New polydentate trimethylsilyl chalcogenide reagents for the assembly of polyferrocenyl architectures

Article abstract of DOI:10.1002/chem.201400185

A series of polychalcogenotrimethylsilane complexes Ar(CH ₂ESiMe₃)_n, (Ar=aryl; E=S, Se; n=2, 3, and 4) can be prepared from the corresponding polyorganobromide and M[ESiMe ₃] (M=Na, Li). These represent the first examples of the incorporation of such a large number of reactive -ESiMe₃ moieties onto an organic molecular framework. They are shown to be convenient reagents for the preparation of the polyferrocenylseleno- and thioesters from ferrocenoyl chloride. The synthesis, structures, and spectroscopic properties of the new silyl chalcogen complexes 1,4-(Me₃SiECH₂) ₂(C₆Me₄) (E=S, 1; E=Se, 2), 1,3,5-(Me ₃SiECH₂)₃(C₆Me₃) (E=S, 3; E=Se, 4) and 1,2,4,5-(Me₃SiECH₂)₄(C ₆H₂) (E=S, 5; E=Se, 6) and the polyferrocenyl chalcogenoesters [1,4-{FcC(O)ECH₂}₂(C₆Me ₄)] (E=S, 7; E=Se, 8), [1,3,5-{FcC(O)ECH₂} ₃(C₆Me₃)] (E=S, 9; E=Se, 10) and [1,2,4,5-{FcC(O)ECH₂}₄(C₆H₂)] (E=S, 11 illustrated; E=Se, 12) are reported. The new polysilylated reagents and polyferrocenyl chalcogenoesters have been characterized by multinuclear NMR spectroscopy (¹H, ¹³C, ⁷⁷Se), electrospray ionization mass spectrometry and, for complexes 1, 2, 3, 4, 7, 8, and 11, single-crystal X-ray diffraction. The cyclic voltammograms of complexes 7-11 are presented.

Full text of DOI:10.1002/chem.201400185

DOI: 10.1002/chem.201400185
Full Paper
&
Molecular Frameworks
New Polydentate Trimethylsilyl Chalcogenide Reagents for the
Assembly of Polyferrocenyl Architectures
Mahmood Azizpoor Fard,[a] Bahareh Khalili Najafabadi,[a] Mahdi Hesari,[a]
Mark S. Workentin,[a, b] and John F. Corrigan*[a, b]
Abstract: A series of polychalcogenotrimethylsilane com-
plexes Ar(CH2ESiMe3)n, (Ar=aryl; E=S, Se; n=2, 3, and 4)
can be prepared from the corresponding polyorganobro-
mide and M[ESiMe3] (M=Na, Li). These represent the first ex-
amples of the incorporation of such a large number of reac-
tive ꢀESiMe3 moieties onto an organic molecular framework.
They are shown to be convenient reagents for the prepara-
tion of the polyferrocenylseleno- and thioesters from ferro-
cenoyl chloride. The synthesis, structures, and spectroscopic
properties of the new silyl chalcogen complexes 1,4-
(Me3SiECH2)2(C6Me4) (E=S, 1; E=Se, 2), 1,3,5-(Me3SiECH2)3-
(C6Me3) (E=S, 3; E=Se, 4) and 1,2,4,5-(Me3SiECH2)4(C6H2)
(E=S, 5; E=Se, 6) and the polyferrocenyl chalcogenoesters
[1,4-{FcC(O)ECH2}2(C6Me4)] (E=S, 7; E=Se, 8), [1,3,5-
{FcC(O)ECH2}3(C6Me3)] (E=S, 9; E=Se, 10) and [1,2,4,5-
{FcC(O)ECH2}4(C6H2)] (E=S, 11 illustrated; E=Se, 12) are re-
ported. The new polysilylated reagents and polyferrocenyl
chalcogenoesters have been characterized by multinuclear
NMR spectroscopy (1H, 13C, 77Se), electrospray ionization
mass spectrometry and, for complexes 1, 2, 3, 4, 7, 8, and
11, single-crystal X-ray diffraction. The cyclic voltammograms
of complexes 7–11 are presented.
Introduction
In a complementary vein for this work, the preparation of
polyferrocenylthio- and selenoesters has been pursued.[21] The
chemistry of chalcogenoesters has had a strong development,
due to the importance of these types of compounds as inter-
mediates in synthetic organic chemistry.[22–24] Chalcogenoesters
The chemistry of ferrocene (Fc)-containing molecules and ma-
terials continues to develop due to the favorable electronic
(redox) properties of ferrocene and its ease of functionaliza-
tion.[1–3] Such systems have a wide range of applications in ma-
terials science including use as sensors,[4] catalysts,[4a,5] electro-
active materials[6] and aerospace materials,[7] in cancer thera-
peutics[8] and other medicinal applications,[9] and as a smokeless
fuel additive.[10]
have been employed as acylating reagents in synthesis of cor-
26]
responding acids,[25] esters,[25] amides,[25a,b,
ketones,[27,28] and
aldehydes.[29,30] Acyl chalcogenides are also employed as build-
ing blocks for the synthesis of asymmetric aldols[31] and hetero-
cyclic compounds such as oxazoles[32] and b-lactone.[33] Chalco-
genoesters also have been applied to the synthesis of natural
compounds such as proteins[34] and alkaloids.[35]
Much research focus has been placed on polyferrocene ar-
chitectures in which the organometallic units are linked with
different organic spacers such as alkenes,[11] alkynes,[12]
arenes,[13] heterocycles,[14] annulenes,[15] and even larger mole-
cules such as C60.[16] These types of complexes are suitable for
investigating intramolecular electronic interactions in the cor-
responding mixed-valent species between the ferrocenyl units
through the organic backbone.[14a–e,17] Efforts have also been
devoted to the incorporation of multiple ferrocene units into
polymers,[18] dendrimeric frameworks,[19] and inorganic nano-
clusters.[20]
Developed methodologies for the incorporation of these
molecules into organic compounds generally involve the prep-
aration of acyl radicals[36,37] and anions[38] under mild condi-
tions. New methods for the synthesis of thio- and selenoesters
are still being developed; organo(trimethylsilyl) chalcogenides
have been shown to be a convenient source of organochalco-
genide (REꢀ)[39] including for the synthesis of chalcogenoester-
s,[21a] and are of course well-developed for the preparation of
metal chalcogen complexes.[40] The preparation of new frame-
works with multiple ꢀESiMe3 moieties would offer routes to
the assembly of polythio- and selenoesters. Rimpler first re-
ported that the sulfur silane reagent Me3SiOC(O)CH2SSiMe3
reacts directly with acyl chloride under ambient conditions to
yield the corresponding thioester Me3SiOC(O)CH2SC(O)R via the
formation of Me3SiCl.[41] Aryl- and alkyl(trimethylsilyl)chalcoge-
nides offer a convenient, easily handled source of “ArEꢀ” and
“REꢀ” (E=S, Se, Te), respectively. Ogura and co-workers demon-
strated a similar methodology for the heavier congener telluri-
um reagent PhTeSiMe3.[42] Twelve years later, reductive cleavage
[a] M. A. Fard, B. Khalili Najafabadi, M. Hesari, Prof. Dr. M. S. Workentin,
Prof. Dr. J. F. Corrigan
Department of Chemistry, The University of Western Ontario
London, ON, N6A 5B7 (Canada)
Fax: (+1)519-661-3022
E-mail: corrigan@uwo.ca
[b] Prof. Dr. M. S. Workentin, Prof. Dr. J. F. Corrigan
Centre for Advanced Materials and Biomaterials Research
The University of Western Ontario, London, ON (Canada)
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of the SeꢀSi bond in arylselenotrimethylsilane PhSeSiMe3 was
reported by Zhang and Zhang as a novel method for the syn-
thesis of selenoesters.[43]
In contrast to sulfur and tellurium, the chemistry of selenium
Ar-/R-SeSiMe3 has not been as extensively developed for the
preparation of chalcogenoesters. Recently the use of nucleo-
philic fluoride anion to increase the reactivity of PhSeSiMe3 in
the reaction with acid chloride has been demonstrated.[44] Con-
comitantly, we reported a new series of diselenoesters from
the simple reaction of mono- or di(acid chlorides) with di- or
monosubstituted organochalcogen–silane reagents in both sol-
vent and under solvent-free conditions.[21a] The synthesis of an
oligoselenoester complex in this work outlined the potential of
this chemistry for the formation of polyselenoester complexes,
including small oligomers. Herein, we describe the preparation
of a new class of di-, tri-, and tetrasubstituted thio- and seleno-
trimethylsilanes and demonstrate their utility for the assembly
of a series of polysubstituted ferrocenylthio- and selenoesters,
via their reaction with ferrocenoyl chloride.
