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Record W2085230192 · doi:10.1021/jp800139g

Bond Multiplicity in Transition-Metal Complexes: Applications of Two-Electron Valence Indices

2008· article· en· W2085230192 on OpenAlexaff
Artur Michalak, Roger L. DeKock, Tom Ziegler

Bibliographic record

VenueThe Journal of Physical Chemistry A · 2008
Typearticle
Languageen
FieldMedicine
TopicMetal complexes synthesis and properties
Canadian institutionsUniversity of Calgary
Fundersnot available
KeywordsMultiplicity (mathematics)Transition metalValence (chemistry)Valence electronElectronValence bond theoryMetalGeneralized valence bondChemistryMaterials scienceChemical physicsPhysicsMathematicsQuantum mechanicsMetallurgyAtomic orbitalOrganic chemistryGeometry

Abstract

fetched live from OpenAlex

In the present study the applicability of the bond multiplicities from the Nalewajski and Mrozek valence indices was demonstrated for a variety of transition metal-based systems. The Nalewajski-Mrozek valence indices and bond multiplicity indices have been implemented in the Amsterdam Density Functional program. Selected examples comprise the carbonyl complexes (selected tetra- and hexacarbonyls, binary monocarbonyls of the first-row transition metals), phosphines, the ligands' trans-influence, as well as multiple metal-ligand and metal-metal bonds. The results show that the calculated bond multiplicity indices correspond well to experimental predictions based on bond lengths and vibrational frequencies for all discussed classes of complexes. Almost perfect linear correlation between the bond indices and vibrational frequencies was observed for carbonyls and the oxo complexes; the calculated bond multiplicity reproduces the accepted order for the trans-influence of different ligands, rationalizes unusually low vibrational freqencies in the [OsO 3N] (-)complex compared to other nitrido complexes, explains the geometrical asymmetry in the MoO 3 solid, and confirms the multiple character of the metal-metal bond in the [Re 2Cl 8] (2-) complex. Thus, the Nalewajski and Mrozek method can be successfully used as a supplementary analysis tool for electronic structure for studies involving transition metal complexes.

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 machine prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.

metaresearch head score (Codex)0.001
metaresearch head score (Gemma)0.002
Version: metacan-v3-hybrid-931329e0061cValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Theoretical or conceptual · Consensus signal: none
GenreCandidate signal: Empirical · Consensus signal: none
Teacher disagreement score0.002
Threshold uncertainty score0.007

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0010.002
Meta-epidemiology (narrow)0.0010.000
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0010.001
Science and technology studies0.0000.000
Scholarly communication0.0010.001
Open science0.0010.001
Research integrity0.0000.001
Insufficient payload (model declined to judge)0.0020.000

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 head0.027
GPT teacher head0.282
Teacher spread0.255 · 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 source (direct Gemma or distilled Codex), not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designTheoretical or conceptual
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

Citations242
Published2008
Admission routes1
Has abstractyes

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Same venueThe Journal of Physical Chemistry ASame topicMetal complexes synthesis and propertiesFrench-language works237,207