A Phosphine‐Mediated Through‐Space Exchange Coupling Pathway for Unpaired Electrons in a Heterobimetallic Lanthanide–Transition Metal Complex
Bibliographic record
Abstract
The reaction of P(CH2OH)3 with methyl anthranilate NH2C6H4-2-CO2Me produced the ligand precursor P(CH2NHC6H4-2-CO2Me)3 (1). The reaction of 1 with [Y{N(SiMe3)2}3] produced hexadentate yttrium complex [Y{P(CH2NC6H4-2-CO2Me)3}] (2), in which the metal centre is coordinated by three amido donors and the three carbonyl oxygen atoms of the ester groups. The 31P{1H} NMR spectrum features 1J Y,P=15 Hz, and DFT calculations demonstrate that through-space interaction between the minor lobe of the phosphine lone pair and the yttrium centre allows a large Fermi contact contribution to this spin coupling constant. The EPR spectrum of the analogous paramagnetic Gd complex [Gd{P(CH2NC6H4-2-CO2Me)3}] (3) can be modelled by using a B20 crystal field parameter of +/-0.19 cm(-1). Heterodinuclear complexes were prepared by the reactions of 1 and 3 with [5,10,15,20-tetrakis(4-methoxyphenyl)porphinato]cobalt(II), by binding of the phosphine lone pair to the d(7) cobalt centre. The solid-state EPR spectrum of the heterodinuclear yttrium complex 4 exhibits large superhyperfine coupling to the phosphorus nucleus, indicative of an S=1/2 complex in which the unpaired electron resides in the cobalt dz2 orbital directed at the phosphine donor. The magnetic susceptibility of the heterodinuclear Gd-Co complex 5 demonstrates that through-space antiferromagnetic coupling occurs between unpaired electrons on the gadolinium and cobalt centres.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot 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.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.002 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.009 | 0.000 |
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.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
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".