzoate)8(THF)6] 1. Yield 0.19 g, 78%. Crystals
of 1 were extremely sensitive to air and elevated temper-
atures preventing further analytical investigations and
were selected under perfluoroether oil. Within approxi-
mately 10 s, the crystal was mounted and placed under
the cryosystem of the diffractometer.
85%H3PO4) ꢀ8.2 br. s, ꢀ12 br. s (PPh2); 1H NMR
(400 MHz, CDCl3, 25 °C, TMS) 7.7–6.9 (m, 22H ar.),
3.8 (m, 4H, THF), 3.2 (br. m, 2H, Ph2PCH2PPh2), 1.9
(m, 4H, THF), 1.4 (s, 18H, OtBu); 13C{H} NMR
(400 MHz, CDCl3, 25 °C, TMS) 175.7, 161.9 (COO,
COOtBu), 132.9–128.7 (C ar.), 68.1 (s, O–C, THF),
31.0 (s, CH2CH2O, THF), 28.1 (CH3–C); the
methylene group of dppm and the quarternary C atom
of tert-butoxy groups could not be identified in the
13C NMR.
3. To a solution of 0.12 g (0.50 mmol) 1,4,5,8-naph-
thyldianhydride in DME (5 mL) was added a solution
of 0.14 g (1.00 mmol) [CuOtBu] in DME (5 mL). The
resulting yellow solution was heated to reflux for 1 h
and a colour change to orange was observed. Then, a
solution of 0.40 g (1.00 mmol) dppm in DME (10 mL)
was added. A colour change from orange to yellow
was observed. The solution was stirred for 1 h and fil-
tered. After filtration the solvent was reduced to approx-
imately 5 mL and the reaction was stored at room
temperature for one week producing colourless crystals
of [Cu2{(CO2)2C10H4(Boc)2}dppm2]2 3 (5 molecules of
2. To a solution of 0.14 g of (1.00 mmol) [CuOtBu] in
toluene (5 mL) was added a solution of 0.11 g (0.50
mmol) pyromellitic anhydride in toluene (10 mL). The
resulting yellow solution was briefly heated to reflux
and then a solution of 0.40 g (1.00 mmol) dppm in tolu-
ene (5 mL) was added. The solution was stirred for 2 h
at room temperature. After filtration the solvent was re-
duced to approximately 3 mL. Addition of THF (3 mL)
to the concentrated solution and storage at ꢀ40 °C for
2 days produced colourless crystals of [Cu2{(CO2)2
Table 1
Details of the X-ray data collection and refinements
Compound
1
2
3
4
Formula
Formula weight
T (K)
C
80H88Cu8O22
C180H216Cu4O27P8
3313.45
150(2)
C164H182Cu4O26P8
3071.02
150(2)
C84H108Mn3O30
1762.52
203(2)
1909.82
200(2)
Crystal system
triclinic
monoclinic
P21/c
14.286(3)
22.927(5)
28.716(6)
90
98.54(3)
90
9301(3)
2
triclinic
triclinic
ꢀ
ꢀ
ꢀ
Space group
P1
P1
P1
˚
a (A)
12.0525(15)
12.1080(11)
15.0812(16)
105.406(9)
109.102(11)
101.474(9)
1903.6(4)
1
12.996(3)
17.257(4)
20.513(4)
108.73(3)
93.92(3)
90.18(3)
4345.1(15)
1
10.4668(12)
15.1254(18)
16.0495(19)
117.332(13)
91.311(14)
96.124(14)
2236.9(5)
1
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
3
˚
V (A )
Z
qcalc (g/cm3)
1.666
2.266
976
1.183
0.582
3496
1.174
0.618
1610
1.308
0.495
927
l (mmꢀ1
F(000)
)
2h Range (°)
Reflections collected
Unique data
Rint
7.54–63.26
15332
10702
0.0707
993
2.86–54.18
50971
20213
0.0753
871
3.9–50.0
13309
10398
0.0744
856
4.64–51.72
14075
8035
0.0524
530
Parameters
wR2 (all data)
S (Goodness-of-fit)
R1 [I > 2r(I)]
0.1799
0.988
0.0722
0.966, ꢀ0.756
0.2137
0.962
0.0687
0.843, ꢀ0.626
0.2735
1.015
0.0867
1.096, ꢀ0.615
0.1332
1.033
0.0495
0.389, ꢀ0.465
ꢀ3
˚
Peak, hole (e A
)

C.E. Anson et al. / Inorganica Chimica Acta 358 (2005) 3967–3973
3969
disordered DME as lattice-bound solvent). Yield 0.55 g,
70%; m.p. 185 °C; Anal. Calc. for C156H162Cu4O22P8
(three lattice-bound DME molecules per complex re-
mained after isolation under reduced pressure): C,
64.8; H, 5.6. Found: C, 64.5; H, 5.3%. IR (KBr)
ture, a disproportionation reaction occurred producing
elemental copper, Cu(II)benzoate and tert-butylbenzo-
ate. Storage of the reaction at ꢀ40 °C, however, produced
the extremely air-sensitive, solvated Cu(I)benzoate 1
(Scheme 1, Fig. 1).
