Synthesis and characterisation of dinuclear nickel(II) and cadmium(II) complexes of N-alkylated derivatives of hexaazadithiophenolate macrocycles

Article abstract of DOI:10.1002/ejic.200600318

The effect of N-alkylation on the ligating properties of the Robson-type 24-membered hexaazadithiophenolate macrocycle H₂L¹ [13,27-bis(tert-butyl)-3,6,9,17,20,23-hexaazatricyclo[23.3.1^11,15] triaconta-1(28),11,13,15(30),25,26-hexaene-29,30-dithiol] has been examined. Two new derivatives (H₂L³ and H₂L⁴) of H₂L¹ have been prepared. H₂L³ is a dimethylated derivative of H₂L¹ and H₂L ⁴ is a tetraethylated derivative of H₂L³. A series of complexes of the type [(L^R)M^II ₂(μ-Cl)]⁺ [R = 1, M = Cd (10), R = 3, M = Ni (8), M = Cd (12), R = 4, M = Ni (9), M = Cd (13)] have been prepared and structurally characterised. The X-ray crystal structure determination of these dioctahedral complexes with an N₃M(S)₂(μ-Cl)MN₃ core structure has revealed two conformations of the supporting ligands. In 8, 9, 10 and 12 the ligands adopt a folded C_s-symmetric conformation of type A whereas in the cadmium complex 13 the alternative C_2v-symmetric bowl-shaped conformation (type B) is present. A structural comparison has allowed us to determine the factors that determine the ligand conformations. It has been established that the ligand conformations adopted depend not only on the co-ligand but also on the metal ion radius and the N-alkylation grade. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Full text of DOI:10.1002/ejic.200600318

FULL PAPER
DOI: 10.1002/ejic.200600318
Synthesis and Characterisation of Dinuclear Nickel(II) and Cadmium(II)
Complexes of N-Alkylated Derivatives of Hexaazadithiophenolate Macrocycles
Mathias Gressenbuch[a] and Berthold Kersting*[a]
Keywords: Macrocyclic ligands / N ligands / S ligands / Nickel / Cadmium
The effect of N-alkylation on the ligating properties of the
Robson-type 24-membered hexaazadithiophenolate macro-
cycle H2L1 [13,27-bis(tert-butyl)-3,6,9,17,20,23-hexaazatri-
cyclo[23.3.111,15]triaconta-1(28),11,13,15(30),25,26-hexaene-
29,30-dithiol] has been examined. Two new derivatives (H2L3
and H2L4) of H2L1 have been prepared. H2L3 is a dimeth-
ylated derivative of H2L1 and H2L4 is a tetraethylated deriva-
tive of H2L3. A series of complexes of the type [(LR)MII2(µ-
Cl)]+ [R = 1, M = Cd (10), R = 3, M = Ni (8), M = Cd (12), R = 4,
M = Ni (9), M = Cd (13)] have been prepared and structurally
characterised. The X-ray crystal structure determination of
these dioctahedral complexes with an N3M(S)2(µ-Cl)MN3
core structure has revealed two conformations of the support-
ing ligands. In 8, 9, 10 and 12 the ligands adopt a folded Cs-
symmetric conformation of type A whereas in the cadmium
complex 13 the alternative C2v-symmetric “bowl-shaped”
conformation (type B) is present. A structural comparison has
allowed us to determine the factors that determine the ligand
conformations. It has been established that the ligand confor-
mations adopted depend not only on the co-ligand but also
on the metal ion radius and the N-alkylation grade.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
Introduction
pendent on the conformations of the supporting ligands.
This is of importance for a number of applications, since
often only one of several possible conformational isomers
exhibits the desired property.[7] Thus, in macrocyclic chem-
istry it is of importance to establish the factors that are
responsible for the stabilisation/destabilisation of the vari-
ous structural forms.
Macrocyclic ligands containing 14 or more ring atoms
are known to have a rather flexible structure, and it is often
observed that such ligands can adopt several different con-
formations.[1,2] Typical examples are the N4 macrocycle cy-
clam and its countless N-alkylated derivatives,[3] which can
have planar (trans) or folded (cis) conformations in octahe-
dral complexes.[4–6] It is well-known that the physical and
We recently reported the synthesis of the hexaazadithio-
chemical properties of macrocyclic complexes are highly de- phenolate macrocycle H2L1 and its permethylated derivative
Scheme 1. Ligands and complexes studied in this work.
H2L2 (Scheme 1)[8] and their use in the preparation of dinu-
[a] Institut für Anorganische Chemie, Universität Leipzig,
Johannisallee 29, 04103 Leipzig, Germany
clear transition metal complexes for regioselective substrate
Fax: +49-341-973-6199
transformations.[9,10]
E-mail: b.kersting@uni-leipzig.de
90
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NiII and CdII Complexes of Hexaazadithiophenolate Macrocycles
FULL PAPER
Examination of the structures of the chlorido-bridged mation of type
A (e.g. complexes 6 and 7, see
[(LR)MII2(µ-Cl)]+ complexes has revealed that the octadent- Scheme 2).[11,12] Very recently, however, the alternative C2v-
ate ligands most often adopt a folded Cs-symmetric confor- symmetric “bowl-shaped” conformation of type B was de-
tected for the chlorido-bridged cadmium complex 11.[13]
These findings encouraged us to look for the factors that
determine these ligand conformations.
In this study we describe the synthesis and characterisa-
tion of a series of chlorido-bridged Ni and Cd complexes
of the type [(LR)M2(µ-Cl)]+ supported by 24-membered
hexaazadithiophenolate ligands (LR)2– with different N-al-
kylation grades and patterns (see Scheme 1 for ligand ab-
breviations). We have obtained single crystals of the com-
plexes 8, 9, 10, 12 and 13 suitable for X-ray structure deter-
minations, which has allowed us to study the ligating prop-
erties of the supporting ligands as a function of the N-alky-
lation grade. The solution-state structures of the cadmium
complexes 10–13 derived from NMR studies and the solid-
state structure of one proligand are also presented.
Results and Discussion
Ligand Synthesis
The synthetic route to the new ligands H2L3 and H2L4
is outlined in Scheme 3. The bicyclic macrocycle 3 was pre-
Scheme 2. Schematic representation of the two ligand conforma-
tions of the octadentate macrocycles (LR)2– observed in the
pared by a [2 + 1] condensation reaction between tetraalde-
chlorido-bridged [(LR)M2(µ-Cl)]+ complexes 6, 7 and 11.[11,13]
hyde 1[14] and bis(aminoethyl)methylamine (2) in an etha-
Scheme 3. Synthesis of the ligands H2L3 and H2L4.
Eur. J. Inorg. Chem. 2007, 90–102
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91

M. Gressenbuch, B. Kersting
FULL PAPER
nol/dichloromethane mixed solvent system, followed by re- are similar but not identical. Each compound displays three
duction of the intermediate imine functions with NaBH4. weak absorption bands above 500 nm. The absorption band
To prevent the formation of higher condensation products in the range 620–670 nm can be attributed to the ν2 transi-
3
the cyclisation reaction was performed under high dilution tion [3A2g(F) Ǟ T1g(F)] of an octahedral nickel(II) (d8)
conditions. Thus, proligand 3 was obtained in nearly quan- ion. The bands between 900 and 1100 nm can be assigned
3
titative yield upon workup. Subsequent deprotection of the to the ν1 transition [3A2g(F) Ǟ T2g(F)], which is split pre-
thioether functions was achieved in the usual way,[14] with sumably due to lower symmetry. The slight differences in
sodium in liquid ammonia followed by acidic workup. The the positions of the d–d transitions indicate that each com-
second ligand system was prepared according to a protocol plex retains its integrity in solution. This is also supported
used for the alkylation of triazacyclononane[15] and cy- by the NMR spectroscopic data for the cadmium complexes
clam.[16] Acylation of the four benzylic nitrogen donors of 10, 12 and 13 described below.
3 was accomplished with acetic anhydride. The subsequent
Table 1. Synthesised complexes, their labels, structure type and se-
lected UV/Vis data.
LiAlH4 reduction of the resulting tetraamide 4 furnished
the tetraethylated macrobicycle 5 in good yield. The final
deprotection of the masked thiophenolate functions with
sodium in liquid ammonia followed by acidic workup gave
H2L4 as its hexahydrochloride salt. These new ligands were
obtained in good overall yields without the need for metal
templates. All new compounds were characterised by ele-
Complex
Structure
type
λmax [nm]
Ref.
(ε [–1 cm–1])[a]
[11]
[11]
6 [(L1)Ni2(µ-Cl)]+
7 [(L2)Ni2(µ-Cl)]+
8 [(L3)Ni2(µ-Cl)]+
9 [(L4)Ni2(µ-Cl)]+
10 [(L1)Cd2(µ-Cl)]+
11 [(L2)Cd2(µ-Cl)]+
12 [(L3)Cd2(µ-Cl)]+
13 [(L4)Cd2(µ-Cl)]+
A
A
A
A
A
B
625 (58), 894 (54), 941 (56)
658 (41), 920 (59), 1002 (80)
623 (76), 902 (63), 960 (68) this work
675 (31), 928 (62), 1013 (82) this work
1
mental analysis, IR, H and 13C NMR spectroscopy (see
this work
Exp. Sect.), and compound 5 also by X-ray crystallography.
The hydrochloride salts of the ligands H2L3 and H2L4 could
not be obtained in analytically pure form. Nevertheless,
they were of sufficient purity for metal complex syntheses.
[13]
A
B
this work
this work
[a] The UV/Vis spectra were recorded for the perchlorate salts.
Spectra were recorded in CH3CN solution at 295 K for solutions
with a concentration of about 1.0ϫ10–3  for 6 and 7 and
1.9ϫ10–3  for complex 8.
Synthesis of Complexes
A series of chlorido-bridged nickel(II) and cadmium(II)
complexes of the type [(LR)M2(µ-Cl)]+ were prepared in or-
der to systematically investigate the effect of N-alkylation
on metal ion complexation and metal complex structures.
The synthesised complexes and their labels are collected in
Scheme 1. Of these, [(L1)Ni2(µ-Cl)]+ (6),[11] [(L2)Ni2(µ-Cl)]+
(7)[17] and [(L2)Cd2(µ-Cl)]+ (11)[13] have been reported pre-
viously. The complexation reactions of the macrocycles with
NiCl2·6H2O (or CdCl2·H2O) in the presence of triethyl-
amine proceeded smoothly and yielded yellow or colourless
solutions of the respective [(LR)M2(µ-Cl)]+ monocations,
which could be readily isolated as their crystalline perchlo-
rate or tetraphenylborate salts. The new compounds gave
satisfactory elemental analyses and were characterised by
spectroscopic methods (IR, UV/Vis, 1H and 13C NMR
spectroscopy) and compounds 8[BPh4], 9[BPh4], 10[BPh4],
12[BPh4] and 13[BPh4] also by X-ray structure analysis.
