Synthesis and coordination studies of new aminoalcohol functionalized tertiary phosphines
Bibliographic record
Abstract
The synthesis of two new aminoalcohol functionalized tertiary phosphines o-Ph2PCH2N(H)C6H4(OH) (I) and o-Ph2PCH2N(H)C6H4(CH2OH) (II) are reported. Oxidation with aqueous H2O2 gave the corresponding phosphine oxides o-Ph2P(O)CH2N(H)C6H4(OH) (III) and o-Ph2P(O)CH2N(H)C6H4(CH2OH) (IV) (31P NMR evidence only). The ligating ability of I, II and, in several cases, the known ligand 2,3-Ph2PCH2N(H)C5H3N(OH) (V), was investigated with a range of late transition-metal precursors. Accordingly, reaction of 2 equiv of I (or II) with [MCl2(cod)] (M = Pd or Pt, cod = cycloocta-1,5-diene) gave the corresponding dichloro metal(II) complexes [MCl2(I)2] (M = Pd 1; M = Pt 2) and [MCl2(II)2] (M = Pd 3; M = Pt 4) in which I (and II) P-coordinate. Solution NMR studies reveal that 2 and 4 are exclusively cis whereas 1 and 3 are present as a mixture of cis and (or) trans isomers [4.7:1 (for 1); 2.2:1 (for 3)]. Reaction of 2 equiv of II with [Pt(CH3)2(cod)] gave the neutral complex [Pt(CH3)2(II)2] (5) whose X-ray structure confirmed a cis disposition of "hybrid" ligands. In contrast, reaction of I with [Pt(CH3)2(cod)] gave initially [Pt(CH3)2(I)2] (6) which, upon standing, afforded several products possibly reflecting an increased acidity of the phenolic groups of ligated I. Chloro bridge cleavage reactions of [{Ru(µ-Cl)Cl(p-cymene)}2] or [{Rh(µ-Cl)Cl{C5(CH3)5}}2] with I (or II) proceeds smoothly and gave the mononuclear complexes [RuCl2(p-cymene)I] (7), [RuCl2(p-cymene)II] (8), [RhCl2{C5(CH3)5}I] (9), and [RhCl2{C5(CH3)5}II] (10) in good yield. X-ray crystallography confirms both ruthenium complexes bear P-coordinated I (or II) ligands. Molecules of 7 are linked into linear chains via O-H···Clcoord intermolecular hydrogen bonding, a feature absent in the closely related compound 8. Reaction of [AuCl(tht)] (tht = tetrahydrothiophene) with 1 equiv of I (or II) gave the corresponding gold(I) complexes [AuCl(I)] (11) and [AuCl(II)] (12). Bridge cleavage of the cyclometallated palladium(II) dimers [{Pd(µ-Cl)(C~N)}2] [C~N = C,N-C6H4CH2N(CH3)2, C,N-C10H6N(CH3)2, C,N-C6H4N=NC6H5] with V (or I) gave the neutral complexes [PdCl(C~N)V] (13-15) (or [PdCl(C9H12N)I] (16)), respectively. Chloride abstraction from 13 (or 15) with Ag[BF4] gave the cationic complexes [Pd(C~N)V][BF4] (17) (or 18) in which V P,N pyridyl-chelates to the palladium(II) metal centre. The X-ray structures of 13 and 18 have been determined and confirm the expected coordination environments. An array of intra- and intermolecular H-bonding contacts are also observed. All compounds have been characterized by a combination of spectroscopic and analytical studies.Key words: phosphines, crystal structures, alcohols, precious metals.
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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".