Absolute asymmetric synthesis of five-coordinate complexes

Lennartson, Anders; Håkansson, Mikael

doi:10.1039/c5nj00254k

Cited by 9 publications

(8 citation statements)

References 38 publications

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“…This is the case, for instance, in [Zn(S 2 CNEt 2 ) 2 (vinim)] (vinim = 1-vinylimida- . 408 Werner metal complexes with octahedral coordination may exist as Δ and Λ enantiomers. In the crystalline state, such materials may exist as conglomerates.…”

Section: Discrete Coordination Complexesmentioning

confidence: 99%

“…However, when coupled with a conglomerate crystallization, this stereochemical lability can give rise to a spontaneous resolution. This is the case, for instance, in [Zn(S 2 CNEt 2 ) 2 (vinim)] (vinim = 1-vinylimidazole), [Cd(S 2 CNEt 2 ) 2 (lut)] (lut = 2,6-lutidine), and [Cu(sac)(bipy) 2 ](sac)(H 2 O) 2 , (sac = saccharinate, bipy = 2,2′-bipyridine) …”

Section: Organic Conglomeratesmentioning

confidence: 99%

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Spontaneous Deracemizations

et al. 2021

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Spontaneous deracemizations is a challenging, multidisciplinary subject in current chirality research. In the absence of any chiral inductors, an achiral substance or a racemic composition is driven into an enantioenriched or even homochiral state through a selective energy input, e.g., chemical potential, photoirradiation, mechanical grinding, ultrasound waves, thermal gradients, etc. The most prominent examples of such transformations are the Soai reaction and the Viedma deracemization. In this review, we track the most recent developments in this topic and recall that many other deracemizations have been reported for solutions from mesophases to conglomerate crystallizations. A compiled set of simply available achiral organic, inorganic, organometallic, and MOF compounds, yielding conglomerate crystals, should give the impetus to realize new experiments on spontaneous deracemizations. Taking into account thermodynamic constraints, modeling efforts have shown that structural features alone are not sufficient to describe spontaneous deracemizations. As a guideline of this review, particular attention is paid to the physicochemical origin and symmetry requirements of such processes.

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Section: Discrete Coordination Complexesmentioning

confidence: 99%

Section: Organic Conglomeratesmentioning

confidence: 99%

Spontaneous Deracemizations

et al. 2021

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“…Despite both enantiomeric crystals being energetically identical and despite the subtle nature of the chiral origin, remarkably, we have obtained the same conglomerate independently of the origin of the sample and the crystallization method. Only a few authors have reported similar observations; − we hope that further reports of this kind may eventually lead to a scientific explanation for this enantiomeric selectivity. We suspect that the answers to these observations must lie in the nucleation and growth mechanisms of the corresponding crystals; unfortunately, such an assertion is not possible in the light of our present knowledge of the subject.…”

Section: Discussionmentioning

confidence: 70%

The Curious Case of 2-Propyl-1H-benzimidazole in the Solid State: An Experimental and Theoretical Study

et al. 2017

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2-Propyl-1H-benzimidazole (2PrBzIm) is a small molecule, commercially available, which displays a curious behavior in the solid state. 2PrBzIm, although devoid of chirality by fast rotation about a single bond of the propyl group in solution, crystallizes as a conglomerate showing chiroptical properties. An exhaustive analysis of its crystal structure and a wide range of experiments monitored by vibrational circular dichroism spectroscopy eliminated all possibilities of an artifact. What remains is a new example of the unexplained phenomenon of persistent supramolecular chirality.

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“…Kachi‐Terajima et al describe the same phenomenon with equally no satisfactory explanation . This enantiomeric excess has also been observed by other authors in the case of spontaneous resolution . It has been shown that an enantiomeric excess can be induced by various means such as agitation or a competitive reaction .…”

Section: Resultsmentioning

confidence: 81%

“…It has been shown that an enantiomeric excess can be induced by various means such as agitation or a competitive reaction . Similarly, it can be suppressed in some cases by sonication of the reagents . A possible explanation for compound 2 could be the existence of a very fast equilibrium in solution between the two enantiomers which favors the crystallization of an enantiomer as soon as it starts to crystallize .…”

Section: Resultsmentioning

confidence: 99%

A Bis‐Polydentate Oxamate‐Based Achiral Ligand That Can Stabilize a Macrocyclic Mixed Valence Compound or Induce a 1D Helical Chain

Chamoreau

et al. 2020

Eur J Inorg Chem

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The reaction of the N‐(2‐hydroxyphenyl)oxamate ligand (ohpma) has been investigated with cobalt(II) and copper(II) ions. It has led to two coordination compounds, (TMA)3[{CoIII(ohpma)2CoII(MeOH)2}3]·10H2O·5MeOH (1) and (HNEt3)[Cu(ohpma)] (2). Both compounds have been characterized by single‐crystal X‐ray diffraction and magnetometry. The X‐ray diffraction studies have revealed atypical structures that are not commonly observed in oxamate coordination chemistry with a macrocyclic arrangement for the mixed‐valence cobalt‐based complex 1, and a helical chiral chain for compound 2. In the latter, the bis‐polydentate nature of the (ohpma)3– ligand with distinct tridentate and bidentate coordination sites creates a chirogenic center on the copper ion. The investigation of the magnetic properties shows for complex 1 a single‐molecule magnet behavior detectable under static field, while antiferromagnetic interactions dominate the behavior of 2.

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Absolute asymmetric synthesis of five-coordinate complexes

Abstract: Three examples of optical resolution of five-coordinate complexes displaying only achiral mono- or bidentate ligands are reported.

Cited by 9 publications

References 38 publications

Spontaneous Deracemizations

Spontaneous Deracemizations

The Curious Case of 2-Propyl-1H-benzimidazole in the Solid State: An Experimental and Theoretical Study

A Bis‐Polydentate Oxamate‐Based Achiral Ligand That Can Stabilize a Macrocyclic Mixed Valence Compound or Induce a 1D Helical Chain

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