Chiral hexarhodium carbonyl clusters containing heterobidentate phosphine ligands; a structural and reactivity study
Bibliographic record
Abstract
Some intrinsically chiral [Rh6(CO)14(μ,κ2-PX)] clusters have been synthesized, beginning with reactions of [Rh6(CO)16−x(NCMe)x] (x = 1, 2) with PX, where PX represents the bidentate bridging ligands diphenyl(benzothienyl)phosphine (1), diphenyl(2-thienyl)phosphine (2), di(2-thienyl)phenylphosphine (3), tris(2-thienyl)phosphine (4), diphenyl(2-pyridyl)phosphine (5) and diphenylvinylphosphine (6). The ligand tris(2-furyl)phosphine (7) shows no bridging capability. When x = 1 the initial products are the clusters [Rh6(CO)15(κ1-PX)] which undergo spontaneous CO loss to form [Rh6(CO)14(μ,κ2-PX)]. The structures of the [Rh6(CO)15(κ1-PX)] clusters have been elucidated by IR, NMR spectroscopy and FAB-MS spectrometry, and have been found to involve phosphorus atom coordination to a rhodium atom. In addition, the solid state structures of the [Rh6(CO)14(μ,κ2-Ph2P(2-benzothienyl))] (8), [Rh6(CO)14(μ,κ2-Ph2P(2-thienyl))] (9), [Rh6(CO)14(μ,κ2-PhP(2-thienyl)2)] (10) and [Rh6(CO)14(μ,κ2-Ph2P(pyridyl))] (12) clusters have been determined by X-ray crystallography. The various types of chirality exhibited by these clusters are discussed. A simple model is proposed to account for the ratios of stereochemical isomers found in the Rh6(CO)14(μ,κ2-PhP(2-thienyl)2 cluster. The kinetics of formation of the bridged clusters from the monosubstituted [Rh6(CO)15(κ1-PX)] clusters have been studied.
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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".