NMR Spectroscopy
Selected 1H and 13C NMR spectroscopic data for the
cadmium complexes 10, 12 and 13 are presented in Table 2.
The data for complex 11 have been reported previously and
are included for comparative purposes.[13] The 1H NMR
spectra of the dicadmium complexes 10 and 12 are different
from those of 11 and 13. For example, the signals for the
aromatic protons and the tert-butyl protons are split into
two singlets. Similarly, the 13C NMR spectra of 10 and 12
display eight signals for the aromatic carbon atoms labelled
C11–C18, whereas only four signals are seen for the respec-
tive atoms in 11 and 13. These data are indicative of a li-
gand conformation of type A for 10 and 12 and of type B
for 11 and 13. Thus, in contrast to the nickel complexes
above, the ligand conformations in the [(LR)Cd2(µ-Cl)]+
complexes clearly depend on the N-alkylation grade. This
conclusion is also borne out by the single-crystal X-ray
structure determinations of 10, 12 and 13 described below.
Spectroscopic Characterisation: IR and UV/Vis
Spectroscopy
The infrared spectra of all compounds display the bands
expected for the macrocyclic ligands and counterions, but
are not informative with respect to the conformations of
the supporting ligands. The electronic absorption spectra of
X-ray Crystallography
The X-ray crystal structures of the proligand 5 and the
the nickel complexes were recorded in the range 300– complexes 8[BPh4]·3EtOH, 9[BPh4]·5MeCN, 10[BPh4]·
1600 nm in acetonitrile solution. Selected spectroscopic 5MeOH, 12[BPh4]·2MeCN and {13[BPh4]·3.5MeCN}2
data are reported in Table 1. The data for complexes 6 and were determined in order to establish the geometries about
7 have been reported previously and are included for com- the metal ions and the bonding modes of the supporting
parative purposes.[11] The spectra of the nickel complexes ligands.
92
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NiII and CdII Complexes of Hexaazadithiophenolate Macrocycles
FULL PAPER
1
Table 2. Selected H and 13C NMR spectroscopic data for complexes 10–13.[a]
10[ClO4]
11[ClO4]
12[ClO4]
13[ClO4]
1H NMR[a]
C13,13Ј,17,17Ј
H
7.34 s
7.16 s
–
–
1.26
1.32
7.20 s
7.17 s
7.32 s
2.65 s (CH3)
–
1.25 s
1.29 s
7.28 s
R1
2.84 s (CH3)
2.33 s (CH3)
1.26 s
2.83 s (CH3)
1.12 t (CH2CH3)[b]
1.27 s
R2
C1H3, C4H3
13C NMR[c]
C14,18
145.1
145.0
139.1
138.2
137.4
137.3
127.8
127.5
56.0, 55.2
54.2, 49.2
48.9, 47.4
–
147.1
141.8
135.8
131.0
148.21
147.96
140.24
138.45
139.46
138.95
129.01
129.28
60.37, 58.17
58.06, 56.20
55.19, 50.68
49.48 (CH3)
–
146.78
142.13
136.29
130.18
C11,15
C12,12Ј,16,16Ј
C13,13Ј,17,17Ј
C5–10,5Ј–10Ј
63.8
60.8
58.0
50.1 (CH3)
46.0 (CH3)
34.7
58.13
56.65
55.74
50.30 (CH3)
6.63 (CH2), 50.00 (CH3)
34.70
R1
R2
–
33.8
C2,3
34.84
33.7
31.3
34.93
31.61
C1,4
31.6
31.50
31.2
31.74
[a] Spectra were recorded in CD3CN (11–13) or CD3OD (10) solution at 295 K. [b] The resonances for the methylene protons of the
ethyl substituents are obscured by the resonances of the ethylene groups. [c] Spectra were recorded in CD3CN (11–13) or [D6]DMSO
(10) solution at 295 K.
Compound 5
The C–S sulfur bond lengths involving the sp2-hybridized
carbon atoms (C1, C1Ј) [1.786(2) Å] are shorter than the
ones involving the sp3-hybridized carbon atoms [1.820 Å]
C22 and C22Ј. Virtually the same distances are seen in the
permethylated derivative.[19]
The molecular structure of the proligand 5 is shown in
Figure 1. The thioether adopts a highly folded conforma-
tion that is typical for such large macrocycles.[18] The two
phenyl rings are not really coplanar to each other, the dihe-
dral angle being 30.9°. The ethyl substituents bonded to
N(3) and N(3Ј) point into the central cavity, partly filling
the void between the phenyl rings. The distance between
their centroids amounts to 6.216 Å. There are no unusual
[(L3)NiII2(µ-Cl)][BPh4]·3EtOH (8[BPh4]·3EtOH) and
[(L4)NiII2(µ-Cl)][BPh4]·5MeCN (9[BPh4]·5MeCN)
The crystal-structure determinations of the two title
features as far as bond lengths and angles are concerned. compounds reveal the presence of dioctahedral complex
Eur. J. Inorg. Chem. 2007, 90–102
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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93

M. Gressenbuch, B. Kersting
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cations, tetraphenylborate anions and ethanol or acetoni-
trile molecules of solvent of crystallisation. ORTEP plots
of 8 and 9 are displayed in Figures 2 and 3, respectively.
The atomic numbering scheme for the central N3Ni(µ-S)2-
(µ-Cl)NiN3 core in 8 is used throughout to facilitate struc-
tural comparisons. Selected bond lengths and angles are
listed in Tables 3 and 4. The corresponding values for [(L1)-
Ni2(µ-Cl)]+ (6) and [(L2)Ni2(µ-Cl)]+ (7) are included for
comparative purposes.
Figure 1. Molecular structure of compound 5 with atomic number-
ing for key atoms. Hydrogen atoms have been omitted for clarity.
Symmetry codes used to generate equivalent atoms: –x, +y, 0.5 – z
(Ј).
Figure 3. Molecular structure of 9 with atomic numbering for key
atoms (30% probability thermal ellipsoids). Hydrogen atoms have
been omitted for clarity.
The structures of the chlorido-bridged dinickel(II) com-
plexes 8 and 9 are very similar and, with the exception of
the N-alkyl substituents, almost superimposable with those
of 6 and 7.[11] The structure of 8 is representative for all
complexes. As can be seen from Figure 2, the supporting
ligand adopts a saddle-shaped, Cs-symmetric conformation
that is reminiscent of the “partial-cone” conformation of
calixarenes.[20] The metal ions are in a strongly distorted
octahedral N3S2Cl environment, being coordinated by two
sulfur and three facially oriented nitrogen atoms of the
macrocycle and a symmetrically bridging chloride ion to
give an N3NiII(µ-SR)2(µ-Cl)NiIIN3 core. The distortions
from the ideal octahedral geometry are manifested in the cis
and trans L–M–L bond angles, which deviate by as much as
18.2° from their ideal values (see Table 4). The diethylenetri-
amine units coordinate facially with one larger and two
smaller N–M–N bond angles. This is commonly observed
in complexes with this tridentate unit.[21]
As can be seen in Table 3, the metal–ligand bond lengths
in 6–9 clearly depend on the type of nitrogen donor atoms.
Thus, upon conversion of the six secondary amines in 6 to
tertiary amine functions in 9, the average M–N bond length
increases by about 0.15 Å. This, in turn, results in a large
decrease in the M–Cl bond lengths by about 0.25 Å. In
other words, the larger the number of tertiary amine donors
the shorter the distance between the metal ions and the co-
ligand. Similar effects have been reported for nickel com-
plexes of other azamacrocycles and their peralkylated deriv-
Figure 2. Two perspective views of the molecular structure of 8
with atomic numbering for key atoms (30% probability thermal
ellipsoids). Hydrogen atoms (except those bonded to N atoms) have
been omitted for clarity.
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NiII and CdII Complexes of Hexaazadithiophenolate Macrocycles
FULL PAPER
Table 3. Selected bond lengths [Å] in complexes 6–13.
6
7[b]
8
9
10
11
12
13[b]
M(1)–Cl
2.639(2)
2.078(6)
2.103(7)
2.085(6)
2.418(2)
2.419(2)
2.602(2)
2.099(7)
2.141(7)
2.134(7)
2.423(2)
2.405(2)
2.107(7)
2.621(2)
2.416(2)
3.098(2)
2.433(2) [2.516(2)] 2.512(1)
2.352(5) [2.349(5)] 2.129(3)
2.173(5) [2.173(5)] 2.167(3)
2.181(5) [2.167(5)] 2.083(3)
2.471(2) [2.475(2)] 2.453(1)
2.405(2) [2.407(2)] 2.420(1)
2.450(2) [2.455(2)] 2.535(1)
2.171(5) [2.222(5)] 2.081(3)
2.175(6) [2.172(5)] 2.161(3)
2.380(6) [2.357(5)] 2.141(3)
2.498(2) [2.483(2)] 2.458(1)
2.423(2) [2.371(2)] 2.423(1)
2.239(6) [2.240(5)] 2.127(3)
2.442(2) [2.486(2)] 2.524(1)
2.449(2) [2.434(2)] 2.439(1)
3.184(2) [3.217(2)] 3.074(1)
2.4870(4)
2.383(1)
2.163(1)
2.232(1)
2.4843(4)
2.3750(4)
2.4885(4)
2.188(1)
2.165(1)
2.411(1)
2.4968(4)
2.3940(4)
2.257(1)
2.4878(4)
2.4375(4)
3.2400(4)
2.728(2)
2.411(5)
2.354(5)
2.386(5)
2.699(2)
2.637(2)
2.674(3)
2.368(5)
2.372(6)
2.447(6)
2.682(2)
2.664(2)
2.390(5)
2.701(3)
2.671(2)
2.682(1)
2.453(3)
2.424(3)
2.410(4)
2.653(1)
2.699(2)
2.723(1)
2.441(3)
2.388(3)
2.409(3)
2.696(1)
2.659(1)
2.421(4)
2.703(1)
2.677(1)
2.747(3)
2.351(6)
2.460(7)
2.388(7)
2.660(2)
2.656(2)
2.793(3)
2.353(6)
2.440(7)
2.401(8)
2.611(2)
2.662(2)
2.399(7)
2.770(3)
2.647(2)
3.267(1)
2.676(1) [2.703(1)]
2.456(4) [2.410(3)]
2.399(3) [2.395(3)]
2.444(3) [2.508(3)]
2.709(1) [2.685(1)]
2.653(1) [2.693(1)]
2.645(2) [2.648(1)]
2.442(3) [2.464(3)]
2.399(3) [2.399(3)]
2.474(3) [2.473(3)]
2.663(1) [2.656(1)]
2.698(1) [2.713(1)]
2.436(4) [2.442(3)]
2.661(1) [2.676(1)]
2.681(1) [2.687(1)]
3.3550(8) [3.3387(8)]
M(1)–N(1)
M(1)–N(2)
M(1)–N(3)
M(1)–S(1)
M(1)–S(2)
M(2)–Cl
M(2)–N(4)
M(2)–N(5)
M(2)–N(6)
M(2)–S(1)
M(2)–S(2)
M–N[a]
M–Cl[a]
M–S[a]
M···M
3.2666(17) 3.3584(9)
[a] Average values. [b] There are two crystallographically independent molecules A and B in the asymmetric unit. Values in square brackets
refer to molecule B.
