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Record W3199960958 · doi:10.1021/acs.jchemed.1c00323

Covalent d-Block Organometallics: Teaching Lewis Structures and sd/sd <sup>2</sup> Hybridization Gives Students Additional Explanations and Powerful Predictive Tools

2021· article· en· W3199960958 on OpenAlexafffund
Ulrich Fekl

Bibliographic record

VenueJournal of Chemical Education · 2021
Typearticle
Languageen
FieldChemistry
TopicOrganometallic Complex Synthesis and Catalysis
Canadian institutionsUniversity of Toronto
FundersNatural Sciences and Engineering Research Council of CanadaUniversity of Toronto
KeywordsChemistryAtomic orbitalCovalent bondBlock (permutation group theory)Electron pairComputational chemistryCrystallographyOrganic chemistryPhysicsElectronCombinatoricsQuantum mechanicsMathematics

Abstract

fetched live from OpenAlex

Despite tremendous efforts by instructors and textbook authors, students find it difficult to develop useful chemical intuitions about structures and key properties of the important d-block organometallic species that have a d6, d8, or d10 d-electron count. A full molecular orbital analysis is not always practical, and crystal field theory, while generally useful, is too limited here. It would be helpful to give students of organometallic chemistry an additional toolkit for understanding highly covalent d-block compounds. Hybridization arguments involving s and d orbitals (such as sd/sd2 hybridization for d8/d6 systems) provide useful insight, as is known from the research literature but rarely taught in undergraduate courses. This article makes descriptions of bonding that are based on s,d-hybridized orbitals more accessible, targeted toward undergraduate teaching. Geometries of unusual low-coordinate structures can be predicted. An in-depth physical explanation for the trans influence is provided. A clear explanation is given for the higher stability of the cis isomers versus the trans isomers in square-planar d8 complexes MR2L2 (R = alkyl/aryl, L = relatively weakly bonded neutral ligand) and for the fac versus mer isomers in octahedral d6 complexes MR3L3. Relevant to catalysis, it is explained why strongly donating ligands do not always facilitate oxidative addition and why 12-electron and 14-electron Pd(0) species are thermodynamically much more accessible than expected. The method capitalizes on first year knowledge, namely, the ability to write Lewis structures and to use hybridization arguments. It ties into the upper-year experience, including graduate school, where covalent d-block complexes may be encountered in research and where hybridization schemes will naturally emerge from using the natural bond orbital (NBO) formalism. It is discussed where the method might fit into the inorganic curriculum.

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)0.000
metaresearch head score (Gemma)0.001
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesInsufficient payload (model declined to judge)
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 score0.141
Threshold uncertainty score0.991

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.001
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0100.000

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 head0.011
GPT teacher head0.259
Teacher spread0.248 · 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.

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

Citations3
Published2021
Admission routes2
Has abstractyes

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