Thiacrown ethers with oxygen and sulfur for coordination: Formation of the Pd and Pt complexes and pseudorotaxane with dialkylammonium

Article abstract of DOI:10.1002/ejic.201402465

Mono-, di- tri-, and tetrathiadibenzo[24]crown-8-ethers with eight oxygen or sulfur atoms within the 24-menbered ring have been synthesized by using 1,2-benzenedithiol and 2-hydroxythiophenol as the starting materials. The thia[24]crown ethers form [2]pseudorotaxanes with dibenzylammonium salts, the association constants of which vary depending on the numbers and positions of the sulfur and oxygen atoms. The [2]pseudorotaxane of 1,4-dithiadibenzo[24]crown-8-ether (1,4-DTC) was converted into its Pd complex [PdCl₂(1,4-DTC)] by the addition of [PdCl₂(cod)] (cod = 1,5-cyclooctadiene), accompanied by the liberation of dibenzylammonium. Subsequent addition of PPh₃ to the mixture led to regeneration of the [2]pseudorotaxane. A [2]pseudorotaxane composed of 1,4-DTC and dialkylammonium with two vinyl groups at both ends of the axis component underwent a cross-metathesis reaction with an acrylate ester to form the corresponding [2]rotaxane with an interlocked structure. Mono-, di-, tri-, and tetrathiacrown ethers form pseudorotaxanes with dialkylammonium salts and transition-metal complexes with palladium(II) and platinum(II). The pseudorotaxanes of di- and tetrathiacrown ethers undergo decomplexation/complexation cycles by competitive metal coordination with PdCl₂.

Full text of DOI:10.1002/ejic.201402465

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DOI:10.1002/ejic.201402465
Thiacrown Ethers with Oxygen and Sulfur for
Coordination: Formation of the Pd and Pt Complexes and
Pseudorotaxane with Dialkylammonium
Hiroyuki Nagai,[a] Yuji Suzaki,[a] and Kohtaro Osakada*[a]
Keywords: Supramolecular chemistry / Crown compounds / Rotaxanes / Palladium / Platinum
Mono-, di- tri-, and tetrathiadibenzo[24]crown-8-ethers with
eight oxygen or sulfur atoms within the 24-menbered ring
have been synthesized by using 1,2-benzenedithiol and 2-
hydroxythiophenol as the starting materials. The thia[24]-
crown ethers form [2]pseudorotaxanes with dibenzylammo-
nium salts, the association constants of which vary de-
[PdCl2(1,4-DTC)] by the addition of [PdCl2(cod)] (cod = 1,5-
cyclooctadiene), accompanied by the liberation of dibenz-
ylammonium. Subsequent addition of PPh3 to the mixture led
to regeneration of the [2]pseudorotaxane. A [2]pseudorotax-
ane composed of 1,4-DTC and dialkylammonium with two
vinyl groups at both ends of the axis component underwent
pending on the numbers and positions of the sulfur and oxy- a cross-metathesis reaction with an acrylate ester to form the
gen atoms. The [2]pseudorotaxane of 1,4-dithiadibenzo[24]-
crown-8-ether (1,4-DTC) was converted into its Pd complex
corresponding [2]rotaxane with an interlocked structure.
ethers.[13] Recently we reported that 1,4-dithiadibenzo[24]-
crown-8-ether (1,4-DTC) forms both a pseudorotaxane
with dialkylammoniums and an (S,S)-coordinated Pd com-
plex.[14] In this paper, we present full details of the reaction
by comparison of the structures and functions of various
thiacrown ethers.
Introduction
Rotaxanes and pseudorotaxanes composed of a macro-
cyclic molecule threaded by a linear molecule have attracted
increasing attention because of their interlocked structures
as well as their unique physical and chemical properties.[1,2]
Crown ethers, the cyclic polyethers first synthesized by Ped-
ersen in 1967, were found to include alkali metals such as
lithium, sodium, and potassium, as well as secondary am-
moniums in their cavity.[3] Dibenzo[24]crown-8-ether
(DB24C8) has a larger cavity than the original crown ether
and forms stable pseudorotaxanes and rotaxanes with sec-
ondary ammoniums. The supramolecules are stabilized by
intermolecular O···H–N hydrogen bonding as well as by
auxiliary O···H–C attractive interactions.[4–7] Azide-alkyne
Huisgen cycloaddition reactions have been used in the syn-
thesis of rotaxanes.[7–9] Thiacrown ethers, in which the oxy-
gen atoms of the crown ether are partially replaced by
sulfur atoms, form coordination compounds with soft tran-
sition metals such as palladium and platinum.[10–12] Dithia-
[18]crown-6-ether has been reported to form a 1:1 complex
with Ag+ with a larger association constant (Ka = 2.2ϫ
104 m–1) than that with K+ (Ka = 1.4ϫ 10 m–1).[10] Lee and
co-workers synthesized supramolecular networks contain-
ing di- or trithia[23]crown ethers and AgI, CuI, or HgII by
the formation of exocyclic metal–sulfur coordination bonds
between the transition metals and thiacrown ethers.[12]
However, far fewer rotaxanes and pseudorotaxanes of
thiacrown ethers have been reported than of crown
Results and Discussion
Scheme 1 shows the structures of dibenzo[24]crown-8-
ether (DB24C8) and the thiacrown ethers employed in this
study: 1-Thiadibenzo[24]crown-8-ether (MTC), 1,4-DTC,
1,16-dithiadibenzo[24]crown-8-ether (1,16-DTC), 1,4,13-tri-
thiadibenzo[24]crown-8-ether (TriTC), 1,4,13,16-tetrathia-
dibenzo[24]crown-8-ether (TetraTC), and 1,4-dithiabenzo-
[12]crown-4-ether (DT12C).
Details of the synthesis of MTC and 1,4-DTC by cycliza-
tion reactions using the Williamson ether synthesis are pre-
sented in Table 1. The synthesis of 1,4-DTC has been de-
scribed previously in a preliminary report;[14] the reaction
of C6H4-1,2-(SH)2 (1a) and C6H4-1,2-[O(CH2CH2O)3Ts]2
(Ts = MeC6H4-4-SO2) in the presence of K2CO3 yielded
1,4-DTC in 58% yield, which is higher than the yields ob-
tained by using Na2CO3 (45%) and Cs2CO3 (47%; en-
tries 1–3). The differences in the yields has been attributed
to the template effect of the macrocycle for including the
metal cations K+, Na+, or Cs+ during the cyclization.[3] The
yield of 1,4-DTC was also affected by the solvent employed
[THF (58%), acetone (51%), MeCN (38%); entries 3–5].
The reaction of C6H4-1,2-(SH)(OH) (1b) and C6H4-1,2-
[a] Chemical Resources Laboratory, Tokyo Institute of Technology,
4259 R1-3 Nagatsuta, Midoriku, Yokohama 226-8503, Japan
E-mail: kosakada@res.titech.ac.jp
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SCH2 (δ = 33.4 ppm) at a higher magnetic field than those
of OCH2 (δ = 69.1, 69.7, 70.4, 70.7 ppm). The positions
of the SCH2 carbon signals are similar for TetraTC (δ =
33.3 ppm), TriTC (δ = 32.0, 33.3, 33.4 ppm), 1,4-DTC (δ =
33.4 ppm), 1,16-DTC (δ = 32.1 ppm), DT12C (δ =
35.2 ppm), and MTC (δ = 32.3 ppm).
