A new C-anionic tripodal ligand 2-{bis(benzothiazolyl)(methoxy)methyl}phenyl and its bismuth complexes

Article abstract of DOI:10.1039/d1dt01071a

A new tripodal C-anionic ligand, 2-{bis(benzothiazolyl)(methoxy)methyl}phenyl (L), was stably generated by the reaction of the ligand precursor (L′), the corresponding bromide (2-BrC₆H₄)(MeO)C(C₇H₄NS)₂(C₇H₄NS = 2-benzothiazolyl), withnBuLi at ?104 °C in the presence of TMEDA (N,N,N′,N′-tetramethylethylenediamine). The ligand lithium salt reacted with BiCl₃to give a 2?:?1 complex L₂BiCl. A 1?:?1 complex LBiCl₂was obtained in good yield by the redistribution reaction between L₂BiCl and BiCl₃. X-ray diffraction analysis revealed that the ligand L coordinated in an expected κ³-C,N,N′ coordination mode in LBiCl₂, while it coordinated in κ³-C,N,O and κ²-C,O coordination modes in L₂BiCl. The ligand precursor reacted with BiX₃(X = Cl, Br) to give 1?:?1 complexes L′BiX₃and was found to act as a neutral tripodal C(π),N,N-ligand.

Full text of DOI:10.1039/d1dt01071a

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A new C-anionic tripodal ligand
2-{bis(benzothiazolyl)(methoxy)methyl}phenyl
and its bismuth complexes†
Cite this: Dalton Trans., 2021, 50,
7949
Received 31st March 2021,
Accepted 18th May 2021
c
Shigeru Shimada, *a Shuang-Feng Yin b and Ming Bao
DOI: 10.1039/d1dt01071a
rsc.li/dalton
A new tripodal C-anionic ligand, 2-{bis(benzothiazolyl)(methoxy) type ligands. Organobismuth compounds have attracted
methyl}phenyl (L), was stably generated by the reaction of the increasing interest as reagents8,9 as well as catalysts10 in
ligand precursor (L’), the corresponding bromide (2-BrC6H4)(MeO) organic transformations. Since bismuth forms relatively weak
C(C7H4NS)2 (C7H4NS = 2-benzothiazolyl), with nBuLi at −104 °C in Bi–E (E = elements) bonds,11 the selection of ligands is impor-
the presence of TMEDA (N,N,N’,N’-tetramethylethylenediamine). tant to obtain stable bismuth compounds suitable for such
The ligand lithium salt reacted with BiCl3 to give a 2 : 1 complex applications. Cyclic organobismuth compounds bearing a bis
L2BiCl. A 1 : 1 complex LBiCl2 was obtained in good yield by the (aryl)-type ligand with additional intramolecular coordination
redistribution reaction between L2BiCl and BiCl3. X-ray diffraction by
a
donor atom, such as RN(CH2C6H4)2Bi–R,10a,b,c,12
analysis revealed that the ligand L coordinated in an expected S(CH2C6H4)2Bi–R,10b,e,13 SO2(C6H4)2Bi–R,9b,e,10f,h,14 and SO
κ3-C,N,N’ coordination mode in LBiCl2, while it coordinated in (vNR)(C6H4)2Bi–R,10f generally have high thermal stability
κ3-C,N,O and κ2-C,O coordination modes in L2BiCl. The ligand and are often used as reagents and catalysts. Monoaryl pincer-
precursor reacted with BiX3 (X = Cl, Br) to give 1 : 1 complexes type ligands such as 2,6-(R2NCH2)2C6H3
15
and 2,6-
10d,g,i,16
L’BiX3 and was found to act as a neutral tripodal C(π),N,N-ligand.
(RNvCR′)2C6H3
are also useful to stabilize bismuth
compounds.17 However, no bismuth compound bearing a tri-
podal aryl ligand has been reported.18 In this paper, we report
the synthesis of a new carbon anionic aryl tripodal ligand 1
(Fig. 1) and its bismuth complexes.
Tripodal ligands constitute one of the important classes of
ligands in coordination chemistry.1 Various types of tripodal
ligands have been synthesized and are used in various fields
including catalysis, bioinorganic chemistry, medicinal chem-
istry and materials science.1,2 These ligands mainly possess
neutral or anionic N, P, O, and S atoms as coordination sites.
