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Record W2062065568 · doi:10.1002/qua.21910

On the origin of the trans‐influence in square planar d<sup>8</sup>‐complexes: A theoretical study

2008· article· en· W2062065568 on OpenAlexaff
Mariusz P. Mitoraj, Hongjuan Zhu, Artur Michalak, Tom Ziegler

Bibliographic record

VenueInternational Journal of Quantum Chemistry · 2008
Typearticle
Languageen
FieldChemistry
TopicCrystallography and molecular interactions
Canadian institutionsUniversity of Calgary
Fundersnot available
KeywordsChemistryElectronegativityValence (chemistry)Atomic orbitalCrystallographyLigand (biochemistry)Molecular orbitalPi bondInverseNatural bond orbitalStereochemistryHOMO/LUMONon-bonding orbitalBond lengthComputational chemistryPhysicsMoleculeCrystal structureDensity functional theoryBond orderQuantum mechanicsGeometryElectron

Abstract

fetched live from OpenAlex

Abstract The trans influence of ligands T in trans‐[Ni(Cl)2NH3T]n complexes with T−B(Me) , H−, CP−, CH2CH , CN−, HCC−, Cl−, F− for n = −1 and TPF3, PH3, P(CH3)3, CO for n = 0 has been analyzed with the help of the extended transition state (ETS) energy decomposition scheme as well as the natural orbitals for chemical valence (NOCV) method. The TCl2NiNH3 bond is made up of the bonding interaction between the empty σNi acceptor orbital on the [TCl2Ni]n fragment and the σNH3 donor orbital. The σNi orbital is in turn an out‐of‐phase combination between d on the metal and an occupied σT orbital: σNi = d − C1 × σT. It is shown that the trans influence is related to the contribution (C1) to σNi from σT. Thus, the smaller the contribution C1 to σNi the larger the <σNi|σNH3> overlap and the stronger the TCl2NiNH3 bond. The contribution C1 is in turn related to the orbital energy ε(σT) of T. Thus the lower ε(σT) is, the smaller is C1. There is thus an inverse relation between the trans influence of a ligand T and its electronegativity. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009

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)0.000
metaresearch head score (Gemma)0.000
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: Theoretical or conceptual
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.006
Threshold uncertainty score0.020

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0010.001
Scholarly communication0.0010.001
Open science0.0010.001
Research integrity0.0010.000
Insufficient payload (model declined to judge)0.0060.000

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 head0.018
GPT teacher head0.280
Teacher spread0.262 · 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

Citations82
Published2008
Admission routes1
Has abstractyes

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