Results and Discussion
Various synthetic methods for chalcogenoesters have been re-
ported and are usually based on the reactions of acyl chloride
or acid anhydrides with a source of chalcogenide anion such
as chalcogenols (by deprotonation),[45] dichalcogenides (by re-
duction),[46] or alkali metal chalcogenolates.[47,48] Additional
methods, including metal-catalyzed reactions, have also been
reported.[49–57] The demonstrated reactivity of disubstituted
1,1’-bis(trimethylsilylseleno)ferrocene and related reagents for
the preparation of diselenoesters[21a,58] suggests that polychal-
cogenosilanes could behave efficiently in transferring chalco-
geno moieties for the formation the polychalcogenoester-
s.[20a,b,59]
Scheme 1. Synthesis of 1–6.
and tri- substituted complexes 1–4 are similar, although they
differ slightly compared to those of the corresponding tetra-
substituted aromatics 5–6. The chemical shifts of the Si(CH3)3
moieties in the selenium complexes appear to lower field in
both 1H and 13C{1H} NMR spectra versus the corresponding
sulfur complexes. The 1H NMR spectra display the expected sin-
glet for the equivalent methylene groups. All ꢀCH2ꢀ groups in
analogous compounds show similar chemical shift values in
The polychalcogenosilanes of the general formula Ar(-
CH2ESiMe3)n (Ar=aryl; E=S, Se; n=2–4) 1–6 are readily pre-
pared in good yield by the reaction of lithium (trimethylsilyl)
chalcogenolate Li[ESiMe3] with the corresponding di-, tri-, and
tetra-bromobenzyl arene (Scheme 1). Li[ESiMe3] is first pre-
pared in situ through the addition of bis(trimethylsilyl)chalco-
genide E(SiMe3)2 to a stirred solution of nBuLi in tetrahydrofur-
an at 08.[60] The portion-wise addition of organobromine re-
agents to the solution of Li[ESiMe3] in Et2O at room tempera-
ture, followed by stirring for 12 h, yielded 1, 3, and 5 (white
powders) and 2, 4, and 6 (pale-yellow powders) upon extrac-
tion with a hydrocarbon solvent. Similar reactions to
1
their H NMR spectra (1, 2=3.72, 3.75 ppm; 3, 4=3.72 ppm;
and 5, 6=3.83 ppm), but the corresponding resonances in the
13C{1H} NMR spectra of the selenides have lower chemical shift
values (1, 3, and 5=25.9–27.5 ppm; 2, 4, and 6=18.0–
18.7 ppm). The 77Se{1H} chemical shift for tetrasubstituted 6 is
significantly shifted (ꢀ19.0 ppm) compared to the correspond-
ing values for the di- and trisubstituted complexes 2 and 4
(ꢀ70.2 and ꢀ70.7 ppm, respectively); this is likely to be due to
interamolecular Se···Se nonbonding interactions in solution, as
described for complementary systems.[62]
substitute the bromine centers by using Na[ESiMe3][61]
are equally effective in the formation of 1–6. The ad-
dition of the organobromine reagents to a suspension
of Na[ESiMe3] in tetrahydrofuran at room tempera-
ture, and production of NaBr, makes the extraction of
1–6 somewhat easier, with comparable yields of
products. All six compounds are highly air sensitive;
however, they are stable for several days in solution
at room temperature under an inert atmosphere.
The solution NMR chemical shifts of 1–6 are re-
ported in Table 1. The chemical shift values of the di-
Table 1. NMR spectroscopic data for 1–6 in CDCl3. Chemical shifts are reported in
ppm.
