Synthesis, spectroscopic characterization, and structural studies of new Cu(I) and Cu(II) complexes containing organophosphorus ligands, and crystal structures of (Ph<sub>3</sub>P)<sub>2</sub>Cu[S<sub>2</sub>PMe<sub>2</sub>], (Ph<sub>3</sub>P)<sub>2</sub>Cu[(OPPh<sub>2</sub>)<sub>2</sub>N], Cu[(OPPh<sub>2</sub>)<sub>2</sub>N]<sub>2</sub>, and Cu[(OPPh<sub>2</sub>)(SPPh<sub>2</sub>)N]<sub>2</sub>
Bibliographic record
Abstract
The Cu(I) complexes, (Ph 3 P) 2 CuL (L = [S 2 PMe 2 ] - , [OSPR 2 ] - (R = Me, Ph), [(XPR 2 )(YPR' 2 )N] - (X, Y, R, R' = O, O, Ph, Ph; O, S, Ph, Ph; O, S, OEt, Ph; S, S, Me, Me)) and Cu(II) complexes, CuL 2 (L = [(XPR 2 )(YPR' 2 )N] - (X, Y, R, R' = O, O, Ph, Ph; O, S, Ph, Ph)), have been prepared. The Cu(I) derivatives were characterized by multinuclear NMR spectroscopy and in two cases by X-ray crystallography. (Ph 3 P) 2 Cu[S 2 PMe 2 ] (1) crystallizes in the orthorhombic space group P2 1 2 1 2 1 (No. 19) with cell parameters a = 9.782(2), b = 17.808(4), c = 20.216(4) Å, V = 3521(6) Å 3 and Z = 4, and (Ph 3 P) 2 Cu[(OPPh 2 ) 2 N] (4) in the triclinic space group P[Formula: see text] (No. 2) with cell parameters a = 9.8079(2), b = 12.9141(3), c = 22.5666(5) Å, α = 75.714(2), β = 79.465(2), γ = 68.2770(8)°, V = 2559.9(1) Å 3 and Z = 2. In both cases the phosphorus ligands are bidentate, thus resulting in monomeric molecules that contain tetrahedral CuP 2 S 2 and CuP 2 O 2 cores. The molecular structures of two of the Cu(II) derivatives were also determined. Cu[(OPPh 2 ) 2 N] 2 (8) and Cu[(OPPh 2 )(SPPh 2 )N] 2 (9) crystallize in the triclinic space group P[Formula: see text] (No. 2) with cell parameters a = 8.887(2), b = 10.739(2), c = 12.477(3) Å, α = 77.61(3), β = 76.15(5), γ = 79.46(3)°, V = 1118.3(4) Å 3 and Z = 1 for 8, and a = 9.626(2), b = 14.151(3), c = 24.752(5) Å, α = 88.23(3), β = 79.93(3), γ = 89.77(3)°, V = 3181(1) Å 3 and Z = 3 for 9. The molecule of Cu[(OPPh 2 ) 2 N] 2 (8) has a planar CuO 4 core, while in Cu[(OPPh 2 )(SPPh 2 )N] 2 (9) both planar and tetrahedral copper cores are observed in a ratio of 1:2.Key words: structure, copper, thiophosphinates, oxo- and thio-imidodiphosphinates
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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 | 0.009 | 0.009 |
| Meta-epidemiology (narrow) | 0.022 | 0.024 |
| Meta-epidemiology (broad) | 0.026 | 0.009 |
| Bibliometrics | 0.010 | 0.015 |
| Science and technology studies | 0.012 | 0.014 |
| Scholarly communication | 0.008 | 0.011 |
| Open science | 0.013 | 0.007 |
| Research integrity | 0.012 | 0.018 |
| Insufficient payload (model declined to judge) | 0.001 | 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".