Table 4. Selected bond angles [°] in complexes 6–13.
6
7[c]
8
9
10
12
11
13[c]
N(1)–M(1)–
N(2)
N(1)–M(1)–
N(3)
N(2)–M(1)–
N(3)
N(4)–M(2)–
N(5)
82.7(3)
78.9(2)
83.17(12)
78.55(5)
75.9(2)
76.3(3)
N(1)–M(1)–N(2) 75.2(1)
75.4(1)
[78.6(2)]
100.2(2)
[100.6(2)]
83.2(2)
[82.6(2)]
82.4(2)
[82.5(2)]
101.8(2)
[100.7(2)]
79.5(2)
[78.4(2)]
87.7(2)
[87.2(2)]
9.7(2)
[9.9(2)]
90.8(1)
[90.4(1)]
105.2(1)
[107.2(1)]
99.9(1)
[101.1(1)]
91.4(1)
[91.4(1)]
91.0(1)
[91.9(2)]
106.9(2)
[106.8(2)]
88.7(2)
[90.5(1)]
101.7(2)
[98.7(1)]
97.0(2)
[97.3(2)]
7.3(2)
[7.3(2)]
94.2(1)
[95.7(2)]
92.0(1)
[93.8(2)]
93.6(2)
[92.5(2)]
93.2(2)
[76.0(1)]
102.8(1)
[102.1(1)]
76.4(1)
[75.1(1)]
75.5(1)
[76.1(1)]
103.6(1)
[101.4(1)]
75.2(1)
[76.0(1)]
84.8(1)
[84.5(1)]
14.0(1)
[14.3]
101.6(3)
82.4(3)
81.6(3)
101.7(3)
82.7(3)
88.8(3)
8.9(3)
97.97(12)
83.07(11)
83.21(11)
98.83(12)
82.40(12)
88.11(12)
7.49(12)
91.80(9)
104.45(9)
98.13(9)
89.39(8)
88.83(8)
104.92(9)
92.59(9)
99.53(9)
96.21(9)
6.65(9)
102.09(5)
82.94(5)
82.92(5)
100.97(5)
78.77(5)
87.6(5)
9.99(5)
89.95(3)
107.57(4)
100.94(4)
90.52(4)
90.69(4)
107.82(4)
89.53(4)
101.69(3)
97.34(4)
7.47(4)
95.20(4)
92.99(4)
94.95(4)
94.70(4)
100.0(2) 89.0(2)
N(1)–M(1)–N(3) 99.4(1)
N(2)–M(1)–N(3) 76.5(1)
N(4)–M(2)–N(5) 76.0(1)
N(4)–M(2)–N(6) 99.8(1)
N(5)–M(2)–N(6) 76.8(1)
84.0(1)
76.2(2)
76.1(2)
99.9(2)
75.4(2)
73.5(3)
73.5(2)
107.9(2)
75.6(3)
N(4)–M(2)–
N(6)
N(5)–M(2)–
N(6)
N–M–N[a]
83.9(2) 82.6(3)
12.7(2) 13.37(3)
Dev[b]
12.5(1)
N(1)–M(1)–S(1) 95.0(2)
N(2)–M(1)–S(1) 105.8(2)
N(1)–M(1)–S(2) 96.2(2)
N(3)–M(1)–S(2) 88.2(2)
N(4)–M(2)–S(2) 87.7(2)
N(5)–M(2)–S(1) 106.4(2)
N(6)–M(2)–S(1) 92.8(2)
N(6)–M(2)–S(2) 98.6(2)
87.0(1)
87.2(2)
N(1)–M(1)–S(1) 87.52(9)
86.29(9)
[87.24(8)]
111.9(2) 109.5(2)
N(2)–M(1)–S(1) 102.53(9) 103.29(9)
[98.70(8)]
N(2)–M(1)–S(2) 100.59(9) 102.1(1)
[104.67(9)]
97.9(1)
86.4(1)
86.1(1)
113.2(2)
85.0(2)
87.1(2)
N(3)–M(1)–S(2) 87.81(9)
86.99(9)
[86.11(8)]
85.16(8)
[87.73(8)]
N(4)–M(2)–S(2) 88.12(9)
112.4(1) 107.1(2)
87.2(1) 87.3(2)
N(5)–M(2)–S(1) 101.04(9) 102.45(9)
[99.78(8)]
86.99(8)
N(6)–M(2)–S(1) 87.12(9)
N(5)–M(2)–S(2) 104.0(1)
94.84(9)
[85.66(8)]
100.46(9)
[99.58(9)]
94.22(9)
[93.68(8)]
7.86(9)
[7.00(9)]
98.3(1)
[95.52(8)]
97.25(8)
100.1(2) 103.8(2)
96.1(1) 97.5(2)
6.95(1) 10.9(2)
N–M–S[a]
96.3(2)
7.4(2)
92.6(2)
83.6(2)
85.7(2)
89.6(2)
Dev[b]
7.20(9)
Cl–M(1)–N(2)
Cl–M(1)–N(3)
Cl–M(2)–N(4)
Cl–M(2)–N(5)
91.03(9)
85.82(9)
84.91(9)
91.01(9)
99.2(2)
93.2(1)
92.2(1)
96.7(1)
90.1(2)
104.7(2)
84.1(2)
100.1(2)
Cl–M(1)–N(1)
Cl–M(1)–N(3)
Cl–M(2)–N(4)
Cl–M(2)–N(6)
99.97(9)
96.2(1)
[102.03(8)]
97.34(9)
[97.21(8)]
100.4(1)
100.4(1)
94.41(9)
[95.9(2)]
[100.64(9)]
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95

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Table 4. (continued).
6
7[c]
8
9
10
12
11
13[c]
Cl–M–N[a]
Dev[b]
87.9(2)
93.3(2)
[94.5(2)]
3.3(2)
88.19(9)
94.46(4)
95.3(1)
94.8(2)
97.8(1)
98.3(1)
[98.85(8)]
8.3(1)
3.4(2)
2.83(9)
4.46(4)
5.3(1)
7.7(2)
7.8(1)
[4.5(2)]
80.39(7) 78.26(6)
[76.53(6)]
89.45(7) 88.29(6)
[86.32(6)]
81.05(8) 77.42(7)
[77.52(6)]
90.64(7) 87.47(6)
[88.51(6)]
85.38(7) 82.94(6)
[82.22(6)]
[8.85(8)]
84.41(4)
[85.91(4)]
85.71(4)
[84.49(3)]
85.93(4)
[87.62(4)]
85.43(4)
[85.17(3)]
85.37(4)
[85.79(4)]
4.67(4)
[4.21(4)]
83.67(4)
[84.39(5)]
83.69(4)
[84.55(5)]
83.68(4)
[84.47(5)]
6.32(4)
Cl–M(1)–S(1)
Cl–M(1)–S(2)
Cl–M(2)–S(1)
Cl–M(2)–S(2)
Cl–M–S[a]
Dev[b]
85.20(4)
88.22(5)
84.60(4)
87.63(4)
86.41(4)
3.59(4)
76.48(1)
87.16(2)
76.23(1)
86.71(1)
81.65(1)
8.36(1)
80.97(6) 80.21(8)
91.50(6) 86.49(7)
82.26(6) 80.21(8)
92.11(6) 85.45(7)
86.71(6) 83.09(8)
Cl–M(1)–S(1)
Cl–M(1)–S(2)
Cl–M(2)–S(1)
Cl–M(2)–S(2)
85.54(4)
85.46(5)
83.90(5)
85.43(5)
85.08(5)
4.92(5)
84.97(4)
84.90(5)
84.94(5)
5.06(5)
170.23(9)
170.37(9)
172.41(9)
169.60(9)
171.51(9)
172.00(8)
4.94(7)
7.14(6)
[7.78(6)]
S(1)–M(1)–S(2) 84.03(8) 80.48(6)
[79.01(6)]
S(1)–M(2)–S(2) 84.22(8) 79.58(6)
[79.54(6)]
5.10(6)
6.91(8)
82.96(4)
82.79(4)
82.88(4)
7.12(4)
79.23(1)
78.63(1)
78.93(1)
11.07(1)
162.72(4)
173.14(4)
165.55(4)
161.83(4)
166.40(4)
173.55(4)
167.20(4)
12.80(4)
81.16(1)
85.60(1)
83.38(1)
6.62(1)
86.30(7) 92.67(7)
86.09(5) 93.68(7)
86.19(6) 93.18(7)
S(1)–M(1)–S(2)
S(1)–M(2)–S(2)
S–M–S[a]
84.13(8) 80.03(6)
[79.29(6)]
9.97(6)
[10.73]
172.4(2) 165.2(1)
[163.6(1)]
Dev[b]
5.87(8)
3.81(6)
3.18(7)
[5.53(5)]
169.5(1)
Cl–M(1)–N(1)
172.61(9)
172.47(8)
168.37(8)
171.94(9)
166.83(8)
172.01(8)
170.71(9)
9.29(9)
164.2(1) 157.2(2)
160.0(2) 156.7(2)
170.5(1) 174.4(2)
163.3(2) 165.0(2)
170.2(1) 164.1(2)
160.4(1) 159.1(2)
164.8(1) 162.8(2)
Cl–M(1)–N(2)
N(1)–M(1)–S(2)
N(3)–M(1)–S(1)
Cl–M(2)–N(5)
N(4)–M(2)–S(1)
N(6)–M(2)–S(2)
[170.04(9)]
168.79(9)
[171.61(8)]
170.37(8)
[166.98(8)]
170.17(9)
[171.52(9)]
168.09(8)
[170.53(7)]
168.65(8)
[168.40(8)]
N(2)–M(1)–S(2) 170.1(2) 174.2(1)
[173.8(1)]
N(3)–M(1)–S(1) 162.3(2) 167.4(1)
[166.7(1)]
168.4(2) 161.8(2)
[164.7(2)]
N(4)–M(2)–S(1) 164.4(2) 167.2(2)
[166.9(2)]
Cl–M(2)–N(6)
N(5)–M(2)–S(2) 169.3(2) 173.5(2)
[173.0(2)]
X–M–Y[a]
167.8(2) 168.2(2)
[168.1(2)]
171.02(9) 169.26(9)
[169.85(9)]
Dev[b]
12.2(2)
11.8(2)
[11.9(2)]
M(1)–S(1)–M(2) 79.55(7) 79.70(6)
[80.90(6)]
M(1)–S(2)–M(2) 79.90(7) 82.51(6)
[84.63(6)]
15.2(1)
17.2(2)
8.98(9)
10.74(9)
[10.15(9)]
77.29(4)
[77.37(4)]
77.66(3)
[76.28(4)]
77.48(4)
[76.83(4)]
12.52(4)
[13.17(4)]
78.18(4)
77.50(4)
78.78(4)
78.14(4)
11.86(4)
75.03(4)
74.75(5) 76.60(6)
76.07(5) 75.81(6)
75.41(5) 76.21(6)
14.59(5) 13.79(6)
74.41(5) 72.27(6)
M(1)–S(1)–M(2) 77.78(4)
M(1)–S(2)–M(2) 77.63(4)
77.71(4)
M–S–M[a]
79.73(7) 81.11(6)
[82.77(6)]
10.27(7) 8.89(6)
[7.23(6)]
72.46(6) 81.38(6)
[80.66(6)]
Dev[b]
12.29(4)
M(1)–Cl–M(2)
81.27(1)
M(1)–Cl–M(2)
76.83(4)
[77.20(3)]
[a] Average values. [b] Average deviations from the ideal 90° or 180° L–M–L bond angles of a perfect octahedron. [c] There are two
crystallogrphically independent molecules in the asymmetric unit. Values in square brackets refer to molecule B.