Scheme 1. Structures of dibenzo[24]crown-8-ether (DB24C8) and
the thiacrown ethers MTC, 1,4-DTC, 1,16-DTC, TriTC, TetraTC,
and DT12C.
[O(CH2CH2O)3Ts]2 at a higher temperature and for a
longer time (110 °C, 96 h) yielded MTC (47%; entries 6 and
7).
Table 1. Optimization of the conditions for the synthesis of 1,4-
DTC and MTC.
Entry
1
Base/solvent Temp. [°C]/time Product, yield
[h]
[%]
Scheme 2. Synthesis of (A) TetraTC and TriTC, (B) 1,16-DTC, and
(C) DT12C.
1
2
1a Na2CO3/
THF
1a Cs2CO3/
THF
1a K2CO3/THF
1a K2CO3/acet-
one
1a K2CO3/
MeCN
50/72
1,4-DTC, 45
50/72
1,4-DTC, 47
The reaction of 1,4-DTC with [PdCl2(cod)] (cod = 1,5-
cyclooctadiene) in CHCl3 yielded [PdCl2(1,4-DTC)] in 72%
yield (Scheme 3, A). Similar reactions with [PdCl2-
(MeCN)2], Na2[PdCl4], and [PdCl2(nbd)] (nbd = norborna-
diene) also gave [PdCl2(1,4-DTC)] in yields of 38, 42, and
62%, respectively. The reaction of 1,4-DTC with K2[PtCl4]
in CH2Cl2/MeOH/H2O led to the formation of [PtCl2(1,4-
DTC)] in 88% yield. The 1H NMR spectrum of [PdCl2(1,4-
DTC)] shows aryl hydrogen signals at δ = 7.86 and
3
4
50/72
50/72
1,4-DTC, 58
1,4-DTC, 51
5
50/72
1,4-DTC, 38
6
7
1b K2CO3/THF
1b K2CO3/
DMF
50/72
110/72
MTC, 0
MTC, 47
The procedures for the synthesis of TriTC, TetraTC, 7.38 ppm, which are located at lower magnetic fields than
1,16-DTC, and DT12C are summarized in Scheme 2. those of 1,4-DTC (δ = 7.34, 7.13 ppm). The peaks assigned
TetraTC was synthesized in 33% yield from the reaction of to SCH2 or OCH2 are broad and observed between δ = 4.27
1a and C6H4-1,2-[S(CH2CH2O)3Ts]2 (2a), which was pre- and 3.54 ppm. The positions of the 1H NMR signals of
pared by the reaction of 1a and Cl(CH2CH2O)3H (3) in a [PtCl2(1,4-DTC)] (δ = 4.09–4.21, 3.42–3.89 ppm) are similar
ratio of 1:2, followed by tosylation using TsCl. TriTC was to those of [PdCl2(1,4-DTC)]. The reaction of K2[PtCl4],
synthesized by a similar reaction of 1a with C6H4-1,2- DT12C, and NH4PF6 yielded the dicationic platinum(II)
[O(CH2CH2O)3Ts][S(CH2CH2O)3Ts] (2b) in 46% yield, complex [Pt(DT12C)2](PF6)2 in 27% yield (Scheme 3, B).
which is higher than that achieved by using 1b and 2a (28%; The high-resolution electrospray ionization mass spectrum
Scheme 2, A). 1,16-DTC was synthesized in 19% yield from (HR-ESI-MS) of [Pt(DT12C)2](PF6)2 shows peaks at m/z =
the reaction of TsO(CH2CH2O)3Ts (4) and [(O-C6H4-2- 353.5435 and 852.0499, which have been assigned to [Pt-
SCH2CH2OCH2)2]2–, generated in situ from 1b and 4 (DT12C)2]2+ [calcd. 353.5411 (z
=
2)] and [Pt-
(Scheme 2, B). The 1:1 reaction of 1a and 4 yielded DT12C (DT12C)2](PF6)+ [calcd. 852.0469 (z = 1)], respectively. The
with a 12-membered ring (34%; Scheme 2, C). The 13C{1H} 13C{1H} NMR spectrum of [Pt(DT12C)2](PF6)2 in CD3CN
NMR spectrum of 1,4-DTC contains a signal assigned to contains six methylene carbon signals at δ = 45.4 (SCH2),
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45.8 (SCH2), 64.3 (OCH2), 67.3 (OCH2), 70.2 (OCH2), and
71.1 ppm (OCH2) and six aromatic carbons at δ = 132.3,
132.9, 133.5, 133.8, 134.1, and 134.6 ppm (C6H4), which
suggests the presence of two isomers due to the orientation
of oxymethylene chains.
Scheme 3. Synthesis of (A) [MCl2(1,4-DTC)] (M = Pd, Pt) and
(B) [Pt(DT12C)2](PF6)2.
Figure 1 depicts the molecular structures of [PdCl2(1,4-
DTC)][14] and [PtCl2(1,4-DTC)] determined by X-ray crys-
tallography. The crystals of [PdCl2(1,4-DTC)] and
[PtCl2(1,4-DTC)] are isomorphous with the space group of
P21/n (no. 14, monoclinic). The sulfur atoms of the C6H4S2
unit coordinate to PdCl2 and PtCl2, which adopt a square-
planar coordination geometry. The distances between H5
and O3, and H5 and O4, are 2.581 and 2.812 Å {in
[PdCl2(1,4-DTC)]} and 2.593 and 2.826 Å {in [PtCl2(1,4-
DTC)]} respectively, which are close to the sum of the
van der Waals radii of hydrogen and oxygen (2.72 Å).[15]
The angles of the two aromatic planes in [PdCl2(1,4-DTC)]
and [PtCl2(1,4-DTC)] are 79 and 78°, respectively. The Pd–
Cl and Pd–S bond lengths in [PdCl2(DTC)] [Pd1–Cl1
2.3153(6), Pd1–Cl2 2.3098(7) Å, Pd1–S1 2.2456(7), Pd1–S2
2.2502(6) Å] are similar to those of [PdCl2{C6H4-1,2-
(SPh)2}] [Pd–Cl 2.3159(6), 2.3116(5) Å, Pd–S 2.2679(5),
2.2719(6) Å].[16] The aromatic ring of C6H4S2 in [PdCl2(1,4-
DTC)] and [PtCl2(1,4-DTC)] is oriented to occupy the cav-
ity of the thiacrown ether. The preliminary results of the X-
ray crystallographic analysis of [Pt(DT12C)2](BF4)2 sug-
gested a square-planar structure with an anti orientation of
the oligoethylene oxide groups of the two ligands.[17] The
structure is consistent with the spectroscopic data.