1H
13C
77Se
Si(CH3)3 CH3 CH2 CH Si(CH3)3 CH3 CH2 ꢀCꢀ
Sulfides
1
3
5
2
4
6
0.41
0.40
0.34
0.49
0.47
0.44
2.32 3.72
2.46 3.72
3.83 7.21 0.9
2.32 3.75
2.42 3.72
0.7
0.7
16.1 26.1 132.7, 135.1
15.6 25.9 134.2, 134.7
27.5 131.8, 137.4
16.1 18.4 132.6, 135.2 -70.7
16.0 18.0 133.6, 134.9 -70.2
18.7 132.1, 137.5 - 19.0
Selenides
1.6
1.6
3.83 7.09 1.8
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Table 2. Crystallographic data and parameters for compounds 1–4, 6–8 and 11.[a]
1
2
3
4
6
7
8
11
formula
formula weight
crystal system
space group
a [ꢁ]
b [ꢁ]
c [ꢁ]
a [8]
b [8]
C18H34S2Si2
370.75
triclinic
C18H34Se2Si2
464.55
triclinic
C21H42S3Si3
475.00
triclinic
C21H42Se3Si3
615.70
triclinic
C22H46Se4Si4
738.79
monoclinic
P21/c
11.5701(11)
6.5046(5)
21.8713(18)
90
95.733(5)
90
1637.8(2)
2
C34H34Fe2O2S2
650.43
triclinic
C34H34Fe2O2Se2
744.23
monoclinic
P21/c
5.748(2)
23.046(10)
21.718(8)
90
95.791(10)
90
2862.3(19)
4
C54H46Fe4O4S4
1110.55
triclinic
¯
P1
¯
P1
¯
P1
¯
P1
¯
P1
¯
P1
6.4020(5)
7.3238(4)
11.9751(9)
103.313(4)
97.665(3)
92.821(5)
539.64(7)
1
6.2310(3)
7.5548(4)
12.1830(7)
103.265(2)
97.939(3)
93.901(3)
549.88(5)
1
10.0634(1)
11.5851(2)
13.0520(2)
86.4372(9)
68.2215(9)
79.5821(9)
1389.75(4)
2
10.125(2)
11.630(2)
13.257(3)
87.81(3)
67.71(3)
82.00(3)
1430.2(6)
2
8.0896(16)
10.354(2)
18.010(4)
94.803(15)
100.219(10)
98.517(14)
1458.8(5)
2
5.7476(5)
13.3324(12)
14.9342(13)
91.675(4)
100.183(4)
93.298(4)
1123.60(17)
1
g [8]
V [ꢁ3]
Z
1cal [gcmꢀ3
]
1.141
0.354
202
1.403
3.468
238
1.135
0.402
516
1.430
3.990
624
1.498
4.636
740
1.481
1.168
676
1.727
3.588
1496
1.641
1.501
570
M (MoKa) [mmꢀ1
F(000)
]
temperature [K]
qmin, qmax [8]
total reflns
unique reflns
R(int)
150
3.0, 27.8
4614
2492
0.025
150
2.8, 27.7
4460
2510
0.024
150
1.7, 39.8
90834
16840
0.071
150
150
110
1.2, 28.0
20483
20483
0.000
110
110
1.4, 27.5
21808
5171
0.061
2.2, 27.6
11696
6548
1.8, 25.0
47682
2880
2.8, 26.4
47265
5860
0.034
0.252
0.094
R1
0.0405,
0.0932
0.0551
0.1007
1.046
0.0397,
0.1021
0.0470
0.1051
1.173
0.0543,
0.1269
0.1550
0.1736
0.992
0.0496,
0.1198
0.0816
0.1360
1.042
0.0438,
0.0714
0.1195
0.0856
0.913
0.0525,
0.0952
0.1081
0.1138
1.008
0.0415,
0.0838
0.0754
0.0955
1.016
0.0639
0.1683
0.0904
0.1935
1.079
wR2 [Iꢁ2s (I)]
R1 (all data)
wR2 (all data)
GOF
min peak
max peak
-0.298
0.284
-0.596
0.546
-0.626
1.012
-0.687
1.494
-0.601
0.134
-0.534
0.529
-0.562
0.855
-0.699
2.064
2
2
[a] R1 =ꢀ(jFojꢀjFcj)/ꢀFo, wR2 =[ꢀ(w(Fo ꢀFc2)2)/ꢀ(wFo2)]1/2, GOF=[ꢀ(w(Fo ꢀFc2)2)/(NobservnsꢀNparams)]1/2
.
To date, only a few crystal structures with ꢀCESiMe3 groups
have been reported,[59a,63] although the structural chemistry of
Ar(CH2ER)n in general is more mature.[64] The structures of 1–4
and 6 were confirmed by X-ray crystallographic analyses. Crys-
tallographic data and data collection parameters are summar-
ized in Table 2. Complexes 1–4 crystallized in the triclinic space
¯
group P1. Complex 6 crystallized in the space group P21/c. The
molecular structures of 1–4 and 6 and some of the selected in-
termolecular bond distances and angles are provided in
Figure 1, Figure 2, Figure 3, and Figures S1 and S2 in the Sup-
porting Information. The SꢀSi [2.1387(7)–553(7) ꢁ], SeꢀSi
[2.276(2)–87(2) ꢁ], SꢀC [1.837(2)–52(2) ꢁ] and SeꢀC [1.982(5)–
97(6) ꢁ] distances in these four compounds are typical for the
sulfur–silicon, selenium–silicon, sulfur–carbon and selenium–
carbon single bonds.[65]
Figure 1. Thermal ellipsoid plot (40% probability level) of 2 with the atom
numbering scheme. The chalcogenoesters reside about crystallographic in-
versions center relating the two halves of the molecules. Selected bond dis-
tances [ꢁ] and angles [8]: C(4)ꢀSe(1) 1.995(4), Se(1)ꢀSi(1) 2.285(1), C(4)-Se(1)-
Si(1) 97.5(1).
Examination of the structures of 1 and 2 shows that they
have a crystallographic center of symmetry. The two ꢀESiMe3
groups are held in trans configuration in the crystalline state
and the CꢀEꢀSi moieties are approximately perpendicular to
the central C6 plane (1 87.898, 2 88.858). In the crystal struc-
tures of 3 and 4, two ꢀESiMe3 groups lie on one side of the ar-
omatic ring with the third group on the opposite face. These
patterns mirror the structural features of ArMe6ꢀx(CH2ER)x (R=
alkyl, aryl).[66] The structure of 6 also has a center of symmetry;
in this case adjacent ꢀSeSiMe3 groups are on opposite sides of
the C6 ring;[64a] this conformation minimizes steric constraints.
The demonstrated reactivity of ꢀSeSiMe3 moieties towards
acid chlorides suggested a facile route for the formation of
polyferrocenylchalcogenoesters using 1–6. In the first attempt
to synthesize polyferrocene based chalcogenoesters, 1,4-
[(CH3)3SiSeCH2]2(C6Me4) 2 was reacted with ferrocynoyl chloride
at room temperature in tetrahydrofuran. After stirring for six
hours, workup and purification yielded 1,4-[{FcC(O)SeCH2}2-
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Figure 2. Thermal ellipsoid plot (40% probability level) of 4 with the atom
numbering scheme. Selected bond distances [ꢁ] and angles [8]: C(7)ꢀSe(1)
1.997(6), C(9)ꢀSe(2) 1.982(5), C(11)ꢀSe(3) 1.994(5), Se(1)ꢀSi(1) 2.283(2), Se(2)ꢀ
Si(2) 2.276(2), Se(3)ꢀSi(3) 2.287(2), C(7)-Se(1)-Si(1) 98.7(1), C(9)-Se(2)-Si(2)
102.2(1), C(11)-Se(3)-Si(3) 100.4(1).
Figure 3. Thermal ellipsoid plot (40% probability level) of 6 with the atom
numbering scheme. Selected bond distances [ꢁ] and angles [8]: C(4)ꢀSe(1)
1.9839(1), C(5)ꢀSe(2) 1.9849(2), Se(1)ꢀSi(1) 2.2873(2), Se(2)ꢀSi(2) 2.2857(2),
C(4)-Se(1)-Si(1) 97.64(14), C(5)-Se(2)-Si(2) 102.85(16).