atives.[22] The dependence of the bond angles on the type of Description of the Crystal Structures of [(L1)CdII2(µ-
N donors is not so pronounced. The most visible changes Cl)][BPh4]·5MeOH (10[BPh4]·5MeOH) and [(L3)-
across the series include the M–Cl–M bond angles, which CdII2(µ-Cl)][BPh4]·2MeCN (12[BPh4]·2MeCN)
increase by around 10° upon going from 6 to 9. In sum-
mary, all N6S2 macrocycles support the formation of dinu-
The crystal structure determinations of the two title com-
clear nickel complexes of type A. As we will show below, a pounds revealed the presence of dioctahedral complex cat-
completely different situation is seen in the case of the cad- ions, tetraphenylborate anions and methanol or acetonitrile
mium complexes 10–13.
molecules of solvent of crystallisation. ORTEP plots of 10
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NiII and CdII Complexes of Hexaazadithiophenolate Macrocycles
FULL PAPER
and 12 are displayed in Figures 4 and 5, respectively. Se- (12) are normal for six-coordinate cadmium complexes with
lected bond lengths and angles are collected in Tables 3 and amine donors.[24,25] The same holds for the average Cd–S
4. The structure of the [(L2)Cd2II(µ-Cl)]+ complex 11 has [2.671(2) and 2.647(2) Å][26] and Cd–Cl distances [2.701(3)
been reported previously,[13] and its metrical parameters are and 2.770(1) Å].[27–29] As expected, the Cd–N(secondary
also given for comparison. The conformation adopted by amine) distances in 10 and 12 are shorter (by about 0.04 Å)
the supporting ligands in 10 and 12 is that of type A. For than the corresponding Cd–N(tertiary amine) bonds in 11
reasons that are still unclear, however, the configuration at and 13. The same trend was observed in the series of nickel
N(3) in 12 is opposite to that found in 10 and in the nickel complexes above.
complexes above. Each cadmium atom is coordinated by
two S and three N atoms from the supporting ligand and a
bridging chloride in a severely distorted octahedral fashion.
The distortions from the ideal octahedral geometry are
somewhat more pronounced than in the nickel complexes
above and in the cadmium complexes of type B described
below, which is probably a consequence of the larger ionic
radius of cadmium(II) (CdII: 1.06 Å; NiII: 0.83 Å).[23] The
average Cd–N bond lengths of 2.390(5) (10) and 2.399(7) Å
Figure 5. Two perspective views of the molecular structure of 12
with atomic numbering for key atoms (30% probability thermal
ellipsoids). Hydrogen atoms (except those bonded to N atoms) have
been omitted for clarity.
Description of the Crystal Structure of {[(L4)CdII2(µ-
Cl)][BPh4]·3.5MeCN}2 {13[BPh4]·3.5MeCN}2
Crystals of the title complex grown from a mixed aceto-
nitrile/ethanol solution are monoclinic with space group
P21/n. The asymmetric unit contains two crystallographi-
Figure 4. Two perspective views of the molecular structure of 10
cally independent molecules. A perspective view of the
with atomic numbering for key atoms (30% probability thermal
structure of molecule A is displayed in Figure 6. The struc-
ture of molecule B is identical to that of molecule A and is
ellipsoids). Hydrogen atoms (except those bonded to N atoms) have
been omitted for clarity.
Eur. J. Inorg. Chem. 2007, 90–102
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97

M. Gressenbuch, B. Kersting
FULL PAPER
not considered further. The [(L4)Cd2(µ-Cl)]+ complex 13 is and the N-alkylation grade. Two trends are apparent for the
isostructural with the [(L2)Cd2(µ-Cl)]+ cation 11, with the present [(LR)M2(µ-Cl)]+ cations. In the case of small metal
macrocycle having a type-B conformation. There are no ions such as NiII, the conformation is always that of type
unusual features as far as bond lengths and angles are A, irrespective of the N-alkylation grade, whereas for the
concerned. The average Cd–(µ-Cl) [2.661(1) Å], Cd–N larger CdII ion a clear correlation exists between the N-
[2.436(4) Å] and Cd–S [2.681(1) Å] bond lengths are very alkylation grade and the macrocycle conformation. Here,
similar to the corresponding values in 11. As in 11, the two the higher the N-alkylation grade the more preferred the
metal ions are coordinated in a distorted octahedral fashion conformation of type B. e) Finally, it has also been demon-
by the two fac-N3(µ-S)2 donor sets of the doubly deproton- strated that the complexes exist as single isomers in solu-
ated macrocycle and the bridging chloride. The diethylene tion. Computational studies are underway to determine the
triamine units are facially coordinated, with one larger and energy differences between the two complex conformations.
two smaller N–M–N bond angles. The same situation is
observed in 11 and other complexes with this tridentate
unit.[21] Likewise, the M–N bond lengths involving the four
benzylic nitrogen donors are invariably longer (by around
0.1 Å) than the ones comprising the central nitrogen atoms
of the linking diethylenetriamine units. This is also normal
for complexes of this ligand system. The most salient fea-
ture of the structure of 13 is that (L4)2– adopts a bowl-
shaped, C2v-symmetric conformation, an effect that may be
traced to the more optimal L–Cd–L bond angles. In fact, it
can be readily seen from Table 4 that there is a consistent
decrease in the deviations of the cis- and trans-L–Cd–L
bond angles upon going from 12 to 13 (or from 10 to 11).
Thus, for the present [(LR)M2(µ-Cl)]+ complexes the con-
formation adopted depends not only on the N-alkylation
grade but also on the metal ion radius.
Experimental Section
Materials and Methods: Compounds 1 and H2L1 were prepared as
described in the literature.[14] The syntheses of the metal complexes
were carried out under a protective atmosphere of argon. Melting
points were determined in open glass capillaries and are uncor-
rected. NMR spectra were recorded with a Bruker Avance DPX-
200 spectrometer or a Bruker Avance DRX 400 spectrometer at
298 K. Chemical shifts are referred to solvent signals. Infrared
spectra were recorded with a Bruker Vector 22 FT-IR spectrometer
and electronic absorption spectra with a Jasco V-570 UV/VIS/NIR
spectrometer. Elemental analyses were recorded with a VARIO EL-
elemental analyzer. ESI-FTICR mass spectra were recorded with a
Bruker Apex II instrument using dilute CH2Cl2/MeOH solutions.
CAUTION! Perchlorate salts are potentially explosive and should
therefore be prepared only in small quantities and handled with ap-
propriate care.
Preparation of Compound 3: Solutions of 1,2-bis(4-tert-butyl-
2,6-diformylphenylthio)ethane (1; 3.00 g, 6.37 mmol) in dichloro-
methane (100 mL) and bis(aminoethyl)methylamine (2; 1.51 g,
12.9 mmol) in ethanol (100 mL) were added simultaneously over a
period of 3 h to a mixture of dichloromethane (300 mL) and etha-
nol (300 mL). After complete addition, the reaction mixture was
stirred at room temperature for 18 h. The dichloromethane was re-
moved under reduced pressure and a solution of sodium borohyd-
ride (1.21 g, 32.0 mmol) in ethanol (50 mL) was added. After stir-
ring at room temperature for 2 h, the reaction mixture was acidified
to pH 1 with conc. hydrochloric acid and the resulting colourless
suspension was evaporated to dryness. The residue was taken up
in aqueous potassium hydroxide (3 , 80 mL) and extracted with
dichloromethane (4ϫ100 mL). The combined organic fractions
were dried with magnesium sulfate. Evaporation of the solvent gave
Figure 6. Molecular structure of 13 with atomic numbering for key
atoms (30% probability thermal ellipsoids). Hydrogen atoms have
been omitted for clarity.
1
3 (3.96 g, 97%) as a colourless, foamy solid. M.p. 84 °C. H NMR
(400 MHz, CDCl3): δ = 1.29 [s, 18 H, ArC(CH3)3], 2.31 (s, 6 H,
NCH3), 2.69 (m, 8 H, NCH2 CH2N), 2.93 (m, 8 H, NCH2CH2N),
3.07 [s, 4 H, (ArSCH2)2], 3.99 (s, 8 H, ArCH2N), 7.49 ppm (s, 4 H,
ArH). 13C{1H}NMR (50 MHz, CDCl3): δ = 30.2 [C(CH3)3], 33.6
[C(CH3)3], 34.9 (SCH2), 40.7 (NCH3), 46.6 (ArCH2N), 52.7
(NCH2CH2N), 56.7 (NCH2CH2N), 125.7 (CArH), 127.9 (CArS),
Conclusions
The main findings of this investigation are as follows:
a) N-alkylated variants of H2L1 with different N-alkylation
grades and patterns can be readily prepared by a [2 + 1]
condensation reaction of tetraaldehyde 1 with bis(amino-
ethyl)methylamine followed by acylation and reduction of
the resultant hexaamine dithioether compound 3. b) All li-
gand systems are effective dinucleating ligands that support
the formation of dioctahedral [(LR)M2(µ-Cl)]+ cations (M
= NiII and CdII). c) The macrocycles adopt either a saddle-
shaped (type A) or a bowl-shaped (type B) conformation.
d) The actual conformation adopted depends not only on
143.2 (CArCH2N), 150.9 ppm (CArtBu). IR (KBr): ν = 3425 (w),
˜
3307 (w), 3049 (vw), 2952 (vs), 2902 (s), 2867 (s), 2801 (s), 2370
(w), 2273 (vw), 1641 (vw), 1630 (vw), 1596 (w), 1564 (vw), 1554
(vw), 1534 (vw), 1512 (vw), 1459 (s), 1393 (w), 1362 (m), 1330 (w),
1293 (w), 1262 (m), 1223 (m), 1203 (m), 1119 (s), 1045 (s), 926 (vw),
884 (w), 800 (m), 744 (w), 653 (vw), 631 cm–1 (vw).
