New Insights into the Chemistry of Imidodiphosphinates from Investigations of Tellurium-Centered Systems
Bibliographic record
Abstract
Dichalcogenido-imidodiphosphinates, [N(PR(2)E)(2)](-) (R = alkyl, aryl), are chelating ligands that readily form cyclic complexes with main group metals, transition metals, lanthanides, and actinides. Since their discovery in the early 1960s, researchers have studied the structural chemistry of the resulting metal complexes (where E = O, S, Se) extensively and identified a variety of potential applications, including as NMR shift reagents, luminescent complexes in photonic devices, or single-source precursors for metal sulfides or selenides. In 2002, a suitable synthesis of the tellurium analogs [N(PR(2)Te)(2)](-) was developed. In this Account, we describe comprehensive investigations of the chemistry of these tellurium-centered anions, and related mixed chalcogen systems, which have revealed unanticipated features of their fundamental structure and reactivity. An exhaustive examination of previously unrecognized redox behavior has uncovered a variety of novel dimeric arrangements of these ligands, as well as an extensive series of cyclic cations. In combination with calculations using density functional theory, these new structural frameworks have provided new insights into the nature of chalcogen-chalcogen bonding. Studies of metal complexes of the ditellurido ligands [N(PR(2)Te)(2)](-) have revealed unprecedented structural and reaction chemistry. The large tellurium donor sites confer greater flexibility, which can lead to unique structures in which the tellurium-centered ligand bridges two metal centers. The relatively weak P-Te bonds facilitate metal-insertion reactions (intramolecular oxidative-addition) to give new metal-tellurium ring systems for some group 11 and 13 metals. Metal tellurides have potential applications as low band gap semiconductor materials in solar cells, thermoelectric devices, and in telecommunications. Practically, some of these telluride ligands could be applied in these industries. For example, certain metal complexes of the isopropyl-substituted anion [N(P(i)Pr(2)Te)(2)](-) serve as suitable single-source precursors for pure metal telluride thin films or novel nanomaterials, for example, CdTe, PbTe, In(2)Te(3), and Sb(2)Te(3).
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot 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.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 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 source (direct Gemma or distilled Codex), 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".