(C6Me4)]
8
in 40% yield
(Scheme 2). The reaction of fer-
rocenoyl chloride with the other
silyl–selenium complexes re-
quired more forcing conditions.
Thus, compound 6, with four ꢀ
SeSiMe3 groups about the aryl
ring, reacted cleanly with four
equivalents of [FcC(O)Cl] at 40–
458C to form the corresponding
1,2,4,5-[{FcC(O)SeCH2}4(C6H2)] 12
in 45% yield. Similar reaction
conditions with the sulfur com-
plexes 1, 3, and 5 did not lead
to the formation of thioesters;
higher reaction temperature
yielded only modest evidence of
S–Si activation, as indicated by
1H NMR spectroscopy.
However, when reactions were
performed by heating the silyl
chalcogen reagents at 60–658C
in the presence of ferrocenoyl
chloride (solvent free condi-
tions), both seleno- and thioest-
ers proved readily accessible.
Using this methodology, the pol-
yferrocenyl
complexes
[1,4-
{FcC(O)ECH2}2(C6Me4)] (E=S, 7;
E=Se, 8), [1,3,5-{FcC(O)ECH2}3-
(C6Me3)] (E=S, 9; E=Se, 10) and
[1,2,4,5-{FcC(O)ECH2}4(C6H2)] (E=
S, 11; E=Se, 12) were prepared
(Scheme 2).
Scheme 2. Synthesis of 7–12.
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ed bond lengths and angles for complexes 7 and 8
are presented in Figures 4 and 5, respectively. The C=
O [1.205(6)–1.216(5) ꢁ] and EꢀC [E=S; 1.782(3)–
1.821(4) ꢁ, E=Se; 1.957(5)–1.975(5) ꢁ] distances are
in the range observed for thio- and selenoester com-
plexes.[67,68] Like their corresponding silylated precur-
sors, the chalcogenoester groups are oriented in
a trans configuration; in both complexes, the cyclo-
pentadienyl rings adopting a staggered conforma-
tion.
Table 3. NMR spectroscopic data for 7–12 in CDCl3. Chemical shifts are reported in
ppm.
1H
Fc
13C
CH3 CH2 CH Fc
CH3 CH2 ꢀCꢀ
C=O
Sulfides
7
9
4.24, 4.49, 2.34 4.37
4.87
4.24, 4.51, 2.43 4.37
4.83
68.7, 70.4,71.6, 16.5 29.2 132.0,
193.8
79.0
68.9, 70.8,
72.0, 81.4
133.5
16.6 25.3 133.1,
135.2
195.0
192.8
195.2
193.9
194.0
11 4.17, 4.45,
4.33 7.45 69.0, 70.6,
71.8, 79.0
29.8 132.9,
135.8
4.83
Selenides
8
4.24, 4.51, 2.31 4.38
4.84
68.9, 70.8,
72.0, 81.5
68.9, 70.6,
71.8, 79.1
17.0 25.6 133.3,
133.4
16.5 29.2 131.8,
136.3
In complex 7 the two ferrocenoyl groups are
nearly perpendicular, with an angle of 88.098 be-
tween C5-Fe-C5 vectors. The central arene C6 is not
parallel with either of the two substituted C5H4 rings
(rotated 60.468 and 65.128). With dihedral angles
C13-C12-S1-C11 and C16-C23-S2-C24 of 173.568 and
132.458, respectively, one of the thioester groups is
10 4.22, 4.48, 2.46 4.37
4.86
12 4.20, 4.48,
4.31 7.36 69.0, 70.8,
72.0, 81.2
25.3 132.8,
136.8
4.81
The NMR chemical shifts for the chalcogeno esters 7–12 are
listed in Table 3. The H NMR spectra show one singlet (4.17–
perpendicular to the central C6 whereas the other is rotated by
about 408. The analogous configuration for complex 8 is not
observed in the solid state; here the two selenoester groups
are held in a trans configuration but with the two ferrocenoyl
1
4.24 ppm) and two virtual triplets (4.48–4.87 ppm) assigned to
the C5H5 and substituted Cp rings of ferrocene, respectively.
The chemical shift values of the
CH2 groups are shifted downfield
(4.31–4.38 ppm) compared with
the corresponding silyl–chalco-
gen precursor (3.72–3.83 ppm).
Unlike the downfield shift of
arene CH resonance in 11 and
12 (dDꢂ0.2 ppm), there is no
considerable change in the
chemical shifts of the arene CH3
groups in 7, 8, 9, and 10. The
chemical shift values in the
13C NMR spectra of the methyl-
ene groups for the selenoesters
generally appear downfield of
Figure 4. Thermal ellipsoid plot (40% probability level) of 7 with the atom numbering scheme. Selected bond dis-
tances [ꢁ] and angles [8]: C(12)ꢀS (1) 1.821(4), C(11)ꢀS(1) 1.780(4), C(1)ꢀC(11) 1.469(5), C(23)ꢀS(2) 1.821(4), C(24)ꢀ
S(2) 1.782(3), C(24)ꢀC(25) 1.470(5), C(11)-S(1)-C(12) 101.7(2), C(1)-C(11)-S(1) 113.2(3), C(23)-S(2)-C(24) 101.7(2), C(25)-
C(24)-S(2) 114.0(3), C(1)-C(11)-S(1)-C(12) 178.1(3), C(25)-C(24)-S(2)-C(23) 169.8(3), C(13)-C(12)-S(1)-C(11) 132.4(3),
C(16)-C(23)-S(2)-C(24) 173.6(3).
their respective ꢀSeSiMe3 precur-
sor, with smaller changes ob-
served for the thioesters. The
large downfield shifts in 77Se
NMR of the selenoesters com-
pared to 2, 4, and 6 may be ex-
plained with the introduction of
withdrawing C=O group bonded
to the selenium atom versus
Me3Si. The carbonyl carbon
chemical shifts are observed be-
tween 192–195 ppm in their re-
spective 13C NMR spectra.
The
structure
of
[1,4-
was
{FcC(O)SCH2}2(C6Me4)]
7
solved and refined in the triclinic
¯
space group P1., while [1,4-
Figure 5. Thermal ellipsoid plot (40% probability level) of 8 with the atom numbering scheme. Selected bond dis-
tances [ꢁ] and angles [8]: C(12)ꢀSe(1) 1.975(5), C(11)ꢀSe(1) 1.961(4), C(11)ꢀC(1) 1.458(6), C(23)ꢀSe(2) 1.957(5),
C(24)ꢀSe(2) 1.947(4), C(24)ꢀC(25) 1.461(6), C(11)-Se(1)-C(12) 98.0(2), C(1)-C(11)-Se(1) 113.9(3), C(23)-Se(2)-C(24)
96.2(2), C(25)-C(24)-Se(2) 113.8(3), C(1)-C(11)-Se(1)-C(12) 171.1(3), C(25)-C(24)-Se(2)-C(23) 175.9(3), C(13)-C(12)-Se(1)-
{FcC(O)SeCH2}2(C6Me4)] 8 crystal-
lizes in monoclinic space group
P21/c. The molecular structure in
the crystal together with select- C(11) 124.5(3), C(16)-C(23)-Se(2)-C(24) 150.0(3).