~
m ¼ 1712, 1593 (COO), 1434 (P–Ph), 735, 691 (C–H
In the solid state 1, exhibits a remarkable acentric
structure consisting of two copper(I) benzoate tetramers
held together by l2-bridging THF molecules. The bond-
ing parameters and coordination geometries around the
Cu centres in each tetrameric copper(I) carboxylate unit
are similar to those observed in [Cu4(O2CCF3)4] [5]. 1
represents one of the very few crystallographically char-
acterized ether-solvated Cu(I) carboxylates [10,11].
O(THF)–Cu distances are in the range Cu(8)–O(25)
ar.) cmꢀ1
.
4. To a solution of 0.06 (0.50 mmol) MnCl2 in 10 mL
THF was added a solution of 0.15 g (1.00 mmol) phtha-
lic acid anhydride. A solution of 0.14 g (1.00 mmol)
[CuOtBu] in 10 mL THF was added. The mixture was
heated to reflux for 4 h and filtered. The pink solution
was dried under reduced pressure and the solid residue
was dissolved in 3 mL DME. After two days purple
crystals of 4 were obtained. Yield 0.25 g, 89%; m.p.
135 °C; Anal. Calc. for C80H98Mn3O28: C, 57.4; H, 5.9.
˚
2.370(13) – Cu(2)–O(23) 2.824(11) A. Under reduced
pressure THF is readily released resulting in amorphous
Cu(I)benzoate.
~
Found: C, 56.5; H, 5.9%. IR (KBr) m ¼ 1717, 1608,
1589, 1406, 1306, 1255 (COO) cmꢀ1
.
This initial result and the reported synthesis of [Cu2-
(CO2C2H2-Boc)2 Æ dppm]2 show that insertion reactions
of organic anhydrides and [CuOtBu] result in Cu(I) com-
plexes if the reactions are either kept at low temperature
or performed in the presence of phosphine donors [4]. In
a first attempt to construct more complex aggregates via
this synthetic route, reactions of dianhydrides and
[CuOtBu] were investigated.
2.1. X-ray crystallographic study
Data were collected on a STOE STADI V equipped with
a KMW150 CCD detector (1), a STOE IPDS II (2, 3) and a
STOE IPDS I diffractometer connected to a SCHNEIDER ro-
tary anode X-ray generator (4) using graphite-mono-
The reactions of solutions [CuOtBu] with pyromellitic
anhydride and the anhydride of naphthalene-1,4,5,8-tet-
racarboxylic acid in organic solvents at ca. 70 °C pro-
duce colourless insoluble solids. In the presence of the
tertiary phosphine dppm (dppm = bis-diphenylphosphi-
nomethane), these reactions afforded the phosphine-
stabilized copper salts of 4,6-bis-Boc-isophthalic acid 2
and 5,8-bis-Boc-naphthyl-1,4-dicarboxylic acid 3 in good
yields (Scheme 2).