On the other hand, tripodal ligands bearing an anionic carbon
coordination site are relatively limited. Examples of such
ligands include N,N,C(alkyl) such as bis(pyrazol-1-yl)alkyl,3
N,N,C(aryl) such as 2-{bis(2-pyridyl)methyl}phenyl4 and 2-{bis
(pyrazol-1-yl)methyl}phenyl,5 N,N,C(acyl) such as bis(pyrazol-
1-yl)acetyl,6 and N,N,Cp (Cp = cyclopentadienyl) such as {2,2-
bis(pyrazol-1-yl)ethyl}cyclopentadienyl.7
We have designed 1 as a new carbon-anionic CNN type tri-
podal ligand. The ligand precursor 5 can be easily synthesized
as shown in Scheme 1. Ketone 3 was prepared from methyl
2-bromobenzoate and the lithium salt 2 according to a litera-
ture procedure.19 Introduction of the second benzothiazolyl
group by the reaction of 3 with 2 afforded alcohol 4 in 89%
yield. The conversion of the alcohol to methyl ether proceeded
smoothly with MeI to give the ligand precursor 5 (Fig. S1†) in
85% yield on a more than 30 g scale.
Introduction of ligand 1 on bismuth was not straight-
forward. An initial attempt to generate anion 1 by the reaction
During the course of our study on organobismuth com-
pounds, we had interest in using tripodal monoanionic aryl
aNational Institute of Advanced Industrial Science and Technology (AIST), 1-1-1
Higashi, Tsukuba, Ibaraki 305-8565, Japan. E-mail: s-shimada@aist.go.jp
bState Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry
and Chemical Engineering, Hunan University, Changsha 410082, P. R. China
cState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian
116023, P. R. China
†Electronic supplementary information (ESI) available. CCDC 2073386–2073391
and 2073586. For ESI and crystallographic data in CIF or other electronic format
see DOI: 10.1039/d1dt01071a
Fig. 1 Structure of a new C-anionic tripodal ligand 1.
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(8b : 7b = 86 : 14). The rearranged product 7b became predomi-
nant when the temperature was increased to −15 °C before the
hydrolysis. The structure of 7b was unambiguously confirmed
by single crystal X-ray diffraction (Fig. S2†).
To overcome the rearrangement problem, two other pro-
cedures were examined. One was the use of iPrMgCl/LiCl20
instead of nBuLi to generate anion 1. Screening of the reaction
temperature and reaction time revealed that the reaction of 5
with iPrMgCl/LiCl slowly proceeded at −20 °C without the
rearrangement, while a complex mixture was obtained at room
temperature. After the reaction of 5 with iPrMgCl/LiCl in a 1 : 1
ratio at −20 °C for 26 h (only a partial metallation took place),
the mixture was treated with BiCl3 (1 equiv.), resulting in the
formation of the desired product in a trace amount as crystals.
The other attempt was the pre-coordination of BiX3 to 5 and
subsequent reaction with nBuLi (Scheme 3). Complexes 9a and
9b were cleanly generated by the reaction of 5 and BiX3 in a
1 : 1 ratio in THF at room temperature and isolated in 90% or
higher yields. The molecular structure of 9b was determined
by single crystal X-ray diffraction analysis, showing that the
ligand precursor 5 acted as a neutral tripodal C(π)NN ligand
(vide infra). The subsequent reaction of 9a with nBuLi or tBuLi
at −78 °C in THF afforded the desired complex 6, although the
yield was very low (<10%).
As mentioned above, the rearrangement of the anion from
4 depended on the reaction temperature. Therefore, to sup-
press the rearrangement of anion 1, the effects of reaction
temperature were examined, together with that of TMEDA (the
details are summarized in Table S1†). The reaction of 5 with
nBuLi was examined at −78 to −114 °C in the presence or
absence of TMEDA and then the reaction mixture was hydro-
lyzed at the same temperature. The analysis of the ratio of 7a/
8a by NMR spectroscopy showed that the rearrangement could
be suppressed considerably at −104 °C or lower. Longer reac-
tion time induced more rearrangement. On the other hand,
the lithiation reaction was very slow at −114 °C and the conver-
sion of 5 was only 22% after 9 h. Addition of 1 or 2 equiv. of
TMEDA is effective to retard the rearrangement. Based on
these results, the synthesis of complex 6 was attempted by per-
forming the lithiation of 5 at −104 °C in the presence of
TMEDA (2.2 equiv.) for 30 min and subsequent reaction with
BiCl3 (1 equiv.). One product was obtained with high selecti-
vity, although whose structure was proved not to be 6 but the
2 : 1 complex 10 (Fig. 3) based on elemental analysis and
single crystal X-ray diffraction analysis (vide infra). This result
Scheme 1 Synthetic route of the ligand precursor 5.
of 5 with nBuLi in THF at −78 °C and the subsequent reaction
with BiCl3 did not afford the desired bismuth complex 6
(Scheme 2). Quenching the reaction of 5 and nBuLi with H2O
at −78 °C revealed that the rearrangement of anion 1 cleanly
took place to form 7a (Fig. 2), which has one of the benzothi-
azole groups on the aromatic ring. This rearrangement probably
took place via the intramolecular attack of the aryl anion on
the CvN carbon to form a four-membered ring and sub-
sequent ring opening as shown in Scheme S1.† Then, we tried
to use alcohol 4 instead of 5 to suppress the rearrangement.
