Mixed Bis(μ-silylene) and (μ-Silylene)/(μ-Germylene) Complexes Involving the Rh/Ir Metal Combination: Nature of the Si···Si Interactions in the Bis(μ-silylene) Species
Bibliographic record
Abstract
A series of mixed bis(μ-silylene) complexes of rhodium and iridium [RhIr(CO)(2)(μ-SiHR)(μ-SiR(1)R(2))(dppm)(2)] (R = R(1) = R(2) = Ph (4); R = R(1) = Ph, R(2) = Cl (5); R = R(1) = Ph, R(2) = Me (6); R = 3,5-C(6)H(3)F(2), R(1) = Ph, R(2) = Me (7); R = 3,5-C(6)H(3)F(2), R(1) = 2,4,6-C(6)H(2)Me(3), R(2) = H (8)) have been synthesized by the reaction of the silylene-bridged dihydride complexes, [RhIr(H)(2)(CO)(2)(μ-SiHR)(dppm)(2)] (1, R = Ph; 2, R = C(6)H(3)F(2)), with a number of secondary or primary silanes (Ph(2)SiH(2), PhClSiH(2), PhMeSiH(2), C(6)H(2)Me(3)SiH(3)). The influence of substituents and π-stacking interactions on the Si···Si distance (determined by X-ray crystallography) in this series and the implications regarding the nature of the Si···Si interactions are discussed. A series of novel (μ-silylene)/(μ-germylene) complexes, [RhIr(CO)(2)(μ-SiHPh)(μ-GePh(2))(dppm)(2)] (9) and [RhIr(CO)(2)(μ-SiR(1)R(2))(μ-GeHPh)(dppm)(2)] (R(1) = Ph, R(2) = H (11); R(1) = R(2) = Ph (12); R(1) = Ph, R(2) = Me (13)), have also been synthesized by reaction of the silylene-bridged dihydride complex, [RhIr(H)(2)(CO)(2)(μ-SiHPh)(dppm)(2)] (1), with 1 equiv of diphenylgermane and by reaction of the germylene-bridged dihydride complex, [RhIr(H)(2)(CO)(2)(μ-GeHPh)(dppm)(2)] (3), with 1 equiv of the respective silanes. These complexes have been characterized by multinuclear NMR spectroscopy and X-ray crystallography.
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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 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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".