C36H60N6S2·H2O (641.03 + 18.02): calcd. C 65.61, H 9.48, N 12.75,
S 9.73; found C 65.40, H 9.28, N 12.39, S 10.52.
Preparation of Compound 4: A solution of 3 (3.40 g, 5.30 mmol) in
the type of co-ligand,[30] but also on the metal ion radius acetic anhydride (150 mL) was stirred at 50 °C for 6 h. After re-
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NiII and CdII Complexes of Hexaazadithiophenolate Macrocycles
FULL PAPER
moval of the solvent under reduced pressure, the residue was taken
up in aqueous potassium hydroxide solution (3 , 100 mL) and ex-
tracted with dichloromethane (3ϫ100 mL). The combined organic
phases were dried with magnesium sulfate and the solvents evapo-
rated to dryness. The residue was taken up in methanol and puri-
fied by flash chromatography on silica gel using a methanol/water
product, the residue was triturated with methanol (3ϫ50 mL) and
filtered. The crude product was further purified by recrystallisation
from a mixed methanol/ethanol (1:1) solvent system. This material
(3.55 g, 72%) was used without further purification. M.p. 259 °C.
1H NMR (400 MHz, CD3OD): δ = 1.34 [s, 18 H, C(CH3)3], 3.00 (s,
6 H, NCH3), 3.67 (m, 16 H, NCH2CH2N), 4.64 (s, 8 H, ArCH2N),
(9:1) mixture as eluting solvent. Drying in vacuo gave 4 (3.56 g, 7.80 ppm (s, 4 H, ArH) ppm. 13C{1H} NMR (100 MHz, CD3OD):
83%) as a colourless solid. M.p. 116 °C. 1H NMR (300 MHz, [D6]-
δ = 31.5 [C(CH3)3], 35.9 [C(CH3)3], 42.1 (NCH3), 43.4 (NCH2),
DMSO, 373 K): δ = 1.21 [s, 18 H, C(CH3)3], 2.31 (s, 6 H, NCH3), 52.2 (NCH2), 53.6 (NCH2), 130.4 (CArH), 132.1 (CArS), 135.8
2.49–2.65 (m, 8 H, NCH2CH2N), 2.91 (s, 4 H, ArSCH2), 3.03 (s, (CArCH2N), 153.8 ppm (CArtBu). IR (KBr): ν = 3425 (vs), 2961
˜
12 H, COCH3), 3.34 [m, 8 H, CH3N(CH2CH2N)2], 4.73 (s, 8 H,
(vs), 2869 (s), 2640 (s), 1724 (vw), 1629 (w), 1601 (w), 1512 (vw),
1462 (s), 1366 (w), 1231 (w), 1161 (vw), 1019 (vw), 993 (vw), 895
(vw), 786 (vw), 753 (vw), 663 (vw), 557 cm–1 (vw).
C34H64Cl6N6S2·1.5EtOH (830.28 + 69.04): calcd. C 49.22, H 8.15,
ArCH N), 6.99 ppm (s, 4 H, ArH). IR (KBr): ν = 3442 (w), 2963
˜
2
(s), 2868 (w), 2796 (w), 1649 [vs, ν(CO)], 1559 (vw), 1467 (s), 1413
(s), 1362 (m), 1298 (w), 1261 (m), 1231 (m), 1149 (m), 1083 (w),
1024 (m), 976 (w), 940 (w), 873 (vw), 801 (w), 730 (w), 698 (vw), Cl 23.56, N 9.31, S 7.10; found C 48.8, H 8.38, Cl 23.53, N 9.13,
660 (vw), 602 (w), 572 (vw), 535 (vw), 463 cm–1 (vw). S 7.55.
C44H68N6O4S2·H2O (809.18 + 18.02): calcd. C 63.89, H 8.53, N
10.16, S 7.75; found C 63.77, H 8.28, N 9.88, S 7.52.
Preparation of H2L4·6HCl: The preparation of this ligand was anal-
ogous to that of H2L3·6HCl except that compound 5 was used in-
Preparation of Compound 5: A solution of 4 (620 mg, 0.766 mmol)
stead of 3. Yield: 672 mg (71%). The hexahydrochloride salt could
in tetrahydrofuran (40 mL) was added dropwise to a suspension of
not be obtained in analytically pure form, but it was pure enough
lithium aluminium hydride (429 mg, 11.3 mmol) in tetrahydrofuran
for the preparation of the metal complexes. 1H NMR (200 MHz,
(40 mL). After refluxing the reaction mixture for 12 h, the oil bath
CD3OD): δ = 1.24–1.70 [m, 30 H, C(CH3)3 and NCH2CH3], 2.67–
was removed. Water (5 mL) was carefully added to the hot reaction
3.05 (m, 6 H, NCH3), 3.17–3.99 (m, 24 H, NCH2), 7.42–8.15 ppm
mixture in small portions followed by 3  potassium hydroxide
(m, 4 H, ArH). 13C{1H}NMR (100 MHz, CD3OD): δ = 9.04
solution (20 mL). The reaction mixture was stirred for an ad-
(NCH2CH3), 31.6 [C(CH3)3], 35.2 [C(CH3)3], 41.3 (NCH3), 47.7
ditional hour without heating. The organic layer was decanted off
(NCH2CH3), 50.1 (ArCH2N), 52.5 (NCH2CH2N), 59.5
from a white residue, which was rinsed with boiling tetrahydrofuran
(NCH2CH2N), 132.2 (CArH), 132.6 (CArS), 135.4 (CArCH2N),
(2ϫ50 mL). The solvent was removed by distillation under reduced
148.9 ppm (CArtBu). IR (KBr): ν = 3404 (vs), 2964 (vs), 2870 (s),
2604 (vs), 1633 (w), 1602 (w), 1467 (vs), 1414 (s), 1398 (s), 1366
(m), 1232 (w), 1202 (vw), 1164 (w), 1081 (w), 1046 (m), 992 (vw),
959 (vw), 897 (vw), 795 (w), 737 cm–1 (vw).
˜
pressure. The residue was treated with 3  potassium hydroxide
solution (50 mL) and the resulting mixture was extracted with
dichloromethane (3ϫ50 mL). The combined organic layers were
dried with potassium carbonate. Evaporation of the solvent gave
the product as a colourless, foamy solid (568 mg, 98%). The crude
material was purified by recrystallisation from a dichloromethane/
ethanol (1:1) mixed solvent system. M.p. 146 °C. 1H NMR
Preparation of [(L3)Ni2(Cl)][ClO4] (8[ClO4]) and [(L3)Ni2(Cl)][BPh4]
(8[BPh4]): A solution of NiCl2·6H2O (261 mg, 1.10 mmol) in meth-
anol (2 mL) was added to a suspension of H2L3·6HCl (460 mg,
0.552 mmol) in methanol (15 mL). A solution of NEt3 (448 mg,
4.43 mmol) in methanol (3 mL) was then added dropwise to give a
dark red solution. The solution was stirred for a further 2 d at
room to give a yellow solution. Solid LiClO4·3H2O (882 mg,
5.50 mmol) was added and half of the solvent was removed in
vacuo. The resulting yellow precipitate was filtered off, recrystal-
lised once from a few millilitres of acetonitrile, and dried in vacuo.
3
(200 MHz, CDCl3): δ = 0.87 (t, J = 7 Hz, 12 H, NCH2CH3), 1.22
[s, 18 H, C(CH3)3], 2.19 (s, 6 H, NCH3), 2.30 (q, 3J = 7 Hz, 8
H, NCH2CH3), 2.42–2.52 (m, 16 H, NCH2CH2N), 2.83 (s, 4 H,
ArSCH2), 3.66 (s, 8 H, ArCH2N), 7.36 ppm (s, 4 H, ArH).
13C{1H}NMR (50 MHz, CDCl3): δ = 11.9 (NCH2CH3), 31.3
[C(CH3)3], 34.6 [C(CH3)3], 36.5 (SCH2), 43.6 (NCH3), 47.6
(NCH2CH3), 51.4 (NCH2CH2N), 55.2 (ArCH2), 57.8
(NCH2CH2N), 125.2 (CArH), 128.7 (CArS), 144.2 (CArCH2N),
Yield: 416 mg (87%). M.p. 299 °C (decomp.). IR (KBr): ν = 3430
˜
150.8 ppm (CArtBu). IR (KBr): ν = 3425 (vw), 2965 (vs), 2868 (s),
˜
(m), 3286 (w), 3256 (w), 3095 (vw), 2955 (m), 2870 (m), 2023 (vw),
1629 (w), 1461 (m), 1393 (w), 1363 (w), 1333 (vw), 1307 (vw), 1258
2798 (vs), 1595 (w), 1559 (vw), 1461 (w), 1407 (w), 1384 (m), 1366
(s), 1335 (w), 1312 (m), 1296 (w), 1274 (m), 1260 (m), 1217 (w),
1187 (m), 1163 (w), 1123 (s), 1100 (m), 1081 (m), 1039 (s), 1002
(w), 979 (w), 950 (w), 936 (w), 915 (w), 898 (w), 882 (w), 791 (w),
770 (w), 730 (vw), 683 (w), 653 (w), 607 (vw), 575 (vw), 555 (vw),
529 (vw), 475 cm–1 (vw). C44H76N6S2·H2O (753.24 + 18.02): calcd.
C 68.52, H 10.19, N 10.90, S 8.31; found C 68.35, H 10.16, N
10.57, S 7.92. This compound was additionally characterised by X-
ray crystallography.
Preparation of H2L3·6HCl: A solution of 3 (3.80 g, 5.93 mmol) in
tetrahydrofuran (50 mL) was added dropwise to a solution of so-
dium (2.0 g, 87 mmol) in liquid ammonia (150 mL). The resulting
blue reaction mixture was stirred for a further 3 h at –76 °C. Solid
ammonium chloride was then added to destroy the excess reducing
agent. The resulting colourless suspension was warmed to room
temperature. After 12 h, the remaining solvent was distilled off un-
der reduced pressure. The residue was taken up in water (20 mL)
and the solution was acidified to pH 1 with conc. hydrochloric acid.