The reaction of 4 with 2 equiv. of nBuLi in THF at −78 °C and
subsequent hydrolysis at the same temperature provided the
unrearranged debrominated compound 8b as the main
product, but the rearranged compound 7b was also obtained
Scheme 2 Synthesis of bismuth complex 6.
Fig. 2 Structures of the rearranged and unrearranged compounds 7
and 8.
Scheme 3 Synthesis of bismuth complex 9 and conversion to 6.
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which is defined as the angle between the ring normal and the
vector between Cen1 and Bi1, is 23.4°. Such an inter- and intra-
molecular interaction between bismuth and an aromatic ring
is well known.23,24 In the crystal, the molecules form 1D
chains through chalcogen bonds25 S2⋯Br1 (3.5456(9) Å) and
S2⋯Br3 (3.6120(9) Å) (Fig. S3†). Furthermore, the 1D chains
are connected with each other by an intermolecular C–H⋯π
interaction (C11–H11⋯Cen2, 2.60 Å, α′ = 5.3°; α′ is defined as
the angle between the ring normal and the vector between the
ring centroid and the hydrogen atom) to form 2D sheets
(Fig. S4†).
Fig. 3 Structure of L2BiCl (L = ligand 1) complex 10.
For complex 6, three different single crystals were obtained.
The first one formed in the NMR sample dissolved in THF-d8
and contained no solvent molecule. The second one was
obtained by recrystallization from THF and contained one
molecule of THF. The third one was obtained by crystallization
from the CHCl3 solution followed by washing with a mixture
of toluene and acetone (kept in this mixed solvent for a while)
and it contained one molecule of acetone. Fig. 5 shows the
molecular structure of complex 6 determined using the first
crystal, which clearly proved that ligand 1 acted as a tripodal
monoanionic aryl ligand in an expected κ3-C,N,N′ coordination
mode. The geometry of the Bi atom is square pyramidal with
the carbon atom at the apical position and two chlorine and
two nitrogen atoms at the basal positions. A similar structure
is found in alkylbismuth dichlorides bearing 2,2′-bipyridyl,26
N,N,N′,N′-tetramethylethylenediamine,27 or phenanthroline
ligands.28 The Bi atom lies below the basal plane by 0.2705(8)
Å. The Bi–C bond length (2.239(3) Å) is usual for Bi–Ar
bonds (for example, 2.258(8) Å (average) in BiPh3).29 The
probably originated from the low solubility of BiCl3 in the reac-
tion medium at such a low temperature.
It is well known that the redistribution reaction easily takes
place between BiAr3 and BiX3 (X = halogens) to form BiArnX3−n
(n = 1 or 2).21 By performing this redistribution reaction, we
finally obtained the 1 : 1 complex 6 in good yield; refluxing the
above reaction mixture mainly containing 10 for 1 h in the
presence of excess BiCl3 afforded 6 in 66% isolated yield.
The molecular structure of complex 9b is shown in Fig. 4.
The neutral ligand 5 was found to act as a tripodal C(π),N,N
ligand. The geometry of Bi is distorted octahedral. The three
Bi–Br bond lengths are almost identical and the average value,
2.66 Å, is similar to that found in the monomeric BiBr3(THF)3
(average Bi–Br 2.658 Å), in which three Br atoms are in a facial
arrangement.22 The distance of Bi1–Cen1 (Cen1 is the centroid
of the aromatic C6H4Br ring) is 3.3849(14) Å and the angle α,
Fig. 4 Molecular structure of complex 9b (thermal ellipsoids are shown
at the 50% probability level). Hydrogen atoms are omitted for clarity.
