Synthesis and reactivity of alkaline-earth stannanide complexes by hydride-mediated distannane metathesis and organostannane dehydrogenation
Bibliographic record
Abstract
The synthesis of heteroleptic complexes with calcium- and magnesium-tin bonds is described. The dimeric β-diketiminato calcium hydride complex, [(BDI)Ca(μ-H)]2 (ICa) reacts with Ph3Sn-SnPh3 to provide the previously reported μ2-H bridged calcium stannanide dimer, [(BDI)2Ca2(SnPh3)(μ-H)] (3). Computational assessment of this reaction supports a mechanism involving a hypervalent stannate intermediate formed by nucleophilic attack of hydride on the distannane. Monomeric calcium stannanides, [(BDI)Ca(SnPh3)·OPPh3] (8·OPPh3) and [(BDI)Ca(SnPh3)·TMTHF] (8·TMTHF, TMTHF = 2,2,5,5-tetramethyltetrahydrofuran) were obtained from ICa and Ph3Sn-SnPh3, after addition OPPh3 or TMTHF. Both complexes were also synthesised by deprotonation of Ph3SnH by ICa in the presence of the Lewis base. The calcium and magnesium THF adducts, [(BDI)Ca(SnPh3)·THF2] (8·THF2) and [(BDI)Mg(SnPh3)·THF] (9·THF), were similarly prepared from [(BDI)Ca(μ-H)·(THF)]2 (ICa·THF2) or [(BDI)Mg(μ-H)]2 (IMg) and Ph3SnH. An excess of THF or TMTHF was essential in order to obtain 8·TMTHF, 8·THF2 and 9·THF in high yields whilst avoiding redistribution of the phenyl-tin ligand. The resulting Ae-Sn complexes were used as a source of [Ph3Sn]- in salt metathesis, to provide the known tristannane Ph3Sn-Sn(t-Bu)2-SnPh3 (11). Nucleophilic addition or insertion with N,N'-di-iso-propylcarbodiimide provided the stannyl-amidinate complexes, [(BDI)Mg{(iPrN)2CSnPh3}] (12) and [(BDI)Ca{(iPrN)2CSnPh3}·L] (13·TMTHF, 13·THF, L = TMTHF, THF). The reactions and products were monitored and characterised by multinuclear NMR spectroscopy, whilst for compounds 8, 9, 12, and 13·THF, the X-ray crystal structures are presented and discussed.
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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 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 0.001 |
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".