To remove sodium chloride and ammonium chloride from the
–
(w), 1229 (w), 1156 (m), 1094 [vs, ν(ClO4 )], 1000 (w), 975 (w), 957
(vw), 930 (w), 894 (vw), 871 (w), 854 (w), 806 (vw), 750 (w), 623
(m), 568 (vw), 546 (vw), 472 cm–1 (vw). UV/Vis (CH3CN): λmax
(ε) = 623(76), 902 (63), 960 nm (68 –1 cm–1). C34H56Cl2N6Ni2O4S2
(865.27): calcd. C 47.20, H 6.52, N 9.71, S 7.41; found C 47.20, H
6.29, N 9.32, S 7.10. The tetraphenylborate salt 8[BPh4] was pre-
pared by adding NaBPh4 (342 mg, 1.00 mmol) to a solution of
8[ClO4] (86.5 mg, 0.100 mmol) in methanol (40 mL). The yellow
microcrystalline solid was isolated by filtration, washed with etha-
nol, and dried in air. Yield: 96.2 mg (89%). M.p. 249 °C (decomp).
IR (KBr): ν = 3440 (w), 3275 (m), 3055 (w), 2963 (m), 2872 (m),
˜
1948 (vw), 1658 (w), 1578 (vs), 1479 (m), 1457 (s), 1426 (s), 1392
(w), 1362 (w), 1311 (w), 1260 (w), 1229 (w), 1151 (w), 1081 (m),
1057 (w), 1032 (w), 984 (w), 930 (w), 877 (w), 849 (w), 733 [m,
ν(BPh4 )], 705 [s, ν(BPh4 )], 612 (m), 545 (vw), 464 (vw) cm–1.
C58H76BClN6Ni2S2 (1085.05): calcd. C 64.20, H 7.06, N 7.75, S
5.91; found C 63.81, H 7.14, N 7.44, S 5.64. The tetraphenylborate
salt was additionally characterised by X-ray crystallography.
–
–
Eur. J. Inorg. Chem. 2007, 90–102
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
99

M. Gressenbuch, B. Kersting
FULL PAPER
Preparation of [(L4)Ni2(Cl)][ClO4] (9[ClO4]) and [(L4)Ni2(Cl)][BPh4] 735 (vs), 707 (vs), 612 (m) cm–1. H NMR (400 MHz, CD3OD): δ
1
(9[BPh4]): A solution of NiCl2·6H2O (59.4 mg, 0.250 mmol) in
methanol (2 mL) was added to a suspension of H2L4·6HCl
(118 mg, 0.125 mmol) in methanol (15 mL). A solution of NEt3
(101 mg, 1.00 mmol) in methanol (3 mL) was then added to give a
dark red solution. The solution was stirred for a further 2 d at
room temp. to give a yellow solution. Solid LiClO4·3H2O (200 mg,
1.25 mmol) was added and half of the solvent was removed in
vacuo. The resulting yellow precipitate was filtered off, recrystal-
lised once from a few millilitres of acetonitrile, and dried in vacuo.
= 1.26 (s, 9 H, C1H3 or C4H3), 1.32 (s, 9 H, C1H3 or C4H3), 2.50–
3.75 (m, 20 H, C6–9,6Ј–9ЈH2 + C5,5Ј,10,10ЈHH), 4.35–4.41 (m, 4 H,
–
C5,5Ј,10,10ЈHH), 6.82 (t, J = 8 Hz, 4 H, BPh4 ), 6.96 (t, J = 8 Hz, 8
–
–
H, BPh4 ), 7.16 (s, 2 H, C13,13ЈH or C17,17ЈH), 7.29 (m, 8 H, BPh4 ),
7.33 ppm (s, 2 H, C13,13ЈH or C17,17ЈH). 13C{1H}NMR (100 MHz,
[D6]DMSO): δ = 31.1 (C1 or C4), 31.2 (C1 or C4), 33.7 (C2 or C3),
33.8 (C2 or C3), 47.4, 48.6, 49.1, 49.3, 54.2, 55.2 (C5–10,5Ј–10Ј), 127.5,
127.8 (C13,13Ј,17,17Ј), 138.0, 138.2 (C12,12Ј,16,16Ј), 139.0, 139.9 (C11,15),
140.0, 145.8 (C14,18), 121.5 (BPh4 ), 125.3 (BPh4 ), 135.5 (BPh4 ),
–
–
–
–
Yield: 78 mg (64%). M.p. 296 °C (decomp.). IR (KBr): ν = 3438
164.0 ppm (BPh4 ). This salt was additionally characterised by X-
˜
(m), 2963 (s), 2891 (s), 2018 (vw), 1629 (w), 1460 (s), 1377 (m),
1363 (m), 1314 (w), 1259 (w), 1232 (w), 1201 (vw), 1158 (m), 1098
(vs, νClO4 ), 1058 (m), 1023 (m), 988 (vw), 968 (vw), 955 (vw), 925
ray crystallography.
Preparation of [(L3)Cd2(Cl)][ClO4] (12[ClO4]) and [(L3)-
Cd2(Cl)][BPh4] (12[BPh4]): A solution of CdCl2·H2O (223 mg,
1.10 mmol) in MeOH (2 mL) was added to a suspension of
H2L3·6HCl (460 mg, 0.552 mmol) in MeOH (15 mL). A solution
of triethylamine (445 mg, 4.40 mol) in MeOH (3 mL) was then
added to give a colourless solution. After stirring at ambient tem-
perature for 4 d, solid LiClO4·3H2O (118 mg, 0.735 mmol) was
added to give the perchlorate salt 12[ClO4] as a white microcrystal-
line solid. The precipitate was filtered and purified by recrystalli-
sation from MeCN. Yield: 432 mg (80%). M.p. 332 °C (decomp.).
1H NMR (200 MHz, CD3CN, for atom labels see inset of Table 2):
δ = 1.25 (s, 9 H, C1H3 or C4H3), 1.29 (s, 9 H, C1H3 or C4H3), 2.65
[s, 6 H, CH3(R1)], 2.70–3.60 (m, 20 H, C6–9,6Ј–9ЈH2 + C5,5Ј,10,10ЈH),
4.25–4.43 (m, 4 H, C5,5Ј,10,10ЈH), 7.17 (s, 2 H, C13,13ЈH or C17,17ЈH),
7.32 ppm (s, 2 H, C13,13ЈH or C17,17ЈH). 13C{1H}NMR (75 MHz,
CD3CN): δ = 31.61 (C1 or C4), 31.74 (C1 or C4), 34.84 (C2 or C3),
34.93 (C2 or C3), 49.48 (CH3, R1), 50.68, 55.19, 56.20, 58.06, 58.17,
60.37 (C5–10,5Ј–10Ј), 129.01, 129.28 (C13,13Ј,17,17Ј), 138.95, 139.46
(C12,12Ј,16,16Ј), 138.45, 140.24 (C11,15), 147.96, 148.21 ppm (C14,18).
–
(vw), 907 (w), 883 (w), 809 (vw), 778 (m), 732 (w), 673 (vw), 624
(m) cm–1. UV/Vis (CH3CN): λmax (ε) = 675 (31), 928 (62), 1013
(82 –1 cm–1). C42H72Cl2N6Ni2O4S2·H2O (977.48 + 18.02): calcd. C
50.67, H 7.49, N 8.44, S 6.44; found C 50.5, H 7.51, N 8.09, S
6.56. The tetraphenylborate salt 9[BPh4] was prepared by adding
NaBPh4 (342 mg, 1.00 mmol) to a solution of 9[ClO4] (100 mg,
0.100 mmol) in methanol (40 mL). The yellow microcrystalline so-
lid was filtered, recrystallised from a few millilitres of acetonitrile,
and dried in air. Yield: 113 mg (94%). M.p. 205 °C (decomp). IR
(KBr): ν = 3427 (m), 3055 (m), 3033 (m), 2963 (vs), 2894 (s), 2866
˜
(s), 1816 (vw), 1615 (w), 1579 (w), 1478 (vs), 1461 (vs), 1429 (m),
1379 (m), 1362 (m), 1343 (w), 1312 (w), 1262 (w), 1233 (w), 1201
(vw), 1184 (vw), 1157 (w), 1096 (vs), 1058 (s), 1032 (s), 988 (w),
954 (w), 907 (w), 884 (w), 844 (w), 807 (w), 777 (m), 732 [vs,
–
–
ν(BPh4 )], 704 [vs, ν(BPh4 )], 630 (w) 612 (m) cm–1. UV/Vis
(CH3CN): λmax (ε) = 658 (25), 928 (48), 1018 nm (63 –1 cm–1).
C66H92BClN6Ni2S2·3H2O·CH3CN (1197.26 + 95.10): calcd. C
63.20, H 7.88, N 7.59, S 4.96; found C 62.90, H 7.64, N 7.73, S
5.36. The tetraphenylborate salt was additionally characterised by
X-ray crystal structure analysis.
IR (KBr): ν = 3453 (m), 3283 (m), 2953 (m), 2864 (m), 1629 (w),
˜
1462 (m), 1363 (w), 1300 (vw), 1266 (vw), 1229 (w), 1202 (vw),
1154 (w), 1097 [vs, ν(ClO4 )], 989 (w), 931 (w), 860 (w), 751 (vs),
–
624 (m) cm–1. C34H56Cd2Cl2N6O4S2·2H2O (972.70 + 36.03): calcd.
C 40.48, H 6.00, N 8.33, S 6.36; found C 40.20, H 5.88, N 7.61, S
6.11. The tetraphenylborate salt 12[BPh4] was prepared by adding
NaBPh4 (342 mg, 1.00 mmol) to a solution of 12[ClO4] (97 mg,
0.100 mmol) in methanol (40 mL). The colourless microcrystalline
solid was isolated by filtration, washed with ethanol, and dried in
air. Yield: 82 mg (69%). 1H NMR (200 MHz, CD3CN, for atom
labels see inset Table 2): δ = 1.25 (s, 9 H, C1H3 or C4H3), 1.29 (s,
9 H, C1H3 or C4H3), 2.65 [s, 6 H, CH3(R1)] 2.65–3.60 (m, 20 H,
C6–9,6Ј–9ЈH2 + C5,5Ј,10,10ЈHH), 4.20–4.45 (m, 4 H, C5,5Ј,10,10ЈHH),
Preparation of [(L1)Cd2(Cl)][ClO4] (10[ClO4]):
CdCl2·H2O (402 mg, 2.00 mmol) in MeOH (10 mL) was added to
suspension of H2L1·6HCl (806 mg, 1.00 mmol) in MeOH
(30 mL). A solution of triethylamine (809 mg, 8.08 mmol) in
MeOH (3 mL) was then added. After stirring at ambient tempera-
ture for 2 d, solid LiClO4·3H2O (1.60 g, 10.0 mmol) was added.