Figure 1. ORTEP drawing of (A) [PdCl2(1,4-DTC)] and
(B) [PtCl2(1,4-DTC)]. Hydrogen atoms, except for H5 of [MCl2(1,4-
DTC)] (M = Pd, Pt), have been omitted.
tion of the pseudorotaxane from [NH2(CH2Ph)2]BARF
and 1,4-DTC were estimated to be 12000 m–1 (in CDCl3)
and 45 m–1 (in CD3CN) at 25 °C based on a comparison of
the peak areas of the 1H NMR signals of the NCH2
hydrogens of [{NH2(CH2Ph)2}(1,4-DTC)]BARF and that
of the added internal standard [dibenzyl, δ = 2.92 ppm
(CH2)].[18a] The association constants of the pseudorotax-
anes composed of [NH2(CH2Ph)2]X {X = BARF, Nf [=
N(SO2CF3)2], PF6} and the thiacrown ethers MTC, 1,4-
DTC, 1,6-DTC, TriTC, and TetraTC were determined simi-
larly (Table 2).
The HR-ESI-MS spectrum of a CH2Cl2 solution con-
taining [NH2(CH2Ph)2]BARF {BARF
= B[C6H3-3,5-
(CF3)2]4} and 1,4-DTC (50 μm of each compound) shows a
peak at m/z = 678.2940 assigned to the cationic pseudorot-
axane [{NH2(CH2Ph)2}(1,4-DTC)]+, (calcd. 678.2918;
1
Scheme 4). The H NMR spectrum of a CDCl3 solution of
[NH2(CH2Ph)2]BARF and 1,4-DTC (5.0 mm of each)
shows a signal at δ = 4.67 ppm (Figure 2, A) assigned to
the NCH2 hydrogen atoms of [{NH2(CH2Ph)2}(1,4-DTC)]
BARF, which is at a lower magnetic field than that of
[NH2(CH2Ph)2]BARF (δ = 4.17 ppm), which suggests C–
Scheme 4. Formation of the pseudorotaxanes by the reactions of
[NH2(CH2Ph)2]X (X = BARF, Nf, PF6) with the macrocycles
MTC, 1,4-DTC, 1,16-DTC, TriTC, TetraTC, and DB24C8.
The association constants for the formation of pseudo-
H···O bonding between the NCH2 group and oxygen atoms rotaxanes with MTC, 1,4-DTC, 1,16-DTC, TriTC, or
of 1,4-DTC. The association constants, Ka, for the forma- TetraTC with [NH2(CH2Ph)2]BARF in CDCl3 were esti-
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due to the soft sulfur atoms in 1,4-DTC, MTC, and 1,16-
DTC, which form weaker hydrogen bonds with dibenzylam-
monium than oxygen atoms and generate steric crowding in
the ring cavity as a result of their greater bulk. The trend
in the association constants of DB24C8 and the thiacrown
ethers can be rationalized by the number of sulfur atoms
and the presence of one or two monothiacatechol units. Sul-
fur atoms form weaker hydrogen bonds with secondary am-
moniums[13,19] and therefore an increase in the number of
sulfur atoms in the thiacrown ether leads to a decrease in
the association constant for pseudorotaxane formation. The
presence of monothiacatechol units in the thiacrown ether
also destabilizes the pseudorotaxanes. Thus, the thiacrown
ethers having a monothiacatechol unit, MTC (4000 m–1),
1,16-DTC (860 m–1) and TriTC (280 m–1), show smaller as-
sociation constants than that those without a monothiaca-
techol unit, 1,4-DTC (12000 m–1) and TetraTC (1300 m–1).
A dependence of the counter anions of the dibenzylammo-
niums, [NH2(CH2Ph)2]X (X = BARF, Nf, PF6), on the as-
sociation constants, Ka = 12000 (X = BARF), 620 (X =
Nf), and 480 m–1 (X = PF6) for 1,4-DTC has also been ob-
served; these association constants indicate that weakly co-
ordinating anions enhance pseudorotaxane formation.[20]
The
dialkylammoniums
[NH2(n-C10H21)2]PF6
and
[NH2(CH2C6H4-4-OCH2CH2CH=CH2)2]Nf (5) also form
pseudorotaxanes with 1,4-DTC (Ka = 52 m–1 for [{NH2(n-
C10H21)2}(1,4-DTC)]PF6, 440 m–1 for [5(1,4-DTC)], respec-
tively). The latter pseudorotaxane was employed for the
synthesis of [2]rotaxane (see below). The association con-
stants for the formation of pseudorotaxanes from thiacrown
ethers and dibenzylammoniums in CDCl3 (470–12000 m–1)
are significantly larger than those in CD3CN (25–35 m–1).
The pseudorotaxane formation of DT12C and
[NH2(CH2Ph)2]X (X = PF6, Nf, BARF) was not observed
by 1H NMR spectroscopy, which has been attributed to the
cavity of DT12C being too small to incorporate a dibenz-
ylammonium.
The addition of [PdCl2(cod)] (cod = 1,5-cyclooctadiene)
to a solution of 1,4-DTC and [NH2(CH2Ph)2]X in CDCl3
led to a decrease in the NCH2 hydrogen signal of pseudoro-
taxane (δ = 4.67 ppm) and an increase in that of free di-
benzylammonium (δ = 4.17 ppm; Figure 2, B). The decom-
plexation of the pseudorotaxanes led to the formation of
[PdCl2(1,4-DTC)] and free dibenzylammonium due to the
complexation of 1,4-DTC by PdII and extrusion of the am-
monium from the cavity partially occupied by [PdCl2(1,4-
DTC)]. Successive addition of PPh3 to the above mixture
induced a ligand exchange reaction with [PdCl2(1,4-DTC)]
to yield [PdCl2(PPh3)2] and free 1,4-DTC, which reacted
with [NH2(CH2Ph)2]X to form pseudorotaxanes
(Scheme 5), thereby increasing the NCH2 signal of the pseu-
Figure 2. 1H NMR spectra (300 MHz, CDCl3, c = 5.0 mm for each
compound, 25 °C) of (A) 1,4-DTC and [NH2(CH2Ph)2]BARF,
(B) 1,4-DTC, [NH2(CH2Ph)2]BARF, and [PdCl2(cod)], (C) TriTC
and [NH2(CH2Ph)2]BARF, and (D) TriTC, [NH2(CH2Ph)2]BARF,
and [PdCl2(cod)].
Table 2. Association constants, Ka, for the formation of pseudorot-
axanes by the reactions of [NH2(CH2Ph)2]X (X = BARF, Nf, PF6)
with the macrocyclies MTC, 1,4-DTC, 1,16-DTC, TriTC, TetraTC,
and DB24C8.
