Silyl- and Germyl-Substituted Boranes: Synthesis and Investigation as Potential Atomic Layer Deposition Precursors
Bibliographic record
Abstract
Boranes featuring bulky hypersilyl or supersilyl groups and/or sterically unencumbered trimethylgermyl substituents were synthesized for investigation as potential precursors for atomic layer deposition (ALD) of elemental boron. The envisaged ALD process would employ a boron trihalide coreactant, exploiting the formation of strong silicon-halogen and germanium-halogen bonds as a driving force. The alkali metal silyl and germyl compounds hypersilyl lithium, {(Me 3 Si) 3 Si}Li(THF) 3 ( 1 ), supersilyl sodium, ( t Bu 3 Si)Na(THF) n ( 2, n = 2–3), and trimethylgermyl lithium, {Me 3 GeLi(THF) 2 } 2 ( 3 ), were used for the synthesis of the silyl- and germyl-substituted boranes in this work. Compounds 1 and 2 were synthesized as previously reported, and compound 3 was isolated from the reaction of trimethylgermane with tert -butyl lithium. Compounds 2 and 3 were crystallographically characterized. Reaction of B(NMe 2 )Cl 2 with 2 equiv of 1 afforded previously reported {(Me 3 Si) 3 Si} 2 B(NMe 2 ) ( 4 ), whereas reactions of B(NMe 2 )Cl 2 or {B(NMe 2 )F 2 } 2 with excess 2 only afforded the monosilyl boranes ( t Bu 3 Si)B(NMe 2 )X {X = Cl ( 5 ) and F ( 6 )}. Reaction of 5 with 0.5 equiv of {Me 3 GeLi(THF) 2 } 2 ( 3 ) provided the first example of a mixed silyl/germyl-substituted borane, ( t Bu 3 Si)(Me 3 Ge)B(NMe 2 ) ( 7 ). Attempts to synthesize (Me 3 Ge) 2 B(NMe 2 ) from the 1:1 reaction of B(NMe 2 )Cl 2 with {Me 3 GeLi(THF) 2 } 2 afforded a mixture of two major products, one of which was identified as the tri(germyl)(amido)borate {(Me 3 Ge) 3 B(NMe 2 )}Li(THF) 2 ( 8 ); compound 8 was isolated from the 1:1.5 reaction. Reaction of more sterically encumbered B(TMP)Cl 2 with 1 equiv of {Me 3 GeLi(THF) 2 } 2 afforded the di(germyl)(amido)borane (Me 3 Ge) 2 B(TMP) ( 9 ). Boranes 4, 7, and 9 and borate 8 were crystallographically characterized. The thermal stability and volatility of boranes 4, 7, and 9 was evaluated, the solution reactivity of 4 and 7 with boron trihalides was assessed, and ALD was attempted using 4 in combination with BCl 3 and BBr 3 at 150 and 300 °C.
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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) | 0.000 | 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".