The precipitate was filtered and purified by recrystallisation from
A solution of
a
MeCN. Yield: 432 mg (46%). IR (KBr): ν = 3445 (m), 3229 [s,
˜
ν(NH)], 2953 (s), 2902 (s), 2855 (s), 1623 (m), 1456 (m), 1395 (w),
1363 (m), 1344 (w), 1297 (w), 1268 (vw), 1227 (m), 1151 (m), 1100
(s), 1078 (m), 1024 (m), 942 (m), 910 (m), 873 (m), 850 (m), 812
(w), 780 (w), 747 (vw), 627 (m) cm–1. 1H NMR (400 MHz, CD3OD,
for atom labels see inset of Table 2): δ = 1.26 (s, 9 H, C1H3 or
C4H3), 1.32 (s, 9 H, C1H3 or C4H3), 2.40–3.70 (m, 20 H,
C6–9,6Ј–9ЈH2 + C5,5Ј,10,10ЈHH), 4.30–4.40 (m, 4 H, C5,5Ј,10,10ЈHH),
7.16 (s, 2 H, C13,13ЈH or C17,17ЈH), 7.34 ppm (s, 2 H, C13,13ЈH or
C17,17ЈH). 13C{1H}NMR (100 MHz, [D6]DMSO): δ = 31.2 (C1 or
C4), 31.3 (C1 or C4), 33.7 (C2 or C3), 33.8 (C2 or C3), 47.4, 48.9,
49.2, 54.2, 55.2, 56.0 (C5–10,5Ј–10Ј), 127.5, 127.8 (C13,13Ј,17,17Ј), 137.3,
137.4 (C12,12Ј,16,16Ј), 138.2, 139.1 (C11,15), 145.0, 145.1 (C14,18) ppm.
ESI-MS: m/z 905.3 (100%) [(L1)Cd2(Cl)]+. The tetraphenylborate
salt 10[BPh4] was prepared by adding NaBPh4 (674 mg, 1.97 mmol)
to a solution of 10[ClO4] (186 mg, 0.197 mmol) in methanol
(50 mL). The resulting colourless microcrystalline solid was iso-
lated by filtration, washed with ethanol, and dried in air. Yield:
6.83 (m, 4 H, BPh4 ), 6.99 (m, 8 H, BPh4 ), 7.17 (s, 2 H, C13,13Ј
H
–
–
or C17,17ЈH), 7.28 (m, 8 H, BPh4 ), 7.32 ppm (s, 2 H, C13,13ЈH or
C17,17ЈH). 13C{1H}NMR (75 MHz, CD3CN): δ = 31.49 (C1 or C4),
31.61 (C1 or C4), 34.9 (C2 or C3), 35.0 (C2 or C3), 49.3 [CH3(R1)],
49.4, 50.6, 55.0, 56.1, 58.0, 60.2 (C5–10,5Ј–10Ј), 128.9, 129.1
(C13,13Ј,17,17Ј), 138.5, 140.1 (C12,12Ј,16,16Ј), 139.0, 139.5 (C11,15),
–
–
–
–
147.1, 147.8 (C14,18); 122.7 (BPh4 ), 126.5 (BPh4 ), 136.7 (BPh4 ),
–
165.04 (BPh ) ppm. IR (KBr): ν = 3426 (m), 3275 (s), 3054 (m),
˜
4
2965 (vs), 2867 (s), 2250 (vw), 1618 (vw), 1579 (w), 1479 (s), 1463
(s), 1427 (m), 1391 (w), 1363 (m), 1296 (w), 1267 (w), 1229 (w),
1201 (w), 1153 (m), 1086 (s), 1047 (s), 982 (w), 929 (w), 904 (w),
–
884 (w), 862 (m), 816 (vw), 749 (m), 735 [vs. ν(BPh4 )], 706 [vs.
–
ν(BPh4 )], 680 (vw), 625 (w), 612 (m), 543 (vw), 469 (vw) cm–1.
C58H76BCd2ClNS2·H2O (1192.48 + 18.02): calcd. C 57.55, H 6.49,
N 6.94, S 5.30; found C 57.20, H 7.13, N 7.54, S 5.56. The tet-
raphenylborate salt was additionally characterised by X-ray crystal
structure analysis.
Preparation of [(L4)Cd2(Cl)][ClO4] (13[ClO4]) and [(L4)-
Cd2(Cl)][BPh4] (13[BPh4]): A solution of CdCl2·H2O (43.2 mg,
172 mg (74%). IR (KBr): ν = 3445 [m, ν(OH)], 3279 [s, ν(NH)],
˜
3054 [m, ν(Ar)], [2962 (vs), 2864 (s)] [ν(CH)], 1616 (w), 1580 (w),
1477 (s), 1455 (s), 1394 (w), 1365 (w), 1300 (w), 1253 (w), 1227 (w),
1202 (vw), 1152 (w), 1098 (w), 1072 (w), 1033 (w), 909 (m), 849 (m),
100
www.eurjic.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 90–102

NiII and CdII Complexes of Hexaazadithiophenolate Macrocycles
FULL PAPER
0.215 mmol) in MeOH (2 mL) was added to a suspension of
H2L4·6HCl (101 mg, 0.107 mmol) in MeOH (20 mL). A solution
of triethylamine (86.7 mg, 0.857 mmol) in MeOH (3 mL) was then
added to give a colourless solution. After stirring at ambient tem-
perature for 2 d, solid LiClO4·3H2O (171 mg, 1.07 mmol) was
added to give the perchlorate salt 13[ClO4] as a white microcrystal-
line solid. The precipitate was filtered and purified by recrystalli-
sation from a mixed EtOH/MeCN (1:1) solvent system. Yield:
102 mg (88%). M.p. 328 °C (decomp.). 1H NMR (200 MHz,
3440 (m), 2961 (s), 2867 (m), 1628 (w), 1465 (s), 1383 (m), 1367
(m), 1313 (w), 1268 (w), 1231 (w), 1203 (vw), 1100 (vs, νClO4 ),
–
1052 (s), 985 (w), 948 (vw), 926 (vw), 887 (w), 778 (m), 624 (m)
cm–1. C42H72Cd2Cl2N6O4S2·7H2O (1084.92 + 126.11): calcd. C
41.65, H 7.16, N 6.94, S 5.30; found C 42.1, H 7.01, N 7.09, S
5.54. The tetraphenylborate salt 13[BPh4] was prepared by adding
NaBPh4 (342 mg, 1.00 mmol) to a solution of 13[ClO4] (108 mg,
0.100 mmol) in methanol (40 mL). The colourless microcrystalline
solid was isolated by filtration, washed with ethanol, and dried in
CD3CN, for atom labels see inset Table 2): δ = 1.12 [t, J = 14 Hz, air. Yield: 119 mg (91%). M.p. 231 °C (decomp.). 1H NMR
12 H, NCH2CH3(R2)], 1.27 (s, 18 H, C1H3 + C4H3), 2.36–4.52 (m, (400 MHz, CD3CN, for atom labels see inset Table 2): δ = 1.16 [m,
38 H, NCH2), 2.83 [s, 6 H, CH3(R1)], 7.28 (s, 4 H, C13,13Ј,17,17ЈH) 12 H, CH2CH3(R2)], 1.28 (s, 18 H, C1H3 + C4H3), 2.86 [s, 6 H,
ppm. 13C{1H}NMR (75 MHz, CD3CN): δ = 6.63 [CH2CH3(R2)], CH3(R1)], 2.70–4.47 (m, 38 H, NCH2), 6.85 (m, 4 H, BPh4 ), 7.00
–
–
–
31.5 (C1,4), 34.7 (C2,3), 50.00 [CH2CH3(R2)], 50.30 [CH3(R1)], (m, 8 H, BPh4 ), 7.23 ppm (m, 4 H + 8 H, C13,13Ј,17,17ЈH + BPh4 ).
55.74, 56.55, 58.13 (C5–10,5Ј–10Ј), 130.18 (C13,13Ј,17,17Ј), 136.29 13C{1H}NMR (75 MHz, CD3CN): δ = 6.56 [CH2CH3(R2)], 31.5
(C12,12Ј,16,16Ј), 142.13 (C11,15), 146.78 (C14,18) ppm. IR (KBr): ν =
(C1,4), 34.65 (C2,3), 49.91 [CH2CH3(R2)], 50.21 [CH3(R1)], 55.64,
˜
Table 5. Crystallographic data for 5, 8[BPh4]·3EtOH, 9[BPh4]·5MeCN, 10[BPh4]·5MeOH, 12[BPh4]·2MeCN and {13[BPh4]·3.5MeCN}2.
5
8[BPh4]·3EtOH
9[BPh4]·5MeCN
Formula
C44H76N6S2
753.23
C2/c
24.437(4)
9.734(3)
19.004(4)
90.00
90.52(2)
90.00
C64H94BClN6Ni2O3S2
1223.25
P1
C76H107BClN11Ni2S2
1402.53
P1
Mr [gmol–1]
Space group
a [Å]
¯
¯
14.872(3)
14.949(3)
16.132(3)
71.14(3)
78.41(3)
71.92(3)
3206.1(11)
2
13.3420(5)
14.7530(5)
19.0750(7)
85.653(3)
88.787(3)
84.854(3)
3728.3(2)
2
b [Å]
c [Å]
α [°]
β [°]
γ [°]
V [Å3]
4520.0(18)
4
Z
Dcalcd. [gcm–3]
µ(Mo-Kα) [mm–1]
θ limits [°]
Measured refl.
Independent refl.
Observed refl.[a]
parameters
R1[b] (R1 all data)
wR2[c] (wR2 all data)
Max., min. peaks [e/Å3]
CCDC
1.107
0.154
1.67–28.86
19600
5472
2602
263
0.0585 (0.1281)
0.1579 (0.1908)
0.443/–0.207
600010
1.267
0.742
1.34–28.82
29072
14990
7750
682
0.0511 (0.1144)
0.1197 (0.1461)
0.885/–0.532
600011
1.249
0.646
3.26-31.99
34637
25571
17381
763
0.0403 (0.0627)
0.0999 (0.1054)
1.226/–0.729
600012
10[BPh4]·5MeOH
12[BPh4]·2MeCN
{13[BPh4]·3.5MeCN}2
Formula
C61H92BCd2ClN6O5S2
1324.59
P1
C62H82BCd2ClN8S2
1274.54
P21/c
15.283(3)
28.264(6)
16.995(3)
90.00
107.28(3)
90.00
7010(2)
C146H205B2Cd4Cl2N19S4
2896.65
P1
18.984(4)
20.143(4)
22.112(4)
98.55(3)
115.29(3)
95.67(3)
7434(3)
Mr [gmol–1]
Space group
a [Å]
¯
¯
14.202(3)
17.019(3)
17.928(4)
109.77(3)
105.85(3)
113.66(3)
3288.1(11)
2
b [Å]
c [Å]
α [°]
β [°]
γ [°]
V [Å3]
Z
4
2
Dcalcd. [gcm–3]
µ(Mo-Kα) [mm–1]
θ limits [°]
Measured refl.