Crown ether
Pseudorotaxane
Ka [m–1][a] in CDCl3
(in CD3CN)
MTC
[{NH2(CH2Ph)2}(MTC)]BARF
[{NH2(CH2Ph)2}(MTC)]Nf
4000 (34)[b]
1100 (38)[b]
470 (25)[b]
12000 (45)[b]
620 (38)[b]
480 (28)[b]
440 (–[c])
52 (–[c])
[{NH2(CH2Ph)2}(MTC)]PF6
[{NH2(CH2Ph)2}(1,4-DTC)]BARF
[{NH2(CH2Ph)2}(1,4-DTC)]Nf
[{NH2(CH2Ph)2}(1,4-DTC)]PF6
[5(1,4-DTC)]
[{NH2(n-C10H21)2}(MTC)]PF6
[{NH2(CH2Ph)2}(1,16-DTC)]BARF
[{NH2(CH2Ph)2}(1,16-DTC)]Nf
[{NH2(CH2Ph)2}(1,16-DTC)]PF6
[{NH2(CH2Ph)2}(TriTC)]BARF
[{NH2(CH2Ph)2}(TriTC)]Nf
[{NH2(CH2Ph)2}(TriTC)]PF6
[{NH2(CH2Ph)2}(TetraTC)]BARF
[{NH2(CH2Ph)2}(TetraTC)]Nf
[{NH2(CH2Ph)2}(TetraTC)]PF6
[{NH2(CH2Ph)2}(DB24C8)]PF6
1,4-DTC
1,16-DTC
TriTC
860 (–[c])
72 (–[c])
16 (–[c])
280 (–[c])
49 (–[c])
0 (–[c])
TetraTC
DB24C8
1300 (–[c])
25 (–[c])
0 (–[c])
27000 (420)[d]
dorotaxane (δ
=
4.67 ppm). Further addition of
[a] At 25 °C, Ka = [Pseudorotaxane]/([Axle][Crown ether]). [b] See
[PdCl2(cod)] to this mixture again led to decomplexation
of the pseudorotaxanes to yield [PdCl2(1,4-DTC)] and free
dibenzylammonium. These decomplexation/complexation
ref.[14] [c] Not determined. [d] See ref.[18b]
mated to be 4000, 12000, 860, 280, and 1300 m–1, respec- processes of the pseudorotaxanes underwent four cycles by
tively. These association constants are smaller than that for the successive addition of [PdCl2(cod)] and PPh3 (Scheme 4,
[{NH2(CH2Ph)2}(DB24C8)]PF6 (27000 m–1),[18b] probably Figure 3, A).
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Scheme 5. Decomplexation/complexation reaction of the pseudoro-
taxanes [{NH2(CH2Ph)2}(1,4-DTC)]BARF and [{NH2(CH2Ph)2}-
(TetraTC)]BARF by the successive addition of [PdCl2(cod)] and
PPh3.
Scheme 6. Synthesis of the [2]rotaxanes 7 and 8.
The HR-ESI-MS spectra of 7 and 8 show peaks at m/z
= 1254.5579 and 1286.5113, respectively, which have been
assigned to the cationic [2]rotaxanes [{NH2(CH2C6H4-4-
OCH2CH2CH=CHCOO(CH2An)}2)(DB24C8)]+
(calcd.
1254.5573) and [(NH2{CH2C6H4-4-OCH2CH2CH=CH-
COO(CH2An))2}(1,4-DTC)]+ (calcd. 1286.5116). The 1H
and 13C{1H} NMR signals of 7 were assigned by using 1H-
1H and 13C{1H}-1H COSY spectroscopy. The 1H NMR
spectrum of 7 in CDCl3 shows signals at δ = 2.62, 4.42,
and 7.35 ppm assigned to the OCH2CH2, NCH2, and NH2
hydrogens of the axle component, respectively (Figure 4,
Figure 3. Cycles of fluctuation of concentrations of
(A) [{NH2(CH2Ph)2}(1,4-DTC)]BARF,
(B) [{NH2(CH2Ph)2}-
(TetraTC)]BARF, and (C) [{NH2(CH2Ph)2}(DB24C8)]BARF by
the successive addition of [PdCl2(cod)] and PPh3.
Similarreactionsofthepseudorotaxane[{NH2(CH2Ph)2}- C). The positions of these signals are at lower magnetic
(TetraTC)]BARF can also be induced by the successive ad- fields than those of the corresponding hydrogens of 5 [δ =
dition of [PdCl2(cod)] and PPh3 (Figure 3, B), although the 2.54 (OCH2CH2), 4.00 ppm (NCH2)] (Figure 4, A). The
difference in the concentrations of products is much less shift of the 1H NMR signals has been attributed to the for-
significant than for [{NH2(CH2Ph)2}(1,4-DTC)]BARF. In mation of N–H···O and C–H···O hydrogen bonds between
contrast, the addition of [PdCl2(cod)] to a solution of TriTC DB24C8 and the axle component of 7. The trans configura-
and [NH2(CH2Ph)2]BARF in CDCl3 did not lead to a de- tion of the C=C bond in the axle component of 7 was con-
crease in the NCH2 hydrogen signal of pseudorotaxane (δ firmed by the large 1H-1H coupling constant (J = 16 Hz) of
= 4.65–4.84 ppm) nor to the formation of the complex of the vinylene hydrogen atoms (δ = 5.94 ppm). 13C{1H}
TriTC with PdCl2 (Figure 2, C, D). Thus, dynamic decom- NMR signals of the vinylene carbons of 7 are observed at
plexation/complexation cycles were not observed for δ = 130.7 (OCCH=CH) and 122.9 ppm (OCCH=CH).
1
[{NH2(CH2Ph)2}(TriTC)]BARF, nor for [{NH2(CH2Ph)2}-
The H NMR spectrum of 8 in CDCl3 shows signals at
(DB24C8)]BARF (Figure 3, C) due to the weak coordina- δ = 2.61 (OCH2CH2), 4.52 (NCH2), 5.94 (d, J = 16 Hz,
tion of these thiacrown ethers to the PdII center.
OCCH=CH), and 7.41 ppm (NH2), at similar positions to
1
Scheme 6 shows the synthesis of the [2]rotaxanes com- the corresponding H NMR signals of 7 (Figure 4, D). The
posed of 1,4-DTC or DB24C8 and a dialkylammonium 1H NMR signals of the C6H4SCH2 and C6H4OCH2
bearing terminal 9-anthryl units. The ruthenium carbene hydrogens of 8 are observed at δ = 3.12 and 3.96 ppm,
complex [(H2IMes)(PCy3)Cl2Ru=CHPh] (H2IMes = N,N- respectively, which compare with signals at δ = 3.12
dimesityl-4,5-dihydroimidazol-2-ylidene) catalyzed the (C6H4SCH2) and 4.13 ppm (C6H4OCH2) for the corre-
cross-metathesis
reaction
of
[NH2(CH2C6H4-4- sponding signals of 1,4-DTC. The significant shift of the
OCH2CH2CH=CH2)2]Nf (5) with CH2=CHCOOCH2An signal of C6H4OCH2 to a higher magnetic field (Δδ =
(6, An = 9-anthryl) in the presence of DB24C8 (5 = 0.17 ppm) upon complexation and the negligible shift of
0.10 mmol, 6 = 0.20 mmol, DB24C8 = 0.10 mmol). Heating that of C6H4SCH2 indicate that the catechol oxygens of 1,4-
of the mixture in CH2Cl2 for 18 h at reflux afforded DTC interact more strongly with the axle component than
[{NH2(CH2C6H4-4-OCH2CH2CH=CHCOOCH2An)2}- the S atoms. The anthryl hydrogen peaks of 6, 7, and 8
(DB24C8)]Nf (7) in 12% yield. A similar cross-metathesis are observed at similar positions (e.g., for the 10-anthryl
reaction using 1,4-DTC gave the [2]rotaxane 8 in 7% yield. hydrogen δ = 8.52, 8.49, and 8.50 ppm, respectively). The
Eur. J. Inorg. Chem. 0000, 0–0
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SO2C6H4-4-CH3)[21] were prepared by literature methods. The
methyl derivative of DT12C has been reported.[22] The syntheses of
1,4-DTC, MTC, and [PdCl2(DTC)] have been previously re-
ported.[14] The other chemicals were commercially available. 1H and
13C{1H} NMR spectra were recorded with Varian MERCURY-300
(300 MHz) and Bruker biospinAvance III (400 MHz) spectrome-
ters. HR-ESI-MS were recorded with a micrOTOF II (Bruker)
spectrometer. Elemental analyses were performed with a LECO
CHNS-932 or Yanaco MT-5 CHN autorecorder.