Selected bond lengths (Å) and angles (°): Bi1–Br1 2.6597(4), Bi1–Br2
2.6709(4), Bi1–Br3 2.6459(4), Bi1–N1 2.760(3), Bi1–N2 2.769(3), Bi1–C1
3.804 (3), Bi1–C2 4.131 (4), Bi1–C3 3.980 (4), Bi1–C4 3.542 (4), Bi1–C5
3.146 (3), Bi1–C6 3.241 (3), Bi1–Cen1 3.3849 (14), Br1–Bi1–Br2 101.418(14),
Br1–Bi1–Br3 99.839(12), Br2–Bi1–Br3 92.288(14), Br1–Bi1–N1 92.71(5),
Br1–Bi1–N2 157.05(6), Br2–Bi1–N1 165.51(5), Br2–Bi1–N2 97.77(6),
Br3–Bi1–N1 88.43(6), Br3–Bi1–N2 91.80(6), N1–Bi1–N2 67.73(8).
Fig. 5 Molecular structure of complex 6 (thermal ellipsoids are shown
at the 50% probability level). Hydrogen atoms are omitted for clarity.
Selected bond lengths (Å) and angles (°): Bi1–Cl1 2.5768(7), Bi1–Cl2
2.5536(7), Bi1–N1 2.618(2), Bi1–N2 2.613(2), Bi1–C1 2.239(3), Cl1–Bi1–
Cl2 97.90(2), Cl1–Bi1–N1 91.65(5), Cl1–Bi1–N2 165.91(5), Cl2–Bi1–N1
160.84(5), Cl2–Bi1–N2 92.31(5), Cl1–Bi1–C1 91.94(7), Cl2–Bi1–C1 88.87(7),
N1–Bi1–N2 75.87(7), N1–Bi1–C1 74.17(9), N2–Bi1–C1 78.52(9).
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Bi–N distances (average 2.616 Å) are shorter than those in 9b
(average 2.765 Å), while the N–Bi–N angle (75.87(7)°) is wider
than that in 9b (67.73(8)°). The Bi–Cl bond length (2.57 Å) is
similar to that in 10. In the first crystal, complex 6 forms a
dimer through a weak intermolecular Bi⋯Cl interaction
(Bi1⋯Cl2, 3.9172(8) Å, Fig. S5†), which is shorter than the sum
of the van der Waals radii of both atoms (4.38 Å).30 The dimers
form a 1D chain through an intermolecular S⋯Cl chalcogen
bond (S1⋯Cl1, 3.385(1) Å), C–H⋯Cl interaction (Cl2⋯H20,
2.88 Å), and C–H⋯π interaction (H18⋯Cen1, 2.74 Å, α′ = 12.7°)
(Fig. S6†). The molecular structure of complex 6 in the second
crystal is very similar to that in the first crystal and the differ-
ence in the important bond lengths and angles is less than 2%
on average. Complex 6 also forms a dimer through a weak
intermolecular Bi⋯Cl interaction (Bi1⋯Cl2, 3.9821(19) Å). The
dimers form a 2D sheet through a S⋯Cl chalcogen bond
(S2⋯Cl1, 3.4414(25) Å) (Fig. S7†). Additional Cl⋯H inter-
actions (Cl1⋯H17, 2.81 Å; Cl1⋯H19, 2.89 Å) connect the mole-
Fig. 6 Molecular structure of complex 10 (thermal ellipsoids are shown
at the 50% probability level). Hydrogen atoms except for H35 are
omitted for clarity. Selected bond lengths (Å) and angles (°): Bi1–Cl1
2.5781(11), Bi1–C1 2.289(4), Bi1–C23 2.284(4), Bi1–N3 2.761(4), Bi1–O1
cules three-dimensionally. The third crystal contains one mole- 2.753(3), Bi1–O2 2.882(3), Cl1–Bi1–C1 96.82(11), Cl1–Bi1–C23 87.43(11),
Cl1–Bi1–N3 161.36(8), Cl1–Bi1–O1 73.82(7), Cl1–Bi1–O2 109.30(7), C1–
Bi1–C23 91.48(15), C1–Bi1–N3 86.70(13), C1–Bi1–O1 65.70(12), C1–Bi1–
O2 142.18(12), C23–Bi1–N3 74.15(13), C23–Bi1–O1 147.70(13), C23–
Bi1–O2 63.80(13), N3–Bi1–O1 123.80(10), N3–Bi1–O2 60.14(9), O1–
cule of acetone, which coordinates with the Bi atom through
the oxygen atom (Bi1⋯O2, 3.177(4) Å) and prevents the dimer
formation through the intermolecular Bi⋯Cl interaction
(Fig. S8†). The molecular structure of complex 6 in the third
crystal is very similar to those in the first and second crystals
and the difference in the important bond lengths and angles
is less than 2% on average. In the crystal, the molecules are
Bi1–O2 147.10(8).