˚
chromated Mo Ka radiation (m = 0.71073 A). The
structures were solved by direct methods and refined
by full-matrix least-squares on F2 (all data) using the
SHELXTL program package [9]. Hydrogen atoms were
placed in calculated positions, non-hydrogen atoms
were assigned anisotropic thermal parameters. Disor-
dered components (lattice-bound solvent) were refined
with isotropic thermal parameters. The structure of 1
ꢀ
is acentric, space group P1, and a correction for racemic
Initially, an infrared study of both compounds indi-
cated the formation of the diester–dicarboxylate/phos-
phine complexes. This was verified for 2 by an NMR
study. Solid samples of 3, however, are insoluble once
isolated and the molecular structures of 2 and 3 were fi-
nally determined by X-ray crystallography. In the solid
state, 2 consists of two [Cu2(dppm)2] units [Cu(1)ꢁ ꢁ ꢁ
twinning was made. Several atoms of the THF ligands
had anisotropic temperature factors that indicated the
presence of disorder. No attempt was made to model
this, in order to maintain an adequate data:parameter
ꢀ
ratio, given the space group P1 (see Table 1).
˚
Cu(2) 2.93(1), Cu–P av. 2.25 A] held together by a
3. Results and discussion
bidentate carboxylato group [Cu(1)–O(1) 2.142(3),
Cu(2)–O(2) 1.980(3) A] (Fig. 2).
˚
As part of a wider study of reactions between organic
anhydrides and [CuOtBu], the simple model reaction of
[CuOtBu] with benzoic acid anhydride was carried out
in THF. During storage of the reaction at room tempera-
In addition to the O(carboxylate) and two P(dppm)
donor centres around each copper atom, Cu(1) is coordi-
nated by O(7) of the monodentate carboxylate group in
the generated dicarboxylato ligand, resulting in a dis-
torted tetrahedral coordination environment for Cu(1)
and a trigonal planar ligand arrangement around
Cu(2). An increase of the coordination number at
O
O
t
Cu(2) is hindered by the Bu group at O(3). Examples
O
for three-coordinated Cu atoms in Cu(I) dicarboxylates
are found in Cu(I) perfluorosuccinate, copper(I) gluta-
rate and in the ion separated complex [Cu(OAc)(BF4)-
(dppm)2] [12–14]. Three- and four-coordinated Cu atoms
[CuOtBu]
[Cu8(benzoate)8(thf)6]
THF
1
Scheme 1. Synthesis of 1.

3970
C.E. Anson et al. / Inorganica Chimica Acta 358 (2005) 3967–3973
Fig. 1. Molecular structure of 1 in the solid state (view from the side and top; ellipsoids at 50% probability level; hydrogen atoms are omitted for
2
˚
clarity). Selected bond lengths (A) and angles (°): Cu–O(carboxylate) Cu(2)–O(7) 1.845(9), Cu(5)–O(16) 1.891(9), Cu–O(l -THF) Cu(1)–O(21)
2.528(10) and Cu(1)–O(22) 2.751(13), Cu–O(THF) Cu(8)–O(25) 2.370(13), Cu(2)–O(23) 2.824(11); Cu(1)–O(21)–Cu(5) 98.0(3), Cu(1)–O(22)–Cu(5)
94.3(4).
are observed in the complex [Cu2(PhCOO)2(dppm)2]
(all with similar Cu–O and Cu–P bond lengths and angles
to those found in 2) [15]. The monodentate carboxylate
group is in plane with the benzene ring, whereas the
bidentate carboxylate group is slightly twisted meeting
the steric requirements of the [Cu(dppm)]2 units in 2.
One O–C–benzene ring torsion angle of the ester groups
in 2 is ca. 85.05° and larger than torsion angles observed
in the sterically crowded ester hexa-Boc-benzene (O–C–
benzene ring 71.6–80.7°) [16].
O
O
O
O
O
O
[Cu2{(CO2)2C6H2(Boc)2}dppm2]2
THF, dppm
2
O
O
O
O
[CuOtBu]
O
O
[Cu2{(CO2)2C10H4(Boc)2}dppm2]2
DME, dppm
3
The molecular structure of 3 in the solid state consists
of two [Cu(dppm)]2 units bridged by two 1,4-dicarboxy-
Scheme 2. Synthesis of 2 and 3.

