Spontaneous Resolution upon Crystallization and Preferential Induction of Chirality in a Discrete Tetrahedral Zinc(II) Complex Comprised of Achiral Precursors

Rajput, Gunjan; Bisht, Kamal Kumar; Drew, Michael G. B.; Singh, N.

doi:10.1021/acs.inorgchem.9b01934

Cited by 15 publications

(20 citation statements)

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“…In the IR spectra, complexes 1 – 5 display bands at 1596–1547, 1524–1464, and 1118–1027 cm –1 for the ν CO , ν CC and ν C–S vibrations, respectively, diagnostic of a coordinated β-oxodithioester ligand. ,, The free ligands HL1 – HL3 show characteristic bands at 1065–1060, 1591–1576, and 1232–1217 cm –1 for the ν C–OH , ν CC and ν CS frequencies, respectively. The decrease in the ν C–S frequency in complexes 1 – 5 in comparison to HL1 – HL3 is indicative of coordination via the S atom of the −SCSMe group of the dithioester ligands.…”

Section: Resultsmentioning

confidence: 99%

“…Intriguing coordination polymeric structures and photoluminescence properties of Tl(I) β-oxodithioester complexes displaying varied polymeric structures have also been described . Recently, a chiral compound was obtained via spontaneous resolution and chirality induction (using chiral inducers) in a discrete tetrahedral Zn(II) complex containing an achiral β-oxodithioester ligand . Despite their synthetic versatility and practical applicability, the chemistry and photophysical properties of group 12 metal (Zn, Cd, Hg) complexes with β-oxodithioester ligands have been much less explored. , …”

Section: Introductionmentioning

confidence: 99%

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Effect of Substituents on the Crystal Structures, Optical Properties, and Catalytic Activity of Homoleptic Zn(II) and Cd(II) β-oxodithioester Complexes

Singh

Anamika

Rajput³

et al. 2020

Inorg. Chem.

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Five novel zinc(II) and cadmium(II) β-oxodithioester complexes, [Zn(L1)2] (1), [Zn(L2)2] n (2), [Zn(L3)2] n (3) [Cd(L1)2] n (4), [Cd(L2)2] n (5), with β-oxodithioester ligands, where L1 = 3-(methylthio)-1-(thiophen-2-yl)-3-thioxoprop-1-en-1-olate, L2 = 3-(methylthio)-1-(pyridin-3-yl)-3-thioxoprop-1-en-1-olate, and L3 = 3-(methylthio)-1-(pyridin-4-yl)-3-thioxoprop-1-en-1-olate, were synthesized and characterized by elemental analysis, IR, UV–vis, and NMR spectroscopy (1H and 13C{1H}). The solid-state structures of all complexes were ascertained by single-crystal X-ray crystallography. The β-oxodithioester ligands are bonded to Zn(II)/Cd(II) metal ions in an O∧S and N chelating/chelating–bridging fashion leading to the formation of 1D (in 2–4) and 2D (in 5) coordination polymeric structures, but complex 1 was obtained as a discrete tetrahedral molecule. Complex 4 crystallizes in the C2 chiral space group and has been studied using circular dichroism (CD) spectroscopy. The multidimensional assemblies in these complexes are stabilized by many important noncovalent C–H···π (ZnOSC3, chelate), π···π, C–H···π, and H···H interactions. The catalytic activities of 1–5 in reactions involving C–C and C–O bond formation have been studied, and the results indicated that complex 3 can be efficiently utilized as a heterogeneous bifunctional catalyst for the Knoevenagel condensation and multicomponent reactions to develop biologically important organic molecules. The luminescent properties of complexes were also studied. Interestingly, zinc complexes 1–3 showed strong lumniscent emission in the solid state, whereas cadmium complexes 4 and 5 exhibited bright luminescent emission in the solution phase. The semiconducting behavior of the complexes was studied by solid-state diffuse reflectance spectra (DRS), which showed optical band gaps in the range of 2.49–2.62 eV.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Effect of Substituents on the Crystal Structures, Optical Properties, and Catalytic Activity of Homoleptic Zn(II) and Cd(II) β-oxodithioester Complexes

Singh

Anamika

Rajput³

et al. 2020

Inorg. Chem.

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“…The Zn(II) metal ion in complex 4 is situated on a crystallographic 2-fold axis with a distorted 6-coordinate octahedral environment. The metal is bonded to four S atoms from two S,S-chelated dithiocarbamate ligands L4 (Figure a,b) in which the Zn–S distances are 2.4807(5) and 2.5896(6) Å. − , The remaining two mutually cis coordination sites are occupied by two 3-pyridyl(N) atoms from the two neighboring Zn(L4) 2 units, thus resulting in the formation of an intriguing 1D CP structure (Figure c). The Zn–N distances at 2.1768(16) Å are well within the expected range. , The equatorial plane formed by S11, S13, S13′, and N34 show a rms deviation of 0.189 Å, with the metal atom 0.130(1) Å from that plane.…”