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cyclic voltammograms were measured under inert atmosphere
using a glassy carbon working electrode and the potentials
were calibrated using ferrocene as an internal standard (0.34 V
vs. SCE).[69] Figure 7 shows cyclic voltammograms (CVs) of ferro-
cene and complexes 7–11.
The CVs of 7–10 (Figure 7B, C), show what appears to be
single chemically reversible oxidation processes with anodic to
cathodic peak current ratios (Ipa/Ipc) for all four complexes 7–10
near unity. These are due to the reversible oxidation of the fer-
rocene moieties incorporated on these complexes. The current
increases with the increasing ferrocene content of each of the
complexes, with the integrated current area proportional to
the number of ferrocene units in each of the complexes, rela-
tive to ferrocene. The apparent single, chemically reversible ox-
idation for each complex indicates that the ferrocenyl moieties
on them oxidize at the same (or very similar potential) with
little or no interaction between them.[70] The oxidation poten-
tials of 7–12 are shifted to more positive potentials than that
observed for ferrocene (Eo =0.34 V vs SCE) under the same
conditions with peak potential (Ep) values of about 0.68 V (E=
S) and 0.72 V (E=Se), due to the presence of the electron-
withdrawing chalcogenoester groups on the C5H4 rings.[68b] The
CVs for complexes 11 and 12 also show a single oxidation for
the oxidation of the ferrocene moiety, but the reverse scan
shows evidence for adsorption of these compounds onto the
electrode (Figure 7D), likely due to their limited solubility in
this solvent, particularly upon oxidation.
Figure 6. Thermal ellipsoid plot (40% probability level) of 11 with the atom
numbering scheme. Selected bond distances [ꢁ] and angles [8]: C(11)ꢀS(1)
1.7634(2), C(12)ꢀS(1) 1.8067(1), C(12)ꢀC(13) 1.5225(1), C(17)ꢀS(2) 1.7765(1),
C(16)ꢀS(2) 1.8293(1), C(15)ꢀC(16) 1.5013(1), C(11)-S(1)-C(12) 98.66(2), C(1)-
C(11)-S(1) 114.6(3), C(16)-S(2)-C(17) 99.8(2), C(18)-C(17)-S(2) 113.6(3), C(1)-
C(11)-S(1)-C(12) 172.9(3), C(13)-C(12)-S(1)-C(11) 74.0(4), C(18)-C(17)-S(2)-C(16)
168.9(3), C(15)-C(16)-S(2)-C(17) 138.9(3).
Conclusion
groups nearly parallel, with an angle of only 11.748 between
planes defined by the C5 rings.
In summary, we have demonstrated a straightforward synthesis
of a novel series of di-, tri-, and tetra-polychalcogenotrimethyl-
silanes Ar(CH2ESiMe3)n (n=2–4). These have been used as “pro-
tected chalcogenides” for the facile preparation of polyferroce-
nylseleno- and thioester assemblies by reaction with ferrocene
acid chloride. The synthetic methodology is likely to be useful
in the synthesis of other chalcogenoesters, and Ar(CH2ESiMe3)n
[1,2,4,5-{FcC(O)SCH2}4(C6H2)] 11 crystallized in the triclinic
¯
space group P1. with a center of inversion relating two halves
of the molecule. The molecular structure and some of the se-
lected intermolecular bond distances and angles are provided
in Figure 6. As expected the large, adjacent ferrocenylthioester
groups reside on opposite sides of the C6 ring. Two of the
equivalent C5H4 rings (bonded to
Fe1/Fe1A) are rotated 61.678 out
of the plane defined by the cen-
tral C6, while the other two are
nearly perpendicular, twisted by
88.318.
Electrochemistry studies
Given the incorporation of the
ferrocene units onto complexes
7–12, it was incumbent to mea-
sure their electrochemical be-
havior by using cyclic voltamme-
try. To this end, 1 mm solutions
of each polyferrocenyl complex
7–12 in dichloromethane con-
taining 0.1m tetrabuthylammo-
Figure 7. Cyclic voltammograms (CVs) of 1 mm solutions of A) ferrocene, B) compounds 7 (solid) and 8 (dashed),
C) compounds 9 (solid) and 10 (dashed), and D) compound 11 in dichloromethane with 0.1m TBAPF6 as support-
nium
hexafluorophosphate
(TBAPF6) were prepared. The ing electrolyte. All the CVs shown are recorded at 100 mVsꢀ1 and are referenced to ferrocene at 0.34 V vs SCE.
&
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themselves hold enormous potential for the assembly of poly-
nuclear metal–chalcogen (cluster) architectures. We are cur-
rently developing this reaction chemistry.
Synthesis of 1
Method 1:
1,4-bis(bromomethyl)-2,3,5,6-tetramethylbenzene
(0.500 g, 1.56 mmol) and freshly prepared Li[SSiMe3] (3.13 mmol)
were each dissolved in anhydrous diethyl ether (30 mL and 15 mL,
respectively) and cooled to 08C. The solutions were mixed and
stirred for 1 h at this temperature and overnight at room tempera-
ture resulting in an opaque suspension. The solvent was removed
in vacuum and chloroform (30 mL) and pentane (15 mL) were
added to solubilize the product 1. The solid LiBr was removed by
twice passing the mixture through a sintered glass frit packed with
Celite. The solvent was removed in vacuo yielding an off-white
solid.
Experimental Section
All syntheses were carried out under an atmosphere of high-purity
dried nitrogen using standard double-manifold Schlenk line tech-
niques and nitrogen-filled glove boxes unless otherwise stated. Sol-
vents were dried and collected using an MBraun MB-SP Series sol-
vent purification system with tandem activated alumina (tetrahy-
drofuran) and an activated alumina/copper redox catalyst (pen-
tane).