C.E. Anson et al. / Inorganica Chimica Acta 358 (2005) 3967–3973
3971
Fig. 2. Molecular structure of 2 in the solid state (ellipsoids at 50% probability level; hydrogen atoms are omitted for clarity). Selected bond lengths
˚
(A) and angles (°): Cu(1)–O(7) 2.059(3), Cu(1)–O(1) 2.142(3), Cu(1)–P(3) 2.2534(11), Cu(1)–P(1) 2.3061(13), Cu(1)ꢁ ꢁ ꢁCu(2) 2.9251(11), Cu(2)–O(2)
1.980(3), Cu(2)–P(4) 2.2087(12), Cu(2)–P(2) 2.2415(13); O(7)–Cu(1)–O(1) 85.49(10), O(7)–Cu(1)–P(3) 107.12(8), O(1)–Cu(1)–P(3) 129.27(8), O(7)–
Cu(1)–P(1) 101.86(9), O(1)–Cu(1)–P(1) 101.70(8), P(3)–Cu(1)–P(1) 122.02(4), O(7)–Cu(1)–Cu(2) 157.33(8), O(1)–Cu(1)–Cu(2) 72.20(7), O(2)–Cu(2)–
P(4) 126.33(9), O(2)–Cu(2)–P(2) 102.89(9), P(4)–Cu(2)–P(2) 130.28(4).
late ligands in a centrosymmetric cyclic arrangement
(Fig. 3).
slightly twisted out of the plane defined by the naphtha-
lene rings and all copper atoms Cu(1,2) are part of the
macrocyclic arrangement. Presumably, the 1,3-dicarb-
oxylato ligand in 1 favours a smaller macrocyclic arrange-
ment in which Cu(2) is coordinated in the periphery of the
molecule rather than being involved in ring formation.
Bond lengths and angles of Cu atoms in 3 are similar to
The carboxylate ligands are monodentate resulting in
four three-coordinate Cu(I) centres. The Cuꢁ ꢁ ꢁCu dis-
˚
tance in 3 [Cu(1)ꢁ ꢁ ꢁCu(2A) 3.1193(18) A] is slightly larger
than the corresponding distance observed in 2 [Cu(1)ꢁ ꢁ ꢁ
˚
Cu(2) 2.9251(11) A]. All the carboxylate groups in 3 are
Fig. 3. Molecular structure of 3 in the solid-state (ellipsoids at 50% probability level; hydrogen atoms are omitted for clarity). Selected bond lengths
˚
(A) and angles (°): Cu(1)ꢁ ꢁ ꢁCu(2A) 3.1193(18), Cu(1)–O(1) 1.947(6), Cu(1)–P(1A) 2.249(3), Cu(1)–P(3A) 2.246(3), Cu(2)–O(7) 1.983(7), Cu(2)–P(4)
2.242(2), Cu(2)–P(2) 2.254(3); O(1)–Cu(1)–P(1A) 117.2(2), O(1)–Cu(1)–P(3A) 116.7(2), P(1A)–Cu(1)–P(3A) 126.03(10) O(7)–Cu(2)–P(4) 118.4(2),
O(7)–Cu(2)–P(2) 117.4(2), P(4)–Cu(2)–P(2) 123.82(10).

3972
C.E. Anson et al. / Inorganica Chimica Acta 358 (2005) 3967–3973
those observed in 2 and can be compared with corre-
sponding values reported for Cu complexes in the litera-
ture [12–14]. The insertion reactions with the two
organic dianhydrides and [CuOtBu] gave rise to the
Cu(I) salts of 4,6-bis-Boc-isophthalic acid 2 and 5,8-bis-
Boc-naphthyl-1,4-dicarboxylic acid 3 as the major
products in these reactions (formed in yields of ca. 70%
by fractionated crystallization) and the only products
which could be obtained in pure form. It is assumed that
byproducts in these reactions do not crystallize easily and
that there might be a entropic preference for the forma-
tion of the ring architectures found in 2 and 3.
The reactions of [CuOtBu] with dianhydrides repre-
sent a first step in our efforts to synthesize more compli-
cated systems and indicate that the synthetic route
chosen should be applicable to a variety of organic dian-
hydrides or polyanhydrides. Dianhydrides were so far
mainly used as building blocks in condensation reac-
tions with a variety of amines giving rise to supramolec-
ular assemblies [17,18]. Also, hydrothermal syntheses
with dianhydrides producing a range of transition metal
complexes containing tetracarboxylato anions are re-
ported [19].
