Formation of N−I Charge-Transfer Bonds and Ion Pairs in Polyiodides with Imidotellurium Cations
Bibliographic record
Abstract
[((t)BuNH)Te(mu-N(t)Bu)(2)Te(N(t))Bu)][OSO(2)CF(3)] (4a) is obtained in quantitative yields by the treatment of [((t)BuN)Te(mu-N(t)Bu)(2)Te(N(t)Bu)] (1) with HCF(3)SO(3). The reaction of 4a with LiI and iodine in the molar ratio 1:1:4.5 affords a product that, upon recrystallization from acetonitrile, was found to be a solid solution of [((t)BuNH)Te(mu-N(t)Bu)(2)Te(N(t)Bu)](2)I(20) (5a) and [((t)BuNH)Te(mu-N(t)Bu)(2)Te(NH(t)Bu)](2)I(18) (5b). Consequently, the crystal structure is disordered, containing 88.3(1)% of 5a.2MeCN and 11.7(1)% of 5b.2MeCN. The I(20) framework is involved in two symmetry-equivalent N-I-I-I-I fragments, two I(3)(-) ions, and three I(2) molecules that are linked together by I...I secondary bonding interactions. The bonding in the N-I-I-I-I fragment can be considered in terms of the lp(N) --> sigma*(I(2)) and pi(I(2)) --> sigma*(I(2)) charge-transfer interactions involving one [((t)BuNH)Te(mu-N(t)Bu)(2)Te(N(t)Bu)](+) cation and two I(2) units. The N-I bond length of 2.131(7) A, the I-I distances of 3.118(1), 3.095(2), and 2.788(2) A, and the angle I(2)-I(2) angle of 84.75(4) degrees are consistent with this bonding scheme. The I-I bond distances in the two symmetry-equivalent I(3)(-) ions are 3.113(1) and 2.792(2) A, and those in two crystallographically independent I(2) molecules are 2.736(2) and 2.743(1) A. The formal I(18)(4)(-) anion in 5b.2MeCN consists of four I(3)(-) anions and three I(2) molecules linked by I...I secondary bonds. One crystallographically independent I(3)(-) anion is connected to the [((t)BuNH)Te(mu-N(t)Bu)(2)Te(HN(t)Bu)](2+) cation by two hydrogen bonds [H...I = 2.823(5) and 2.983(5) A; N...I = 3.697(8) and 3.857(9) A]. The I(3)(-) anions and I(2) molecules in 5b show virtually identical bond parameters to those in 5a. The treatment of 1 with iodine and the reactions of its methylated derivatives, [((t)BuNMe)Te(mu-N(t)Bu)(2)Te(N(t)()Bu)][OSO(2)CF(3)] and [((t)BuNMe)Te(mu-N(t)Bu)(2)Te(MeN(t)Bu)][OSO(2)CF(3)](2), with LiI and iodine also afford highly moisture-sensitive polyiodides, either by the formation of N-I charge-transfer complexes or by ionic interactions. The crystal structures of the partially hydrolyzed products, [((t)BuIN)Te(mu-N(t))Bu)(2)Te(mu-O)](2)(I(3))(2) (3), [((t)BuMeN)Te(mu-N(t)Bu)(2)Te(mu-O)](2)(I(3))(2) (6), and 6.2MeCN, are also reported.
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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 | 0.000 | 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 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| 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 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".