C6H4-1,2-[S(CH2CH2O)3Ts]2 (2a): A DMF solution (10 mL) of
C6H4-1,2-(SH)2 (1a; 1.46 g, 10 mmol) and potassium carbonate
(4.14 g, 30.0 mmol) was stirred at room temperature for 15 min. A
DMF (10 mL) solution of 2-[2-(2-chloroethoxy)ethoxy]ethanol (3;
3.48 g, 21 mmol) was added to the mixture and stirred at 80 °C
for 64 h. The reaction mixture was filtered and the solvent was
evaporated. The residue was dissolved in THF (20 mL) and then
NaOH (1.61 g, 40 mmol) and TsCl (7.63 g, 40 mmol) were added
to the THF solution and the mixture stirred at 0 °C for 24 h. The
reaction mixture was filtered and evaporated to yield the crude
product, which was partitioned between H2O and AcOEt. The sep-
arated organic phase was dried with MgSO4. The crude product
was purified by column chromatography (SiO2, hexane/AcOEt =
1:2, Rf = 0.40) to yield 2a as a yellow oil (5.17 g, 7.23 mmol, 70%).
1H NMR (300 MHz, CDCl3, 25 °C): δ = 2.43 (s, 6 H, CH3), 3.08
(t, J = 6.6 Hz, 4 H), 3.56–3.68 (16 H, OCH2), 4.13 (m, 4 H,
TsOCH2), 7.15 (m, 2 H, 4,5-C6H4), 7.32 [6 H, 3,6-C6H4, C6H4 (Ts)
overlap], 7.79 [d, J = 7.8 Hz, 4 H, C6H4 (Ts)] ppm. 13C{1H} NMR
(75 MHz, CDCl3, 25 °C): δ = 21.6 (CH3), 32.5 (SCH2), 68.7
(OCH2), 69.3 (OCH2), 69.6 (OCH2), 70.3 (OCH2), 70.6 (OCH2),
126.6 (C6H4), 127.9 [C6H4 (Ts)], 129.3 (C6H4), 129.8 [C6H4 (Ts)],
132.8 [C6H4 (Ts)], 136.6 (C6H4), 144.8 [C6H4 (Ts)] ppm.
C32H42O10S4 (714.92): calcd. C 53.76, H 5.92, S 17.94; found C
53.33, H 5.68, S 17.56.
Figure 4. 1H NMR spectra (CDCl3, 25 °C) of (A) 5, (B) 6, (C) 7,
and (D) 8.
HR-ESI-MS and NMR results show that 7 and 8 maintain
interlocked structures in which the macrocyclic components
of 7 and 8 are located close to the ammonium nitrogen
of the axle moiety as a result of strong hydrogen-bonding
interactions between the ammonium hydrogens and the
oxygen atoms of the macrocyclic components.
C6H4-1,2-[O(CH2CH2O)3Ts][S(CH2CH2O)3Ts] (2b): A DMF solu-
tion (20 mL) of C6H4-1,2-(OH)(SH) (1b; 1.26 g, 10 mmol) and po-
tassium carbonate (3.32 g, 24 mmol) was stirred at room tempera-
ture for 1 h. A DMF (20 mL) solution of 2-[2-(2-chloroethoxy)-
ethoxy]ethanol (3; 3.53 g, 21 mmol) was added to the mixture and
stirred at 110 °C for 92 h. The reaction mixture was filtered and
the solvent was evaporated. The residue was dissolved in THF
(40 mL) and then NaOH (1.21 g, 30 mmol) and TsCl (5.71 g,
30 mmol) were added to the THF solution and stirred at 0 °C for
24 h. The reaction mixture was filtered and evaporated to yield the
crude product, which was partitioned between H2O and CH2Cl2.
The separated organic phase was dried with MgSO4. The crude
product was purified by column chromatography (SiO2, hexane/
AcOEt = 1:2, Rf = 0.48) to yield 2b as a pale-yellow oil (1.74 g,
Conclusions
We have synthesized various mono-, di-, tri-, and tetra-
thiadibenzo[24]crown-8-ethers and compared their complex
formation. The thiacrown ethers form complexes not only
with transition metals such as MIICl2 (M = Pd, Pt) but also
with the dibenzylammonium salts [NH2(CH2Ph)2]X, with
the reactions of 1,4-DTC in competition. 1,16-DTC and
TriTC do not undergo decomplexation/complexation cycles
1
2.5 mmol, 25%). H NMR (400 MHz, CDCl3, 25 °C): δ = 2.44 [s,
6 H, CH3 (Ts)], 3.08 (t, J = 7.2 Hz, 2 H, SCH2), 3.55 (m, 4 H,
because of their poor ability to undergo complexation. End- OCH2), 3.61 (m, 4 H, OCH2), 3.70 (m, 6 H, OCH2), 3.87 (t, J =
5.2 Hz, 2 H, OCH2), 4.16 (m, 6 H, OCH2), 6.86 (dd, J = 0.8,
8.0 Hz, 1 H, C6H4), 6.92 (dt, J = 1.2, 7.6 Hz, 1 H, C6H4), 7.17 (dt,
J = 1.6, 8.0 Hz, 1 H, C6H4), 7.33 [5 H, C6H4, C6H4 (Ts) overlap],
7.79 [d, J = 8.4 Hz, 4 H, C6H4 (Ts)] ppm. 13C{1H} NMR
(100 MHz, CDCl3, 25 °C): δ = 21.4 [CH3 (Ts)], 31.1 (SCH2), 68.1
(OCH2), 68.5 (OCH2 overlap), 69.1 (OCH2), 69.2 (OCH2), 69.4
(OCH2), 69.8 (OCH2), 70.1 (OCH2), 70.5 (OCH2), 70.6 (OCH2),
70.7 (OCH2), 111.9 (C6H4), 121.2 (C6H4), 124.2 (C6H4), 127.2
(C6H4), 127.8 [C6H4 (Ts)], 129.7 [C6H4 (Ts)], 132.9 [C6H4 (Ts)],
144.6 [C6H4 (Ts)], 156.7 (C6H4) ppm. C32H42O11S3 (698.9): calcd.
C 55.00, H 6.06, S 13.76; found C 54.63, H 5.84, S 13.62.
capping reactions of the pseudorotaxane composed of a di-
thiacrown ether and dialkylammonium by the 9-anthryl es-
ter yielded a [2]rotaxane. The dual role of the thiacrown
ether as the host molecule for both transition metals and
ammonium provides a new approach to the design of stimu-
lus-responsive supramolecular systems without a change in
the molecular framework.