Method 2: 0.322 g (2.51 mmol) of Na[SSiMe3] was added portion-
wise to a solution of (0.400 g, 1.25 mmol) 1,4-bis(bromomethyl)-
2,3,5,6-tetramethylbenzene in tetrahydrofuran (40 mL) at room
temperature followed by stirring overnight. The product was ex-
tracted as described above. Platelike, colorless single crystals suita-
ble for X-ray crystallography were obtained from slow evaporation
Chlorinated solvents (dichloromethane, chloroform and [D]chloro-
form) were dried and distilled over P2O5. Chemicals were used as
received from Alfa Aesar and/or Aldrich. [FcC(O)Cl],[71] 1,3,5-tris(bro-
1
of 1 in heptane (91% yield). M.p. 122–1268C; H NMR (400.1 MHz,
momethyl)-2,4,6-trimethylbenzene,[72]
1,2,4,5-tetrakis(bromome-
CDCl3, 238C): d=3.72 (s, 4H, CH2), 2.32 (s, 12H, ArꢀCH3), 0.41 ppm
(s, 18H, SiꢀCH3); 13C{1H} NMR (100.6 MHz, CDCl3, 238C): d=135.1,
132.7 (C6), 26.1 (CH2), 16.1 (ArꢀCH3), 0.7 ppm (SiꢀCH3); HRMS (EI):
m/z calcd for C18H34S2Si2: 370.1640 [M+]; found: 370.1645; elemen-
tal analysis calcd (%) for C18H34S2Si2 (370.76): C 58.31, H 9.24, S
17.30; found: C 58.12, H 9.30, S 17.05.
thyl)benzene,[73] Li[ESiMe3][60] and Na[ESiMe3][61] (E=S, Se) were syn-
thesized according to literature procedures. 1,4-bis(bromomethyl)-
2,3,5,6-tetramethylbenzene was prepared according to similar pro-
cedure
for
1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene.[72]
1H NMR (400.1 MHz, CDCl3, 238C): d=4.61 (s, 4H, CH2), 2.34 ppm (s,
12H, ArꢀCH3); 13C{1H} NMR (100.6 MHz, CDCl3, 238C): d=134.6,
134.0 (C6), 31.0 (CH2), 15.9 ppm (ArꢀCH3).
A BAS 100B\W Electrochemical Analyzer was used for cyclic voltam-
metry (CV) experiments. A homemade glassy carbon (GC, Tokai GC-
20) working electrode 3 mm in diameter was prepared by polish-
ing over silicon carbide papers (500, 1200, 2400, and 4000) fol-
lowed by diamond paste (Struers, 1 and 0.25 mm). The GC electro-
des were stored in ethanol and polished before each set of experi-
ments with the 0.25 mm diamond paste (Struers), rinsed with dry
ethanol (Commercial Alcohols) and sonicated in dry ethanol for
5 min. Platinum wires served as the reference and counter electro-
des. Electrochemical experiments were carried out in dry CH2Cl2
(Caledon) containing 0.1m tetrabutylammonium hexafluorophos-
phate (TBAPF6) as the supporting electrolyte. Potentials are refer-
enced internally to ferrocene (0.342 V vs. SCE) added at the end of
the experiments.
Synthesis of 2
1,4-Bis(bromomethyl)-2,3,5,6-tetramethylbenzene
(0.500 g,
1.56 mmol) in tetrahydrofuran (30 mL) was reacted with Na-
[SeSiMe3] (0.547 g, 3.12 mmol), which was added portion-wise. The
suspension was stirred for 12 h at room temperature resulting in
a white cloudy suspension. The solvent was removed in vacuum
and pentane (50 mL) was added to solubilize 2. NaBr was removed
by passing the mixture through a sintered glass frit packed with
Celite. The solvent was removed in vacuo yielding an off-white
solid (80% yield). Colorless plate like single crystals suitable for X-
ray diffraction were obtained by slow evaporation of 2 in hexanes.
1
M.p. 151–1528C; H NMR (399.8 MHz, CDCl3, 238C): d=3.75 (s, 4H,
CH2), 2.32 (s, 12H, ArꢀCH3), 0.49 ppm (s, 18H, SiꢀCH3); 13C{1H} NMR
(100.6 MHz, CDCl3, 238C): d=135.2, 132.6 (C6), 18.4 (CH2), 16.1 (Arꢀ
CH3), 1.6 ppm (SiꢀCH3); 77Se{1H} NMR (76.2 MHz, CDCl3, 238C): d=
ꢀ70.7 ppm; HRMS (EI): m/z calcd for C18H34[76Se][80Se]Si2: 464.0556
[M+]; found: 464.0555.
Mass spectra and exact mass determinations were performed on
a Bruker micrOTOF II instrument or Finningan MAT 8400. Elemental
analysis was performed by Laboratoire d’Analyze ꢂlementaire de
l’Universitꢃ de Montrꢃal, Montrꢃal, Canada, and Chemisar Laborato-
ries, Guelph, Canada.
Single-crystal X-ray diffraction measurements were completed on
Enraf–Nonius KappaCCD (1, 2, and 4) and Bruker APEX-II CCD (3, 4,
7, 8 and 11) diffractometers equipped with graphite-monochro-
mated MoKa (l=0.71073 ꢁ) radiation. Single crystals of the com-
plexes were carefully selected, immersed in paraffin oil and mount-
ed on MiteGen micromounts. The structures were solved using
direct methods and refined by the full-matrix least-squares proce-
dure of SHELXTL.[74] All non-hydrogen atoms, with the exception of
disordered carbon centers, were refined with anisotropic thermal
parameters. Hydrogen atoms were included as riding on their re-
spective carbon atoms. For 7, the TWIN command in SHELXTL was
used to refine the structure. CCDC-978321 (1), CCDC-978322 (2),
CCDC-978323 (3), CCDC-978324 (4), CCDC-978325 (6), CCDC-
978326 (7), CCDC-978327 (8), and CCDC-978328 (11) 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
Synthesis of 3
1,3,5-Tris(bromomethyl)-2,4,6-trimethylbenzene
(0.500 g,
1.25 mmol) in tetrahydrofuran (30 mL) was reacted with Na[SSiMe3]
(0.482 g, 3.76 mmol) as described for the preparation of 2 (98%
yield). Colorless cubic prism single crystals suitable for X-ray diffrac-
tion were obtained by slow evaporation of 3 in hexanes. M.p. 134–
1
1378C; H NMR (400.1 MHz, CDCl3, 238C): d=3.72 (s, 6H, CH2), 2.46
(s, 9H,ArꢀCH3), 0.40 ppm (s, 27H, SiꢀCH3); 13C{1H} NMR (100.6 MHz,
CDCl3, 238C): d=134.7, 134.2 (C6), 25.9 (CH2), 15.6 (ArꢀCH3),
0.7 ppm (SiꢀCH3); HRMS (EI): m/z calcd for C21H42S3Si3: 474.1756
[M+]; found: 474.1766; elemental analysis calcd (%) for C21H42S3Si3
(475.01): C, 53.10; H, 8.91; S, 20.25; found: C, 52.94; H, 8.67; S,
20.01.
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by column chromatography and eluted using 25:75 acetonitrile:di-
Synthesis of 4
chloromethane (40% yield). M.p. 187–1908C.
1,3,5-Tris(bromomethyl)-2,4,6-trimethylbenzene
(0.500 g,
Method 2: 1,4-(Me3SiSeCH2)2(C6Me4) (0.220 g, 0.473 mmol) was
mixed with 2 equiv of [FcC(O)Cl] (0.235 g, 0.947 mmol) as solids in
a Schlenk tube under vacuum. The sample was placed in a preheat-
ed (658C) oven, whereupon the reagents formed a dark-red solid.