connected three-dimensionally through a S⋯Cl chalcogen (C35–H35⋯N2, 2.60 Å). In the crystal, the dimeric arrange-
bond (S2⋯Cl1, 3.4833(16) Å), three C–H⋯Cl interactions ment of complex 10 was found as shown in Fig. S13,† although
(C5–H5⋯Cl2, 2.88 Å; C17–H17⋯Cl2, 2.82 Å; and C18– the Bi1⋯Cl1 distance, 4.4504(16) Å, is longer than the sum of
H18⋯Cl1, 2.94 Å), and three C–H⋯π interactions (H18⋯Cen1, the van der Waals radii of both atoms (4.38 Å).30 Additional
2.97 Å, α′ = 9.6°; H24A⋯Cen2, 2.86 Å, α′ = 6.6°; and H4⋯Cen3, intermolecular interactions, C–H⋯Cl, C–H⋯S, and C–H⋯π,
2.80 Å, α′ = 11.6°) (Fig. S9†). The molecules form 1D chains connect the molecules three-dimensionally (Fig. S14†). Two
through the intermolecular S⋯Cl chalcogen bond and molecules are connected by the C44–H44B⋯Cl1 interaction
C17–H17⋯Cl2 interaction (Fig. S10†). The 1D chains are (2.88 Å) to form a ring, which is further extended to a 1D
further connected by the C5–H5⋯Cl2 interaction to form 2D columnar structure by C19–H19⋯Cl1 (2.63 Å) and C18–
sheets. The third C–H⋯Cl interaction, C12–H12⋯Cl1, con- H18⋯S1 interactions (2.95 Å) (Fig. S15†). The 1D columns are
nects two sheets to form a 2D bilayer structure (Fig. S11†). The further connected by C–H⋯π interactions (C11–H11⋯Cen1,
2D bilayers are further connected by the three C–H⋯π inter- 2.98 Å, α′ = 12.4°; C42–H42⋯Cen2, 2.64 Å, α′ = 4.7°; and
actions (Fig. S12†).
C39–H39⋯Cen3, 2.60 Å, α′ = 4.5°) (Fig. S14 and S16†).
The molecular structure of complex 10 determined by
In conclusion, a new C-anionic tripodal ligand L (1), 2-{bis
single crystal X-ray diffraction is shown in Fig. 6. In this (benzothiazolyl)(methoxy)methyl}phenyl, was designed and
complex, two ligand 1 bind to the Bi atom in unexpected suitable reaction conditions for its generation from the ligand
coordination modes instead of expected κ3-C,N,N′ or κ2-C,N: precursor 5 were established (lithiation with nBuLi at −104 °C
one in κ3-C,N,O and the other in κ2-C,O coordination modes, in the presence of TMEDA in THF). At higher reaction temp-
resulting in a bismuth complex bound by two C, two O, one N erature, the undesired rearrangement of the ligand took place
and one Cl atoms; such a bismuth complex is not found in the to give 7a. The lithium salt of the ligand reacted with BiCl3 to
Cambridge Structural Database.31 The Bi–O distances (Bi1–O1, give the 2 : 1 complex 10. The 1 : 1 complex 6 was obtained in
2.753(3) Å; Bi1–O2, 2.882(3) Å) are comparable to those of good yield by the redistribution reaction between 10 and BiCl3.
ether-bound organobismuth chlorides such as (2-(MeOCH2) X-ray diffraction analysis revealed that the ligand coordinated
C6H4)2BiCl (2.82 Å),32 MeON(CH2C6H4)2BiCl (2.91–3.07 Å),33 to the Bi atom in an expected κ3-C,N,N′ coordination mode in
and PhBiCl2(SIPr)(THF) (SIPr = 1,3-bis(2,6-diisopropylphenyl)- 6. On the other hand, it coordinated to the Bi atom in un-
4,5-dihydroimidazole-2-ylidene) (2.81 Å),34 in which Bi⋯O is expected κ3-C,N,O and κ2-C,O coordination modes in 10. The
located at the (quasi)-trans position of the Bi–C bond. The ligand precursor 5 reacted with BiX3 (X = Cl, Br) to give 1 : 1
three N atoms not used for binding with the Bi atom form complexes 9a and 9b in high yields. X-ray diffraction analysis
intramolecular S⋯N chalcogen bonds (S2⋯N1, 2.870(4) Å; of bromide 9b revealed that 5 acted as a neutral tripodal C(π),
S3⋯N4, 2.815(4) Å) and an intramolecular C–H⋯N interaction N,N-ligand.
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Conflicts of interest
There are no conflicts to declare.
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7954 | Dalton Trans., 2021, 50, 7949–7954
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