Experimental Section
General: [NH2(CH2Ph)2]X (X = BARF {B[C6H3-3,5-(CF3)2]4}, Nf 1,16-Dithia[24]crown-8-ether (1,16-DTC): A DMF solution (20 mL)
[N(SO2CF3)2], PF6)[4b,20] and C6H4-1,2-{O(CH2CH2O)3Ts}2 (Ts = of C6H4-1,2-(OH)(SH) (1b; 252 mg, 2.0 mmol), Cs2CO3 (1.64 g,
Eur. J. Inorg. Chem. 0000, 0–0
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5.0 mmol), and TsO(CH2CH2O)3Ts (4; 458 mg, 1.0 mmol) was
stirred at 40 °C for 68 h. After the addition of an extra portion of
4 (462 mg, 1.0 mmol), the mixture was stirred further at 110 °C for
42 h. The reaction mixture was filtered and evaporated to yield the
crude product, which was partitioned between H2O and AcOEt.
The separated organic phase was dried with MgSO4, filtered, and
the solvent evaporated. The product was purified by column
chromatography (SiO2, hexane/AcOEt = 2:1, Rf = 0.10) to yield
1,16-DTC as a white solid (90 mg, 0.19 mmol, 19%). 1H NMR
(300 MHz, CDCl3, 25 °C): δ = 3.12 (t, J = 6.9 Hz, 4 H, SCH2),
3.56 (s, 4 H, OCH2), 3.65 (t, J = 6.9 Hz, 4 H, OCH2), 3.85 (s, 4 H,
OCH2), 3.95 (t, J = 4.5 Hz, 4 H, OCH2), 4.19 (t, J = 4.5 Hz, 4 H,
OCH2), 6.85 (m, 4 H, C6H4), 7.18 (dt, J = 1.5, 7.2 Hz, 2 H, C6H4),
7.34 (dd, J = 1.5, 7.2 Hz, 2 H, SCCH) ppm. 13C{1H} NMR
(75 MHz, CDCl3, 25 °C): δ = 32.1 (SCH2), 68.3 (OCH2), 69.5
(OCH2), 70.1 (OCH2), 70.4, (OCH2), 71.0 (OCH2), 111.5 (C6H4),
120.9 (C6H4), 123.5 (C6H4), 128.0 (C6H4), 132.0 (C6H4), 157.6
(C6H4) ppm. HRMS (ESI; eluent: MeCN): calcd. for
[C24H32O6S2Na]+ 503.1533; found 503.1515,. C24H32O6S2 (480.6):
calcd. C 59.98, H 6.71, S 13.34; found C 59.80, H 6.55, S 12.98.
5.6 Hz, 4 H, 4,5-C6H4), 7.31 (dd, J = 3.2, 5.6 Hz, 4 H, 3,6-
C6H4) ppm. 13C{1H} NMR (100 MHz, CDCl3, 25 °C): δ = 33.3
(SCH2), 69.7 (OCH2), 70.6 (OCH2), 126.6 (C6H4), 129.9 (C6H4),
137.3 (C6H4) ppm. C24H32O4S4(H2O)0.5 (521.76): calcd. C 55.25, H
6.38, S 24.58; found C 55.41, H 6.12, S 23.61. .
1,4-Dithiabenzo[12]crown-4-ether (DT12C):
A DMF solution
(100 mL) of 1a (142 mg, 1.0 mmol), K2CO3 (1.17 g, 8.5 mmol), and
TsO(CH2CH2O)3Ts (4; 459 mg, 1.0 mmol) was stirred at 110 °C for
90 h. After removal of insoluble solid by filtration, the solvent was
evaporated under reduced pressure. The obtained oil was dissolved
in CH2Cl2 and washed with water. The separated organic phase
was dried with MgSO4, filtered, and evaporated to yield the crude
product, which was purified by silica gel column chromatography
(hexane/AcOEt = 2:1, Rf = 0.32) to yield DT12C as a colorless oil
1
(88 mg, 0.34 mmol, 34%). H NMR (400 MHz, CDCl3, 25 °C): δ
= 3.21 (t, J = 5.6 Hz, 8 H, SCH2), 3.46 (s, 8 H, OCH2), 3.54 (t, J
= 5.6 Hz, 8 H, SCH2CH2), 7.15 (dd, J = 3.6, 6.0 Hz, 4 H, 4,5-
C6H4), 7.44 (dd, J = 3.6, 6.0 Hz, 4 H, 3,6-C6H4) ppm. 13C{1H}
NMR (100 MHz, CDCl3, 25 °C): δ = 35.2 (SCH2), 69.2 (OCH2),
70.3 (OCH2), 127.1 (C6H4), 133.3 (C6H4), 138.2 (C6H4) ppm.
HRMS (ESI; eluent: CH3CN): calcd. for [C12H16O2S2Na]+
279.0484; found 279.0493; calcd. for [(C12H16O2S2)2Na]+ 535.1076;
found 535.1078. C12H16O2S2 (256.4): calcd. C 56.22, H 6.29, S
25.01; found C 55.89, H 6.06, S 24.12.
1,4,13-Trithia[24]crown-8-ether (TriTC)
Method 1: A THF/H2O solution (20:2 mL) of 2b (69.7 mg,
0.10 mmol), C6H4-1,2-(SH)2 (1a; 14.2 mg, 0.10 mmol), and potas-
sium carbonate (55.0 mg, 0.40 mmol) was stirred at 50 °C for 72 h.
The reaction mixture was evaporated to yield the crude product,
which was partitioned between H2O and CH2Cl2. The separated
organic phase was dried with MgSO4, filtered, and the solvent
evaporated. The product was purified by column chromatography
(SiO2, hexane/AcOEt = 2:1, Rf = 0.19) to yield TriTC as a colorless
oil (22.7 mg, 0.046 mmol, 46%).
[PtCl2(1,4-DTC)]: An aqueous solution (2.0 mL) of K2[PtCl4]
(41.6 mg, 0.10 mmol) was added to a CH2Cl2 solution (1.0 mL) of
1,4-DTC (47.9 mg, 0.10 mmol). MeOH was added to the mixture
to produce a homogeneous solution. This mixture was heated at
reflux for 2 h. The reaction mixture was then evaporated to yield
the crude product, which was recrystallized from CH2Cl2 to yield
[PtCl2(1,4-DTC)] as a yellow solid (65.4 mg, 0.088 mmol, 88%). 1H
NMR (300 MHz, CDCl3, 25 °C): δ = 3.42–3.89 (18 H, SCH2,
OCH2), 4.09–4.21 (6 H, OCH2), 6.93 (br., 4 H, O2C6H4), 7.38 (br.,
1 H, S2C6H4), 7.83 (br., 1 H, S2C6H4), 7.99 (br., 2 H, SCCH) ppm.
13C{1H} NMR (100 MHz, CDCl3, 25 °C): δ = 45.5 (SCH2), 69.3
(OCH2), 70.1 (OCH2), 70.6 (OCH2), 70.7 (OCH2), 71.2 (OCH2),
114.6 (C6H4), 121.8 (C6H4), 131.1 (C6H4), 132.1 (C6H4), 137.5
(C6H4), 149.0 (C6H4) ppm. C24H32Cl2O6PtS2 (746.6): calcd. C
38.61, H 4.32, Cl 9.50, S 8.59; found C 38.32, H 4.12, Cl 9.62, S
8.08.