Independent refl.
Observed refl.[a]
parameters
R1[b] (R1 all data)
wR2[c] (wR2 all data)
Max., min. peaks [e/Å3]
CCDC
1.338
0.800
5.10–31.97
49433
22415
11546
741
0.0922 (0.1596)
0.2259 (0.2670)
2.841/–2.582
622729
1.208
0.744
1.44–29.03
44336
16567
5816
655
0.0720 (0.1981)
0.2013 (0.2551)
1.310/–0.829
600013
1.294
0.710
3.21–28.01
137595
34637
26501
1489
0.0478 (0.0647)
0.1313 (0.1447)
1.331/–1.155
600014
[a] Observation criterion: I Ͼ 2σ(I). [b] R1 = Σ||Fo| – |Fc||/Σ|Fo|. [c] wR2 = {Σ[w(Fo – Fc ) ]/Σ[w(Fo2)2]}1/2
.
2
2 2
Eur. J. Inorg. Chem. 2007, 90–102
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
101

M. Gressenbuch, B. Kersting
FULL PAPER
56.46, 59.02 (C5–10,5Ј–10Ј), 130.10 (C13,13Ј,17,17Ј), 136.20 (C12,12Ј,16,16Ј),
[3]
[4]
M. Meyer, V. Dahaoui-Gindrey, C. Lecomte, R. Guilard, Co-
ord. Chem. Rev. 1998, 178–180, 1313–1405.
B. Bosnich, C. K. Poon, M. L. Tobe, Inorg. Chem. 1965, 4,
1102–1108.
F. Wagner, E. K. Barefield, Inorg. Chem. 1976, 15, 408–417.
M. A. Donnelly, M. Zimmer, Inorg. Chem. 1999, 38, 1650–
1656.
X. Liang, J. A. Parkinson, S. Parsons, M. Weishäupl, P. J.
Sadler, Inorg. Chem. 2002, 41, 4539–4547.
B. Kersting, Z. Anorg. Allg. Chem. 2004, 630, 765–780.
G. Steinfeld, V. Lozan, B. Kersting, Angew. Chem. 2003, 115,
2363–2365; Angew. Chem. Int. Ed. 2003, 42, 2261–2263.
142.06 (C11,15), 146.67 (C14,18); 122.79 (BPh4 ), 126.58 (BPh4 ),
–
–
–
–
136.77 (BPh ), 164.82 (BPh ) ppm. IR (KBr): ν = 3441 (w), 3034
˜
4
4
(m), 3054 (m), 2964 (vs), 2863 (s), 1748 (vw), 1616 (vw), 1580 (w),
1464 (vs), 1383 (m), 1367 (m), 1311 (w), 1267 (w), 1232 (w), 1185
(vw), 1159 (w), 1100 (m), 1053 (vs), 986 (vw), 949 (vw), 925 (vw),
[5]
[6]
–
886 (w), 845 (vw), 777 (m), 734 (s), 705 [vs. ν(BPh4 )], 613 (m)
cm–1. C66H92BCd2ClN6S2 (1304.69): calcd. C 60.76, H 7.11, N 6.44,
S 4.92; found C 60.94, H 6.85, N 6.37, S 5.42. The tetraphenylbo-
rate salt was additionally characterised by X-ray crystal structure
analysis.
[7]
[8]
[9]
Crystal Structure Determinations: Large single crystals of 5 were
obtained by slow evaporation of a CH2Cl2/CH3OH solution. Crys-
tals of 8[BPh4]·3EtOH, 9[BPh4]·5MeCN, 12[BPh4]·2MeCN and
{13[BPh4]·3.5MeCN}2 were obtained by slow evaporation from a
mixed MeCN/EtOH (1:1) solvent system. Crystals of 10[BPh4]·
5MeOH were grown by recrystallisation from MeOH. The diffrac-
tion experiments were carried out with Bruker CCD (for 5, 8 and
12) or STOE IPDS-2T X-ray diffractometers (for 9, 10 and 13).
The intensity data were processed with the programs SAINT (5, 8,
12) or STOE X-AREA (9, 10, 13). Structures were solved by direct
methods and refined by full-matrix least-squares on the basis of all
data against F2 using SHELXL-97.[31] PLATON was used to search
for higher symmetry.[32] H atoms were placed in calculated posi-
tions and treated isotropically using the 1.2-fold Uiso value of the
parent atom, except for methyl protons, which were assigned the
1.5-fold Uiso value of the parent C atoms. Unless otherwise noted,
all non-hydrogen atoms were refined anisotropically. ORTEP-3 was
used for the artwork of the structures.[33] Experimental crystallo-
graphic data are summarised in Table 5. Further data are available
in the Supporting Information.
[10]
S. Käss, T. Gregor, B. Kersting, Angew. Chem. 2006, 118, 107–
110; Angew. Chem. Int. Ed. 2006, 45, 101–104.
B. Kersting, G. Steinfeld, Chem. Commun. 2001, 1376–1377.
B. Kersting, G. Steinfeld, Inorg. Chem. 2002, 41, 1140–1150.
V. Lozan, B. Kersting, Eur. J. Inorg. Chem. 2005, 504–512.
a) M. H. Klingele, G. Steinfeld, B. Kersting, Z. Naturforsch.,
Teil B 2001, 56, 901–907; b) G. Siedle, B. Kersting, Z. Anorg.
Allg. Chem. 2003, 629, 2083–2090.
K. Wieghardt, P. Chaudhuri, B. Nuber, J. Weiss, Inorg. Chem.
1982, 21, 3086–3090.
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
N. W. Alcock, A. C. Benniston, S. J. Grant, H. A. A. Omar, P.
Moore, J. Chem. Soc., Chem. Commun. 1991, 1573–1575.
B. Kersting, Angew. Chem. 2001, 113, 4110–4112; Angew.
Chem. Int. Ed. 2001, 40, 3988–3990.
A. J. Atkins, D. Black, A. J. Blake, A. Marin-Becerra, S. Par-
sons, L. Ruiz-Ramirez, M. Schröder, Chem. Commun. 1996,
457–464.
[19] G. Siedle, B. Kersting, Z. Anorg. Allg. Chem. 2003, 629, 2083–
2090.
[20] C. D. Gutsche, Calixarenes, Royal Society of Chemistry, Cam-
bridge, UK, 1989.
[21] D. A. House, in Comprehensive Coordination Chemistry (Eds.:
G. Wilkinson, R. D. Gillard, J. A. McCleverty), 1996, vol. 2,
pp. 23–72.
[22] a) E. K. Barefield, G. M. Freeman, D. G. Van Derveer, Inorg.
Chem. 1986, 25, 552–558; b) P. Chaudhuri, K. Wieghardt, Prog.
Inorg. Chem. 1986, 35, 329–436.
[23] a) R. D. Shannon, C. T. Prewitt, Acta Crystallogr., Sect. B
1969, 25, 925–946; b) R. D. Shannon, Acta Crystallogr., Sect.
A 1976, 32, 751–767.
[24] O. Schlager, K. Wieghardt, H. Grondey, A. Rufinska, B. Nu-
ber, Inorg. Chem. 1995, 34, 6440–6448.
[25] P. V. Bernhardt, P. Comba, T. W. Hambley, G. A. Lawrance, K.
Varnagy, J. Chem. Soc., Dalton Trans. 1992, 355–359.
[26] H. Strasdeit, A.-K. Duhme, M. Weber, S. Pohl, Acta Crys-
tallogr., Sect. C 1992, 48, 437–440.
In the crystal structure of 5 and 10[BPh4]·5MeOH a tert-butyl
group is disordered over two positions. Two split positions were
successfully refined to give the following site occupancies: C(19a)-
C20(a)C(21a)/C(19b)C20(b)C(21b)
C(26a)C(27a)C(28a)/C(26b)C(27b)C(28b)
=
0.60(1)/0.40(1) (for 5),
0.60(2)/0.40(2) (for
=
10[BPh4]·5MeOH). The C, N, and O atoms of the solvates in
8[BPh4]·3EtOH, 9[BPh4]·5MeCN and {13[BPh4]·3.5MeCN}2 were
refined isotropically.
CCDC-600010 to -600014 and -622729 (see Table 5 for assign-
ments) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
[27] B. Krebs, G. Henkel, Angew. Chem. 1991, 103, 785–804; Angew.
Chem. Int. Ed. Engl. 1991, 30, 769–788.
[28] M. G. B. Drew, O. W. Howarth, G. G. Morgan, J. Nelson, J.
Chem. Soc., Dalton Trans. 1994, 3149–3158.
[29] S. S. Tandon, S. Chander, L. K. Thompson, J. N. Bridson, V.
McKee, Inorg. Chim. Acta 1994, 219, 55–65.
[30] J. Hausmann, M. H. Klingele, V. Lozan, G. Steinfeld, D. Sieb-
ert, Y. Journaux, J. J. Girerd, B. Kersting, Chem. Eur. J. 2004,
10, 1716–1728.
Acknowledgments
We are particularly grateful to Prof. Dr. H. Vahrenkamp, Prof. Dr.
E. Hey-Hawkins and Prof. Dr. H. Krautscheid for providing facili-
ties for NMR and X-ray crystallographic measurements. This work
was supported by the Deutsche Forschungsgemeinschaft (priority
programme “Sekundäre Wechselwirkungen”, KE 585/3-3).
[31] Sheldrick, G. M. SHELXL-97, Computer program for crystal
structure refinement, University of Göttingen, Germany, 1997.
[32] A. L. Spek, PLATON – A Multipurpose Crystallographic Tool,
Utrecht University, Utrecht, The Netherlands, 2000.
[33] L. J. Farrugia, J. Appl. Crystallogr. 1997, 30, 565–568.
Received: April 6, 2006
[1] a) L. F. Lindoy, The Chemistry of Macrocyclic Complexes,
Cambridge University Press, 1989; b) E. C. Constable, Metals
and Ligand Reactivity, VCH, Weinheim, 1995.
[2] P. Comba, B. Martin, Macrocyclic Chemistry – Current Trends
and Future Perspectives (Ed.: K. Gloe), Springer, Dordrecht,
2005.
Published Online: November 21, 2006
102
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Eur. J. Inorg. Chem. 2007, 90–102