Cadmium complexes of thiones. Part II.<sup>1</sup> A synthetic, solution, and solid-state MAS <sup>111/113</sup>Cd NMR study of cadmium complexes of 1,3-thiazolidine-2-thione, and the structures of [tetrakis(1,3-thiazolidine-2-thione)cadmium] trifluoromethanesulfonate ([Cd(C<sub>3</sub>H<sub>5</sub>NS<sub>2</sub>)<sub>4</sub>](CF<sub>3</sub>SO<sub>3</sub>)<sub>2</sub>) and [tetrakis(1,3-thiazolidine-2-thione)cadmium][tetrakis(nitrato-<i>O,O</i><i>'</i>)cadmate] ([Cd(C<sub>3</sub>H<sub>5</sub>NS<sub>2</sub>)<sub>4</sub>][Cd(O<sub>2</sub>NO)<sub>4</sub>])
Bibliographic record
Abstract
Treatment of Cd(O 3 SCF 3 ) 2 with the stoichiometric quantity of 1,3-thiazolidine-2-thione (tztH) allows isolation of [Cd(tztH) 4 ](O 3 SCF 3 ) 2 (1). When tztH:Cd [Formula: see text] 2 the reaction of Cd(NO 3 ) 2 ·4H 2 O with tztH leads to [Cd(tztH) 4 ][Cd(O 2 NO) 4 ] (2). The structures of both 1 and 2 have been determined by single crystal X-ray analysis. Colourless crystals of 1 are orthorhombic, space group Fdd2, with eight molecules per unit cell (Z = 8) of dimensions a = 20.139(3), b = 23.332(5), c = 14.214(3) Å. Those of 2 are tetragonal, space group I [Formula: see text], with four molecules per unit cell (Z = 4) of dimensions a = 13.8853(11), c = 8.077(2) Å. The discrete homoleptic cation [Cd(tztH) 4 ] 2+ is characterized for the first time in 1 and 2. The cations are of point group symmetry C 2 and S 4 in 1 and 2, respectively. In both cases the ligands are S-bound, and the CdS 4 kernel is a squashed tetrahedron. In 2, the eight-coordinate anion [Cd(O 2 NO) 4 ] 2- is characterized for the second time. 113 Cd CP MAS NMR data are reported for solid 1 and 2, and also for solids produced by fusing Cd(NO 3 ) 2 ·4H 2 O with different molar ratios amounts of tztH, and by fusing Cd(O 3 SCF 3 ) 2 with six mol equivalents of tztH. In the Cd(NO 3 ) 2 ·4H 2 O:tztH mixtures, species identified include unreacted cadmium salt 2 ([Cd(tztH) 4 ](NO 3 ) 2 ) and possibly Cd(tztH) 3 (NO 3 ) 2 . [Cd(tztH) 4 ](NO 3 ) 2 becomes the major species only when a significant excess of tztH is used. In the mixtures with tztH:Cd > 4, neither Cd(NO 3 ) 2 ·4H 2 O nor Cd(O 3 SCF 3 ) 2 form complexes containing more than four tztH ligands. Reduced-temperature 111 Cd NMR data are reported for Cd(ClO 4 ) 2 ·6H 2 O:tztH mixtures in MeOH. Species identified are Cd(tztH) w 2+ (solv) (w = 03).Key words: 1,3-thiazolidine-2-thione, cadmium complexes, X-ray analysis, 113 Cd CP MAS NMR, solution 111 Cd NMR, tetrakis(1,3-thiazolidine-2-thione)cadmium(2+) cation, tetrakis(nitrato-O,O')cadmate(2) anion.
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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 | 0.020 | 0.011 |
| Meta-epidemiology (narrow) | 0.018 | 0.018 |
| Meta-epidemiology (broad) | 0.026 | 0.010 |
| Bibliometrics | 0.011 | 0.014 |
| Science and technology studies | 0.009 | 0.016 |
| Scholarly communication | 0.004 | 0.007 |
| Open science | 0.011 | 0.005 |
| Research integrity | 0.010 | 0.020 |
| Insufficient payload (model declined to judge) | 0.000 | 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; both teacher heads agree on what is shown here.
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".