Besides the extension of the synthetic route to dian-
hydrides, an initial aim of our investigation has also
been the incorporation of other metal atoms than Cu
into new complexes. This was achieved by metathesis
reactions of a Cu(I) complex with transition metal salts.
The first result of these efforts represents the metathesis
reaction of [Cu(I)(o-Boc-benzoate)], obtained by the
reaction of [CuOtBu] with phthalic acid anhydride, with
MnCl2 (Scheme 3, Fig. 4).
Fig. 4. Molecular structure of 4 in the solid-state (ellipsoids at 50%
probability level; hydrogen atoms are omitted for clarity). Selected
˚
bond lengths (A) and angles (°): Mn–O(carboxylate) Mn(1)–O(6A)
2.090(2), Mn(1)–O(10) 2.366(2), Mn–O(DME) Mn(1)–O(14) 2.215(2)
and Mn(1)–O(13) 2.285(2); O–Mn–O(trans) O(9)–Mn(1)–O(14)
138.83(8), O(6A)–Mn(1)–O(13) 169.73(8), O(2A)–Mn(1)–O(10) 164.
12(9), O(5)–Mn(2)–O(5A) 180.00(10), O(1)–Mn(2)–O(1A) 180.000(1),
O(9A)–Mn(2)–O(9) 180.000(1), O–Mn–O(cis) O(9)–Mn(1)–O(10)
57.06(7), O(2A)–Mn(1)–O(9) 118.50(9), O(1)–Mn(2)–O(9A) 86.29(9),
O(1)–Mn(2)–O(9) 93.71(9).
tert-butanol and the successive treatment with a mixture
of MnCl2/NEt3.
[Mn3(o-Boc-benzoate)6(DME)2] 4 is produced in
good yield. The solid-state structure of 4 consists of a
typical centrosymmetric arrangement of three octahe-
drally coordinated Mn atoms [20]. The Mn atoms are
bridged by the carboxylate groups of the generated
o-Boc-benzoato ligand with two DME ligands complet-
ing the coordination sphere of the terminal Mn atoms.
Initially formed CuCl is insoluble in DME and was fil-
tered off. Analogous reactions were also performed with
NiCl2, CoBr2, and FeBr2, giving isostructural complexes
to 4. The metathesis reactions involving Cu(I) complexes
have proven to be a useful alternative to those of com-
monly employed alkali metal complexes. In contrast to
alkali metal halides, all Cu(I) halides are insoluble in
ethereal solvents. A different synthetic route to 4 repre-
sents the alcoholysis of phthalic acid anhydride with
4. Conclusions
The insertion reactions of organic anhydrides and
[CuOtBu] produce Cu(I) carboxylate complexes when
performed at low temperature or in the presence of ter-
tiary phosphine ligands. This synthetic route is applica-
ble to dianhydrides. Metathesis reactions of Cu(I)
complexes obtained in these reactions with transition
metal halides offer access to a large number of com-
pounds, which will subsequently be tested for potential
applications once their structural chemistry is further
developed. A combinatorial approach to these com-
pounds currently investigated is the alcoholysis of or-
ganic anhydrides and subsequent metallation by
reactions with transition metal halides.
O
COOtBu
[CuOtBu]
DME
MnCl2
-CuCl
[Mn3(o-Boc-benzoate)6(dme)2]
O
OCu
4
O
O
Scheme 3. Synthesis of 4 via a metathesis reaction of an intermediate Cu(I) complex.

C.E. Anson et al. / Inorganica Chimica Acta 358 (2005) 3967–3973
[8] T. Greiser, E. Weiss, Chem. Ber. 109 (1976) 3142.
3973
5. Supplementary material
[9] G.M. Sheldrick et al., SHELXTL-97, University of Go¨ttingen,
1997.
CCDC Nos. 271634–271637 contain the supplemen-
tary 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 Crystallo-
graphic Data Centre, 12, Union Road, Cambridge CB2
1EZ, UK, fax: (internat.) +44 1223 336 033, e-mail:
deposit@ccdc.cam.ac.uk].
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