Preorganization of tetrathiamacrocyclic ligands: implications from computed and experimentally determined structures

Comba, Peter; Fath, Andreas; Kühner, A.; Nuber, Bernd

doi:10.1039/a607859a

Cited by 36 publications

(21 citation statements)

References 38 publications

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“…The cases of NIZQES (Comba et al, 1997) and PIVDOO (Yao et al, 2007), both of which also include a molecule and its oxidation product (see Fig. 6), are similar.…”

Section: Figurementioning

confidence: 83%

Failures of fractional crystallization: ordered co-crystals of isomers and near isomers

Kelley

Fábián

Brock

2011

Acta Crystallogr B Struct Sci

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A list of 270 structures of ordered co-crystals of isomers, near isomers and molecules that are almost the same has been compiled. Searches for structures containing isomers could be automated by the use of IUPAC International Chemical Identifier (InChI™) strings but searches for co-crystals of very similar molecules were more labor intensive. Compounds in which the heteromolecular A···B interactions are clearly better than the average of the homomolecular A···A and B···B interactions were excluded. The two largest structural classes found include co-crystals of configurational diastereomers and of quasienantiomers (or quasiracemates). These two groups overlap. There are 114 co-crystals of diastereomers and the same number of quasiracemates, with 71 structures being counted in both groups; together the groups account for 157 structures or 58% of the total. The large number of quasiracemates is strong evidence for inversion symmetry being very favorable for crystal packing. Co-crystallization of two diastereomers is especially likely if a 1,1 switch of a methyl group and an H atom, or of an inversion of a [2.2.1] or [2.2.2] cage, in one of the diastereomers would make the two molecules enantiomers.

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“…The cases of NIZQES (Comba et al, 1997) and PIVDOO (Yao et al, 2007), both of which also include a molecule and its oxidation product (see Fig. 6), are similar.…”

Section: Figurementioning

confidence: 83%

Failures of fractional crystallization: ordered co-crystals of isomers and near isomers

Kelley

Fábián

Brock

2011

Acta Crystallogr B Struct Sci

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“…This notion of entatic coordination compounds is perhaps retraceable to an earlier paper in which Comba et al formulate the concept of 'preorganization' of macrocyclic ligands. 21 Originally, Artz and Cram had defined 'the principle of preorganization' as ''the most highly host and guest are organized for binding and for low solvation prior to their complexation, the more stable will be their complexes''. 22 In this context host is a macrocyclic ligand and guest is a metal ion.…”

Section: Bootstrapping Free Coordination Compounds Into Entatic Statesmentioning

confidence: 99%

“…Comba et al subsequently venture that ''in contrast to the original definition of ligand preorganization, we analyze the extent of preorganization as a continuum involving partially and fully preorganized systems''. 21 The claimed contrast is not obvious: in the original definition the words ''the most highly organized'' and ''the most stable'' equally well define a continuum of preorganization. Be that as it may, the point of key relevance here is that 'preorganization' and 'entasis' are orthogonal concepts.…”

Section: Bootstrapping Free Coordination Compounds Into Entatic Statesmentioning

confidence: 99%

Hypothesis: entaticversusecstatic states in metalloproteins

Hagen

2019

Metallomics

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“…In areas where this is relevant, MM is not only an appropriate and efficient technique, but in terms of reliability and accuracy it is also competitive and, indeed, often the only approach to allow a full separation between steric and electronic effects [109]. Important contributions to complex stabilities and metal ion selectivities such as preorganization and complementarity, derived from the shape and size of ligand cavities and their flexibility and elasticity, as well as the corresponding preferences of metal ions, are among those features which have been successfully predicted by using MM [92,[110][111][112]. Redox potentials are related to complex stabilities and, for specific classes of metal complexes, MM has been used to compute redox properties with acceptable accuracies [113][114][115].…”

Section: Computation Of Molecular Propertiesmentioning

confidence: 99%

Interpretation and Prediction of Properties of Transition Metal Coordination Compounds

Comba¹

2011

Modeling of Molecular Properties

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The discovery of transition metal complexes with novel properties is often based on serendipity, and the basis for the further development and optimization of such systems with specific properties is the careful analysis of experimental data. Important approaches in this process are classical methods derived from qualitative molecular orbital and ligand field theory, parameters related to donor-acceptor strengths, and concepts based on geometric and steric effects. The analysis of experimental data of novel systems, based on thorough electronic structure calculations, allows these novel systems to be interpreted and understood. As a result, new models and theories may emerge, possibly leading to rules on how the relevant properties of the new class of compounds may be further improved.There are also examples, where novel types of compounds or novel mechanistic ideas have emerged from theoretical studies; recent examples include the discovery of the first molecular Fe VI species [1], the experimental characterization of HgF 4 [2], the prediction and observation of multistate reactivity in iron-based oxygen activation [3,4], the discovery of an elusive, biologically relevant Cu-O 2 complex [5, 6], the investigation of copper-oxygen intermediates capable of hydroxylating arenes [7], and the search for the elusive high-spin Fe IV ¼O model system [8][9][10][11][12][13][14][15].Importantly, there is an increasing number of studies with a combination of preparative chemistry, the experimental investigation of molecular properties, theory, and modeling. In many areas, a thorough interpretation of experimental dataoften based on electronic structure calculations -has helped to create new models and rules, which then have inspired experimentalists to the synthesis and investigation of new compounds and reactions. The general approach described here, relies on the correlation of structures and properties, the possibility to enforce structures on transition metal centers by well-designed organic ligands and, specifically, a reliable structure prediction, leading to a combination of theory, structural modeling, and experiment [16,17].Modeling of Molecular Properties, First Edition. Edited by Peter Comba.

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Preorganization of tetrathiamacrocyclic ligands: implications from computed and experimentally determined structures

Cited by 36 publications

References 38 publications

Failures of fractional crystallization: ordered co-crystals of isomers and near isomers

Failures of fractional crystallization: ordered co-crystals of isomers and near isomers

Hypothesis: entaticversusecstatic states in metalloproteins

Interpretation and Prediction of Properties of Transition Metal Coordination Compounds

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