Method 2: A DMF solution (20 mL) of 2a (71.6 mg, 0.10 mmol),
C6H4-1,2-(OH)(SH) (1b; 12.8 mg, 0.10 mmol), and caesium carb-
onate (137 mg, 0.42 mmol) was stirred at 110 °C for 69 h. The reac-
tion mixture was evaporated to yield the crude product, which was
partitioned between H2O and AcOEt. The separated organic phase
was dried with MgSO4, filtered, and the solvent evaporated. The
product was purified by column chromatography (SiO2, hexane/
AcOEt = 2:1, Rf = 0.19) to yield TriTC as a colorless oil (14.1 mg,
1
0.028 mmol, 28%). H NMR (400 MHz, CDCl3, 25 °C): δ = 3.10
(m, 6 H, SCH2), 3.57 (s, 4 H, OCH2), 3.65 (m, 4 H, OCH2), 3.73
(m, 6 H, OCH2), 3.90 (m, 2 H, OCH2), 4.16 (m, 2 H, OCH2), 6.82
(dd, J = 1.2, 8.0 Hz, 1 H, SOC6H4), 6.88 (dt, J = 0.8, 7.6 Hz, 1
H, SOC6H4), 7.14 (3 H, SOC6H4, 4,5-S2C6H4 overlap), 7.33 (3 H,
SOC6H4, 3,6-S2C6H4 overlap) ppm. 13C{1H} NMR (100 MHz,
CDCl3, 25 °C): δ = 32.0 (SCH2), 33.3 (SCH2), 33.4 (SCH2), 68.4
(OCH2), 69.6 (OCH2 overlap), 69.7 (OCH2), 70.1 (OCH2), 70.4
(OCH2), 70.5 (OCH2), 70.5 (OCH2), 70.9 (OCH2), 111.7 (C6H4),
121.0 (C6H4), 124.0 (C6H4), 126.6 (C6H4), 126.8 (C6H4), 127.7
(C6H4), 129.9 (C6H4), 130.4 (C6H4), 131.3 (C6H4), 137.0 (C6H4),
137.7 (C6H4), 157.3 (C6H4) ppm. C24H32O5S3(H2O)0.25 (501.2):
calcd. C 57.51, H 6.54, S 19.19; found C 57.60, H 6.33, S 19.70.
[Pt(DT12C)2](PF6)2: A MeOH/H2O solution (2.0 mL/2.0 mL) of
K2[PtCl4] (16.8 mg, 0.041 mmol) and DT12C (20.5 mg,
0.080 mmol) was heated at reflux for 6 h. After cooling to room
temperature, NH4PF6 (128 mg, 0.79 mmol) was added and the mix-
ture stirred for 30 min. The solid that separated from solution was
collected by filtration and washed with water to yield the crude
product, which was purified by reprecipitation from MeCN/Et2O
to yield [Pt(DT12C)](PF6)2 as an off-white solid (10.9 mg,
0.011 mmol, 27%). X-ray crystal analysis was performed for
[Pt(DT12C)2](BF4)2, prepared by anion-exchange of LiBF4 and
[Pt(DT12C)2](PF6)2. 1H NMR (400 MHz, CD3CN, 25 °C): δ =
3.28–3.34 (m, 4 H, CH2), 3.36–3.42 (m, 4 H, CH2), 3.50–3.56 (m,
1,4,13,16-Tetrathia[24]crown-8-ether (TetraTC): A DMF solution
(20 mL) of 2a (71.8 mg, 0.10 mmol), 1a (14.4 mg, 0.10 mmol), and 4 H, CH2), 3.83 (ddd, J = 2.5, 8.2, 14.8 Hz, 4 H, CH2), 3.94 (ddd,
potassium carbonate (55.1 mg, 0.40 mmol) was stirred at 110 °C
for 58 h. The reaction mixture was evaporated to yield the crude
product, which was partitioned between H2O and AcOEt. The sep-
arated organic phase was dried with MgSO4, filtered, and the sol-
vent evaporated. The product was purified by column chromatog-
raphy (SiO2, hexane/AcOEt = 2:1, Rf = 0.18) to yield TetraTC as
a white solid (16.8 mg, 0.033 mmol, 33%). 1H NMR (400 MHz,
CDCl3, 25 °C): δ = 3.09 (t, J = 6.4 Hz, 8 H, SCH2), 3.58 (s, 8 H,
OCH2), 3.70 (t, J = 6.4 Hz, 8 H, SCH2CH2), 7.11 (dd, J = 3.2,
J = 2.6, 5.8, 11.8 Hz, 4 H, CH2), 4.12 (ddd, J = 2.1, 5.7, 14.8,
J(Pt–H) = 72 Hz, 4 H, Pt-SCH2), 7.77 (dd, J = 3.3, 6.0 Hz, 4 H,
C6H4), 8.01 (dd, J = 3.3, 6.0 Hz, 4 H, C6H4) ppm. 13C{1H} NMR
(100 MHz, CD3CN, 25 °C): δ = 45.4 (SCH2), 45.8 (SCH2), 64.3
(OCH2), 67.3 (OCH2), 70.2 (OCH2), 71.1 (OCH2), 132.3 (C6H4),
132.9 (C6H4), 133.5 (C6H4), 133.8 (C6H4), 134.1 (C6H4), 134.6
(C6H4) ppm. HRMS (ESI; eluent: CH3CN): calcd. for
[(C12H16O2S2)2Pt]2+ 353.5411; found 353.5435; calcd. for
[(C12H16O2S2)2PtPF6]+ 852.0469; found 852.0499. (C12H16O2S2)2-
Eur. J. Inorg. Chem. 0000, 0–0
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FULL PAPER
PtP2F12 (997.8): calcd. C 28.89, H 3.23, S 12.85; found C 28.83, H
3.11, S 13.08.
tal StructureTM for Windows program package. All hydrogen atoms
were included at the calculated positions with fixed thermal param-
eters. For [Pt(DT12C)2](BF4)2, the oxymethylene carbon and oxy-
gen atoms of [Pt(DT12C)2](PF6)2 were refined isotropically. The
hydrogen atoms of these oxymethylene carbon atoms were not lo-
cated and not included in refinement.
Control of Formation of Pseudorotaxane by the Reaction of
[PdCl2(cod)] and PPh3: A CDCl3 solution (1.0 mL) of 1,4-DTC
(2.4 mg, 5 μmol) or TetraTC (2.5 mg, 5 μmol), [NH2(CH2Ph)2]X
(X = BARF, Nf, PF6; 5 μmol), and dibenzyl (0.9 mg, 5 μmol) was
prepared. [PdCl2(cod)] (1.4 mg, 5 μmol) was added to the solution
at 25 °C followed by PPh3 (2.6 mg, 10 μmol) also at 25 °C. Each
CCDC-978603 (for [PdCl2(1,4-DTC)]), -1007730 (for [PtCl2(1,4-
DTC)]), and -1007731 (for [Pt(DT12C)2](BF4)2) contain the supple-
mentary 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.
1
reaction was monitored by H NMR spectroscopy.
