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 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) | 0.001 | 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) | 0.005 | 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".