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Record W2020386318 · doi:10.1002/chem.200902599

Ligand Close Packing, Molecular Compactness, the Methyl Tilt, Molecular Conformations, and a New Model for the Anomeric Effect

2010· article· en· W2020386318 on OpenAlexaff
R. J. Gillespie, E. A. Robinson, Julien Pilmé

Bibliographic record

VenueChemistry - A European Journal · 2010
Typearticle
Languageen
FieldChemistry
TopicCrystallography and molecular interactions
Canadian institutionsUniversity of TorontoMcMaster University
Fundersnot available
KeywordsMonatomic ionChemistryLone pairMoleculeLigand (biochemistry)CrystallographyAtom (system on chip)Anomeric effect

Abstract

fetched live from OpenAlex

All the atoms in a molecule attract each other until they reach their equilibrium positions at which point the repulsive forces between the atoms just balance the attractive forces and there are no resultant forces acting on any of the atoms in the molecule. Thus, we can consider that in the equilibrium geometry the atoms in a molecule are arranged as compactly as possible. This is the basis of the ligand close packing (LCP) model according to which three or four monatomic ligands X, such as F, Cl or O (formally =O or O(-)) pack as closely as possible around a small central atom such as a boron or carbon atom giving a truly close-packed equilateral triangular AX(3) molecule or a tetrahedral AX(4) molecules. Such monatomic ligands can, to a good approximation, be described as having a spherical shape with a single ligand radius r(X). In contrast, ligands with donor atoms with lone pairs such as the oxygen atom in an OX group have a less symmetrical electron density requiring two ligand radii, r(O(lp)) in the lone pair direction, and r(O(b)) in the bonding direction, where r(O(lp)) < r(O(b)) for an approximate description. On this basis we propose an explanation for the "methyl tilt", in methanol and many related molecules, and in conjunction with the concept of compactness, a model for explaining the relative energies of the conformations of molecules containing OH and OMe ligands, including molecules that exhibit the anomeric effect. We compare our model for the anomeric effect with the widely accepted "hyperconjugation" model. We also discuss the relationship between the concept of compactness and the concept of hardness.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.001
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.181
Threshold uncertainty score0.753

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0010.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0010.000
Scholarly communication0.0000.000
Open science0.0010.000
Research integrity0.0000.001
Insufficient payload (model declined to judge)0.0000.000

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.012
GPT teacher head0.251
Teacher spread0.240 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one teacher head, not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
Domainnot available
GenreEmpirical

How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".

Quick stats

Citations18
Published2010
Admission routes1
Has abstractyes

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