7:
[NH2(CH2C6H4-4-OCH2CH2CH=CH2)2]Nf
(5;
63 mg,
0.10 mmol) and DB24C8 (45.8 mg, 0.102 mmol) was dissolved in
CH2Cl2 (2.0 mL) followed by the addition of CH2=CHCOO-
(CH2An) (6; 53.6 mg, 0.204 mmol) and a Ru–carbene complex
{[(H2IMes)(PCy3)Cl2Ru=CHPh], H2IMes = N,N-dimesityl-4,5-di-
hydroimidazol-2-ylidene; 3.0 mg, 3.5 μmol}. The mixture was
heated at reflux for 18 h and the solvent removed by evaporation
to give a brown oil. The crude product was purified by preparative
HPLC (CHCl3) to give 7 (19.3 mg, 12.6 μmol, 12%). 1H NMR
Acknowledgments
The authors thank their colleagues at the Center for Advanced Ma-
terials Analysis, Technical Department, Tokyo Institute of Technol-
ogy for NMR (Dr. Yoshihisa Sei), HR-ESI-TOF-MS (Mr. Masato
Koizumi), and elemental analysis (Ms. Chieko Hara). This work
was supported by the Ministry of Education, Culture, Sports, Sci-
ence and Technology (MEXT), Japan (Grants-in-Aid for Scientific
Research for Young Scientists, grant number 21750058 and Scien-
tific Research in Innovative Areas “The Coordination Program-
ming – Science of Supermolecular Structure and Creation of
Chemical Elements”, grant numbers 22108509 and 24108711).
(300 MHz, CDCl3, 25 °C):
δ = 2.62 (d, J = 4 Hz, 4 H,
CH=CHCH2), 3.38 (br., 8 H, C6H4OC2H4OCH2), 3.68 (br., 8 H,
C6H4OCH2CH2), 3.95 (t, J = 4 Hz, 4 H, C6H4OCH2-axis), 4.03
(br., 8 H, C6H4OCH2-DB24C8), 4.42 (br., 4 H, NCH2), 5.94 (d, J
= 16 Hz, 2 H, OCCH=CH), 6.22 (s, 4 H, AnCH2), 6.64 (d, J =
8 Hz, 4 H, C6H4-axis), 6.72 (d, J = 4 Hz, 4 H, C6H4-DB24C8), 6.83
(m, 4 H, C6H4-DB24C8), 7.04 (m, 2 H, OCCH=CH), 7.13 (d, J =
8 Hz, 4 H, C6H4-axis), 7.35 (br., 2 H, NH2), 7.48 (m, 4 H, 3-An),
7.56 (m, 4 H, 2-An), 8.02 (d, J = 8 Hz, 4 H, 4-An), 8.35 (d, J =
8 Hz, 4 H, 1-An), 8.49 (s, 2 H, 10-An) ppm. 13C{1H} NMR
(100 MHz, CDCl3, 25 °C): δ = 31.8 (CH=CHCH2), 51.9 (NCH2),
58.8 (AnCH2), 65.8 (C6H4OCH2-axis), 68.2 (C6H4OCH2-DB24C8),
70.2 (C6H4OCH2CH2), 70.6, 70.7 (C6H4OC2H4OCH2), 112.8
(C6H4-DB24C8), 114.5 (C6H4-axis), 121.7 (C6H4-DB24C8), 122.9
(OCCH=CH), 123.8, 123.9 (1-An), 125.1 (3-An), 126.2, 126.7 (2-
An), 129.1 (4-An), 129.2 (10-An), 130.7 (COCH=CH), 131.1,
131.4, 145.5, 147.4, 159.1, 166.5 (C=O) ppm. MS (ESI; eluent:
MeCN): calcd. for [C78H80NO14]+ 1254.5573; found 1254.5579.
C80H80F6N2O18S2(CHCl3)0.5 (1595.31): calcd. C 60.61, H 5.09, N
1.76, S 4.02; found C 60.81, H 5.73, N 1.79, S 3.69.
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8: Compound 5 (123 mg, 0.20 mmol) and 1,4-DTC (96.4 mg,
0.20 mmol) was dissolved in CH2Cl2 (4.0 mL) followed by the ad-
dition of CH2=CHCOOAn (6; 105 mg, 0.40 mmol) and a Ru–carb-
ene complex [(H2IMes)(PCy3)Cl2Ru=CHPh] (35.6 mg, 42 μmol).
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13.1 μmol, 7%). 1H NMR (400 MHz, CDCl3, 25 °C): δ = 2.61 (br.,
4 H, CH=CHCH2), 3.12 (br., 4 H, SCH2), 3.30 (br., 4 H, OCH2),
3.47 (br., 4 H, OCH2), 3.56 (br., 4 H, OCH2), 3.70 (br., 4 H,
OCH2), 3.96 (br., 8 H, C6H4OCH2), 4.52 (br., 4 H, NCH2), 5.94
(d, J = 16 Hz, 2 H, OCCH=CH), 6.22 (s, 4 H, AnCH2), 6.66 (br.,
4 H, C6H4), 6.80 (br., 4 H, C6H4), 7.06 (br., 2 H, OCCH=CH),
7.18 (br., 8 H, C6H4), 7.41 (br., 2 H, NH2), 7.48 (m, 4 H, 3-An),
7.56 (m, 4 H, 2-An), 8.02 (d, J = 8 Hz, 4 H, 4-An), 8.35 (d, J =
8 Hz, 4 H, 1-An), 8.50 (s, 2 H, 10-An) ppm. HRMS (ESI; eluent:
acetone): calcd. for [C78H80NO12S2]+ 1286.5116; found 1286.5113.
X-ray Structure Analyses of [PdCl2(1,4-DTC)], [PtCl2(1,4-DTC)],
and [Pt(DT12C)2](BF4)2: Crystals of [PdCl2(1,4-DTC)], [PtCl2(1,4-
DTC)], and [Pt(DT12C)2](BF4)2 suitable for X-ray diffraction
study were obtained by recrystallization from CHCl3 and CH2Cl2,
respectively. All measurements were carried out with a Rigaku
AFC-10R Saturn diffractometer with graphite-monochromated
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Eur. J. Inorg. Chem. 0000, 0–0
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¯
= 881.45, triclinic, space group P1(no. 2), a = 9.041(10), b =
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Received: May 26, 2014
Published Online: ᭿
Eur. J. Inorg. Chem. 0000, 0–0
9
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I42465
/KAP1
Date: 30-07-14 17:33:59
Pages: 10
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FULL PAPER
Pseudorotaxane Synthesis
H. Nagai, Y. Suzaki,
K. Osakada* ................................... 1–10
Thiacrown Ethers with Oxygen and Sulfur
for Coordination: Formation of the Pd and
Pt Complexes and Pseudorotaxane with
Dialkylammonium
Mono-, di-, tri-, and tetrathiacrown ethers
form pseudorotaxanes with dialkyl-
ammonium salts and transition-metal com-
plexes with palladium(II) and platinum(II).
The pseudorotaxanes of di- and tetrathia-
crown ethers undergo decomplexation/
complexation cycles by competitive metal
coordination with PdCl2.
Keywords: Supramolecular chemistry
/
Crown compounds
ladium / Platinum
/ Rotaxanes / Pal-
Eur. J. Inorg. Chem. 0000, 0–0
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim