Synthesis and structural characterization of zinc complexes of the imidoamido phosphate anions OP[(NHR)<sub>3</sub><i><sub>x</sub></i>(NR)]<i><sup>x</sup></i><sup></sup> (R = Me, <i>t</i>-Bu; <i>x</i> = 13) and EP[(NH-<i>t</i>-Bu)<sub>2</sub>(N-<i>t</i>-Bu)]<sup></sup> (E = S, NSiMe<sub>3</sub>)
Bibliographic record
Abstract
The reaction of OP(NH-t-Bu) 3 with 1 equiv. of ZnMe 2 generates the dimeric eight-membered ring {MeZn[(µ-NH-t-Bu)(µ-N-t-Bu)P(NH-t-Bu)(µ-O)]} 2 (5) and the cubane {[MeZn] 3 [OP(N-t-Bu) 3 ][OP(NH-t-Bu) 3 ]} (6), which contains the first known trisimidophosphate trianion. A related complex {Zn[ZnMe] 2 [OP(N-t-Bu)(NH-t-Bu) 2 ][OP(N-t-Bu) 3 ]} (7) is obtained by the reaction of OP(NH-t-Bu) 3 with ZnMe 2 in a 2:3 molar ratio. The treatment of OP(NHMe) 3 with 1 equiv. of ZnMe 2 produces the oxide-templated cluster {Zn 4 (µ 4 -O)[OP(NMe)(NHMe) 2 ] 4 [OP(NMe) 2 (NHMe)]} 2 (8). Each half of this centrosymmetric dimer contains a tetrahedral arrangement of four 4-coordinate Zn 2+ ions surrounding the central µ 4 -O 2- anion. The reaction of SP(NH-t-Bu) 3 with ZnMe 2 in a 1:1 molar ratio generates the dimer {MeZn(µ-S)(µ-N-t-Bu)P(NH-t-Bu) 2 } 2 (10), which has a ladder-type structure. When a 2:1 molar ratio of the same reagents is employed, the bis(N,S)-chelated complex {Zn[(µ-S)(µ-N-t-Bu)P(NH-t-Bu) 2 ] 2 } (11) is obtained. The monomeric N,N′-chelated complex {MeZn[(µ-N-t-Bu)(µ-NSiMe 3 )P(NH-t-Bu) 2 ]} (12) results from the reaction of Me 3 SiNP(NH-t-Bu) 3 with 1 equiv. of dimethylzinc. All new compounds have been characterized by multinuclear ( 1 H, 13 C, and 31 P) NMR spectroscopy and, in the case of 5, 6, 7, 8, and 10, by X-ray structural determinations.Key words: zinc, phosphate, imido ligands, sulfur.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.003 | 0.003 |
| Meta-epidemiology (broad) | 0.004 | 0.002 |
| Bibliometrics | 0.001 | 0.002 |
| Science and technology studies | 0.002 | 0.003 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.003 | 0.001 |
| Research integrity | 0.002 | 0.003 |
| 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; both teacher heads agree on what is shown here.
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".