Section: Resultsmentioning

confidence: 99%

Ferrocene-Functionalized Dithiocarbamate Zinc(II) Complexes as Efficient Bifunctional Catalysts for the One-Pot Synthesis of Chromene and Imidazopyrimidine Derivatives via Knoevenagel Condensation Reaction

et al. 2021

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Four new mononuclear/coordination polymeric (CP) zinc(II) complexes (1−4) of ferrocenyl/pyridyl-functionalized dithiocarbamate ligands, N-ferrocenylmethyl-N-butyl dithiocarbamate (L1), N-ferrocenylmethyl-N-ethylmorpholine dithiocarbamate (L2), N-ferrocenylmethyl-N-2-(diethylamino)ethylamine dithiocarbamate (L3), and N-4-methoxybenzyl-N-3-methylpyridyl dithiocarbamate (L4), have been synthesized and characterized by elemental analyses, IR, UV−vis, and 1 H and 13 C{ 1 H} NMR spectroscopic techniques. The solid-state structures of complexes 1, 3, and 4 have been determined by single-crystal X-ray crystallography as well as powder X-ray diffraction. Single-crystal X-ray crystallography revealed a monomeric structure for complex 1 but 1D polymeric structures for complexes 3 and 4. In all complexes, dithiocarbamate ligands are bonded to the Zn(II) metal ion in a S^S chelating mode, and in the CPs, N atoms on the 2-(diethylamino)ethylamine and 3-pyridyl functionalities in the ligands on the neighboring molecules are also bonded to metal centers, leading to the formation of either a discrete tetrahedral molecule in 1 or 1D CP structures in 3 and 4. The Zn(II) metal centers in the polymeric structures exhibited either square-pyramidal or octahedral geometries. The supramolecular structures in these complexes are sustained via C−H•••π (ZnCS 2 , chelate; 3 and 4), C−H•••π, and H•••H interactions. The catalytic performances of complexes have also been assessed in the Knoevenagel condensation and one-pot multicomponent reactions. Catalysis results showed that the CP 3 acts as a heterogeneous bifunctional catalyst with excellent transformation efficiency at low catalyst loading.

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“…To date, considerable studies have been performed on spontaneous resolution for a wide range of chemical species, such as inorganic, organic, and coordination compounds, [11,15–22] and several examples that show the random crystallization of one enantiomer have been reported [23,24] . Bulk homochirality induced by co‐existing chiral agents has also been achieved via spontaneous resolution for some coordination compounds that contain labile metal ions, such as Co II , Cu II , and Zn II [25–27] . However, most examples of spontaneous resolution reported to date have targeted a single racemic species, and binary spontaneous resolution to generate optically active crystals from two kinds of isolated racemic species has rarely been reported, although examples of spontaneous resolution of a pair of enantiomers with two kinds of chiral centers, which are formed from metal species and organic ligands, have appeared in the literature [28–31] …”

Section: Introductionmentioning

confidence: 99%

Racemic Tartrate/Malate Anions Combine with Racemic Complex Cations to Form Optically Active Ionic Crystals

Uno

Kojima

Kuwamura

et al. 2021

Chemistry A European J

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Spontaneous resolution has attracted continuing attention in various research fields since Pasteur's work on the crystallization behavior of racemic tartrate. Here, a unique example of this phenomenon is reported, involving ionic crystals generated from racemic RR/SS‐ tartrate or R/S‐malate and racemic ΔΔ/ΛΛ‐[Ag3Rh2(2‐aminoethanethiolato)6]3+ (ΔΔ/ΛΛ‐[1]3+) in water. RR‐ and SS‐tartrate selectively recognize the ΛΛ and ΔΔ isomers of [1]3+ to produce ionic crystals of (ΛΛ‐[1])2(RR‐tartrate)3 and (ΔΔ‐[1])2(SS‐tartrate)3, respectively, which can undergo spontaneous resolution. While spontaneous resolution also occurs when using R/S‐malate, R‐ and S‐malate select the opposite isomers of [1]3+ to give ionic crystals of (ΔΔ‐[1])2(R‐malate)3 and (ΛΛ‐[1])2(S‐malate)3, respectively. In the presence of S‐aspartate, (ΛΛ‐[1])2(R‐tartrate)3 and (ΔΔ‐[1])2(S‐tartrate)3 are preferentially crystallized from ΔΔ/ΛΛ‐[1]3+ and RR/SS‐tartrate at solution pH values of 6 and 10, respectively. This finding provides significant insight into the optical resolution of chemical species by spontaneous resolution and the origin of homochirality in nature.

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Spontaneous Resolution upon Crystallization and Preferential Induction of Chirality in a Discrete Tetrahedral Zinc(II) Complex Comprised of Achiral Precursors

Cited by 15 publications

References 65 publications

Effect of Substituents on the Crystal Structures, Optical Properties, and Catalytic Activity of Homoleptic Zn(II) and Cd(II) β-oxodithioester Complexes

Effect of Substituents on the Crystal Structures, Optical Properties, and Catalytic Activity of Homoleptic Zn(II) and Cd(II) β-oxodithioester Complexes

Ferrocene-Functionalized Dithiocarbamate Zinc(II) Complexes as Efficient Bifunctional Catalysts for the One-Pot Synthesis of Chromene and Imidazopyrimidine Derivatives via Knoevenagel Condensation Reaction

Racemic Tartrate/Malate Anions Combine with Racemic Complex Cations to Form Optically Active Ionic Crystals

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