After 12 h the mixture was cooled to room temperature. ClSiMe3
was removed in vacuo, and the residue was washed with n-pen-
tane. The residue was purified by column chromatography and
eluted using 25:75 acetonitrile:dichloromethane (50% yield).
Orange platelike single crystals of 8 were obtained by diffusing n-
pentane onto dichloromethane solution. 1H NMR (400.1 MHz,
CDCl3, 238C): d=4.84 (vt, 4H), 4.51 (vt, 4H), 4.38 (s, 4H, CH2), 4.24
(s, 10H, Cp), 2.31 ppm (s, 12H, CH3); 13C{1H} NMR (100.6 MHz,
CDCl3, 238C): d=195.2 (C=O), 133.4, 133.3 (C6), 81.5, 72.0, 70.8,
68.9 (Fc), 25.6 (CH2), 17.0 ppm (CH3); 77Se{1H} NMR (76.2 MHz,
CDCl3, 238C): d=528.4 ppm; HRMS (ESI): m/z calcd for C34H34Fe2O2-
[78Se][80Se]: 743.9596 [M+]; found: 743.9604; elemental analysis
calcd (%) for C34H34Fe2O2Se2 (744.24): C 54.87, H 4.60; found: C
54.59, H 4.70.
1.25 mmol) was reacted with Na[SeSiMe3] (0.658 g, 3.76 mmol, in
80 mL tetrahydrofuran) as described for the preparation of 2 (75%
yield). Single crystals suitable for X-ray diffraction were obtained by
slow evaporation of 4 in hexanes. M.p. 129–1328C; 1H NMR
(400.1 MHz, CDCl3, 238C): d=3.72 (s, 6H, CH2), 2.42 (s, 9H, ArꢀCH3),
0.47 ppm (s, 27H, SiꢀCH3); 13C{1H} NMR (100.6 MHz, CDCl3, 238C):
d=134.9, 133.6 (C6), 18.0 (CH2), 16.0 (ArꢀCH3), 1.6 ppm (SiꢀCH3);
77Se{1H} NMR (76.2 MHz, CDCl3, 238C): d=ꢀ70.2 ppm; HRMS (EI):
m/z calcd for C21H42[78Se][80Se]2Si3: 616.0098 [M+]; found: 616.0084.
Synthesis of 5
1,2,4,5-Tetrakis(bromomethyl)benzene (0.700 g, 1.56 mmol) in di-
ethyl ether (20 mL) was reacted with freshly prepared Li[SSiMe3]
(6.22 mmol in 50 mL diethyl ether) as described for 1 (65% yield).
1
M.p. 104–1078C; H NMR 400.1 MHz, CDCl3, 238C): d=7.21 (s, 2H,
HꢀAr), 3.83 (s, 8H, CH2), 0.34 ppm (s, 36H, SiꢀCH3); 13C{1H} NMR
(100.6 MHz, CDCl3, 238C): d=137.4, 131.8 (C6), 27.5 (CH2), 0.9 ppm
(SiꢀCH3); HRMS (ESI): m/z calcd for C22H46S4Si4: 550.1559 [M+];
found: 550.1552.
Synthesis of 9
A portion of 1,3,5-(Me3SiSCH2)3(C6Me3) (0.116 g, 0.244 mmol) was
reacted with (0.182 mg, 0.732 mmol) of [FcC(O)Cl] in solvent-free
conditions, as described for the preparation of 8 (see above). After
appropriate workup, 9 was isolated as a dark-red solid (60% yield).
M.p. 208–2108C; 1H NMR (400.1 MHz, CDCl3, 238C): d=4.83 (vt,
6H), 4.51 (vt, 6H), 4.37 (s, 6H, CH2), 4.24 (s, 15H, Cp), 2.43 ppm (s,
9H, CH3); 13C{1H} NMR (100.6 MHz, CDCl3, 238C): d=195.0 (C=O),
135.2, 133.1 (C6), 81.4, 72.0, 70.8, 68.9 (Fc), 25.3 (CH2), 16.6 ppm
(CH3); HRMS (ESI): m/z calcd for C45H42Fe3O3S3: 894.0344 [M+];
found: 894.0356; elemental analysis calcd (%) for C45H42Fe3O3S3
(894.54): C 60.42, H 4.73, S 10.75; found: C 59.75, H 4.80, S 10.86.
Synthesis of 6
1,2,4,5-Tetrakis(bromomethyl)benzene (0.600 g, 1.33 mmol) was re-
acted with freshly prepared Li[SSiMe3] (5.34 mmol in 70 mL diethyl
ether) as described for 1 (64% yield). Colorless needlelike single
crystals suitable for X-ray diffraction were obtained by slow evapo-
1
ration of 6 in heptane. M.p. 104–1078C; H NMR (400.1 MHz, CDCl3,
238C): d=7.09 (s, 2H, HꢀAr), 3.83 (s, 8H, CH2), 0.44 ppm (s, 36H,
SiꢀCH3); 13C{1H} NMR (100.6 MHz, CDCl3, 238C): d=137.5, 132.1
(C6), 18.7 (CH2), 1.8 ppm (SiꢀCH3); 77Se{1H} NMR (<76.2 MHz, CDCl3,
238C): d=ꢀ19.0 ppm.
Synthesis of 10
Synthesis of 7
A portion of 1,3,5-(Me3SiSeCH2)3(C6Me3) (0.294 g, 0.478 mmol) was
reacted with (0.356 g, 1.43 mmol) of [FcC(O)Cl] as described for the
preparation of 8 (see above). After appropriate workup, 10 was iso-
lated as dark-red solid (45% yield). M.p. 209–2118C; 1H NMR
(400.1 MHz, CDCl3, 238C): d=4.86 (vt, 6H), 4.48 (vt, 6H), 4.37 (s,
6H, CH2), 4.22 (s, 15H, Cp), 2.46 ppm (s, 9H, CH3); 13C{1H} NMR
(100.6 MHz, CDCl3, 238C): d=193.9 (C=O), 136.3, 131.8 (C6), 79.1,
71.8, 70.6, 68.9 (Fc), 29.2 (CH2), 16.5 ppm (CH3); 77Se{1H} NMR
(76.2 MHz, CDCl3, 238C): d=528.2 ppm; elemental analysis calcd
(%) for C45H42Fe3O3Se3 (1037.2): C 52.21, H 4.09; found: C 52.41, H
4.23.
1,4-(Me3SiSCH2)2(C6Me4) (0.186 g, 0.502 mmol) was mixed with
2 equiv of [FcC(O)Cl] (0.249 g, 1.00 mmol) as solids in an evacuated
Schlenk tube. The sample was placed in a preheated (658C) oven,
whereupon the reagents formed a dark-red solid. After 10 h the
mixture was cooled to room temperature. ClSiMe3 was removed in
vacuo, and the residue was washed with n-pentane. The crude
compound was then purified by column chromatography and
eluted using 25:75 acetonitrile/dichloromethane (60% yield). Small
orange platelike single crystals of 7 were obtained by slow evapo-
ration of 1:20 acetonitrile:dichloromethane solution. M.p. 206–
1
2098C; H NMR (400.1 MHz, CDCl3, 238C): d=4.87 (vt, 4H) (vt=vir-
tual triplet), 4.49 (vt, 4H), 4.37 (s, 4H, CH2), 4.24 (s, 10H, Cp),
2.37 ppm (s, 12H, CH3); 13C{1H} NMR (100.6 MHz, CDCl3, 238C): d=
193.8 (C=O),133.5, 132.0 (C6), 79.0, 71.6, 70.4, 68.7 (Fc), 29.2 (CH2),
16.5 ppm (CH3); HRMS (ESI): m/z calcd for C34H34Fe2O2S2: 650.0699
[M+]; found: 650.0700; elemental analysis calcd (%) for
C34H34Fe2O2S2 (650.45): C 62.78, H 5.27, S 9.86; found: C 62.89, H
5.44, S 9.86.
Synthesis of 11
1,2,4,5-(Me3SiSCH2)4(C6H2) (0.101 g, 0.183 mmol) was mixed with
[FcC(O)Cl] (0.182 g, 0.731 mmol) at 258C in a Schlenk tube under
vacuum. The sample was placed in a preheated (60–658C) oven.
After 14 h, the mixture became solid. ClSiMe3 was removed in
vacuo, and the residue was washed with n-pentane. After appropri-
ate workup, 11 was isolated as a dark-red solid (66% yield). The
residue was purified in two steps by silica and alumina column
chromatography and eluted using 25:75 acetonitrile:dichlorome-
thane and 12.5:87.5 heptane/dichloromethane, respectively. Small
orange needlelike single crystals of 11 were obtained by slow
evaporation of 1:5 heptane/dichloromethane solution (50% yield).
Synthesis of 8
Method 1: To 1,4-(Me3SiSeCH2)2(C6Me4) (0.093 g, 0.200 mmol) in tet-
rahydrofuran (10 mL),
a
solution of [FcC(O)Cl] (0.100 mg,
0.401 mmol, 2 equiv) in tetrahydrofuran (10 mL) was mixed at
258C. After 2 h of stirring at room temperature, the solvent and
volatile ClSiMe3 were removed under vacuum. After washing the
residue with n-pentane, the remaining dark-red solid was purified
1
M.p. 185–1898C; H NMR (400.1 MHz, CDCl3, 238C): d=7.45 (s, 2H,
ArꢀH), 4.83 (vt, 8H), 4.45 (vt, 8H), 4.33 (s, 8H, CH2), 4.17 ppm (s,
20H, Cp); 13C{1H} NMR (100.6 MHz, CDCl3, 238C): d=192.8 (C=O),
&
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ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Full Paper
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135.8, 132.9 (C6), 79.0, 71.8, 70.6, 69.0 (Fc), 29.8 ppm (CH2); HRMS
(ESI): m/z calcd for C54H46Fe4O4S4: 1109.9676 [M+]; found:
1109.9655; elemental analysis calcd (%) for C54H46Fe4O4S4 (1110.6): C
58.40, H 4.17, S 11.55; found: C 57.29, H 3.96, S 11.83.
Synthesis of 12
Method 1: To 1,2,4,5-(Me3SiSeCH2)4(C6H2) (0.111 g, 0.150 mmol) in
tetrahydrofuran (15 mL),
a
solution of [FcC(O)Cl] (0.150 g,
0.601 mmol, 4 equiv) in tetrahydrofuran (10 mL) was mixed at
258C. After 4 h of stirring at room temperature, the solvent and
ClSiMe3 were removed under vacuum. The red solid was washed
with n-pentane and the product was purified by column chroma-
tography, eluted using 25:75 acetonitrile:dichloromethane (45%
yield). M.p. 198–2018C.
Method 2: 1,2,4,5-(Me3SiSeCH2)4(C6H2) (0.174 g, 0.236 mmol) was
mixed with [FcC(O)Cl] (0.234 g, 0.943 mmol, 4 equiv) as solids in an
evacuated Schlenk tube. The sample was placed in a preheated
(60–658C) oven, whereupon the reagents formed a dark-red solid.
After 14 h, the mixture was cooled to room temperature. ClSiMe3
was removed in vacuo and after appropriate workup, 12 was iso-
lated as a dark-red solid (63% yield). 1H NMR (400.1 MHz, CDCl3,
238C): d=7.36 (s, 2H, ArꢀH), 4.81 (vt, 8H), 4.48 (vt, 8H), 4.31 (s,
8H, CH2), 4.20 ppm (s, 20H, Cp); 13C{1H} NMR (100.6 MHz, CDCl3,
238C): d=194.0 (C=O), 136.8, 132.8 (C6), 81.2, 72.0, 70.8, 69.0 (Fc),
25.3 ppm (CH2); 77Se{1H} NMR (400 MHz, CDCl3, 238C): d=
528.4 ppm; HRMS (ESI): m/z calcd for C54H46Fe4O4[78Se][80Se]3:
1299.7462 [M+]; found: 1299.7465; elemental analysis calcd (%) for
C54H46Fe4O4Se4 (1298.2): C 49.96, H 3.57; found: C 49.11, H 3.80.
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We are grateful for financial support from the Natural Sciences
and Engineering Research Council of Canada (NSERC) for this
research. NSERC, the Government of Ontario, The University of
Western Ontario and the Canada Foundation for Innovation
are thanked for equipment funding.
Keywords: chalcogen
· cyclic voltammetry · ferrocene ·
polydentate · selenoester · thioester
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Received: January 16, 2014
Published online on && &&, 0000
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FULL PAPER
Bond after bond: A series of polychal-
cogenotrimethylsilane complexes Ar(-
CH2ESiMe3)n, (Ar=aryl; E=S, Se; n=2,
3, and 4) have been prepared that in-
corporate a large number of reactive ꢀ
ESiMe3 moieties onto an organic molec-
ular framework (see figure). They are
shown to be convenient reagents for
the preparation of the polyferrocenylse-
leno- and thioesters from ferrocenoyl
chloride.
&
Molecular Frameworks
M. A. Fard, B. Khalili Najafabadi,
M. Hesari, M. S. Workentin, J. F. Corrigan*
&& – &&
New Polydentate Trimethylsilyl
Chalcogenide Reagents for the
Assembly of Polyferrocenyl
Architectures
Polyferrocenyl architectures……are prepared from
a series of new poly(trimethylsilylchalcogen) reagents
and ferrocenoyl chloride. As described in the Full Paper
by J. F. Corrigan et al. on p. &&&& ff., The assemblies
are formed via thioester or selenoester linkages, teth-
ering the ferrocenyl fragments to a central ring.
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Chem. Eur. J. 2014, 20, 1 – 12
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12
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!