Synthesis and coordination studies of new aminoalcohol functionalized tertiary phosphines
Bibliographic record
Abstract
The synthesis of two new aminoalcohol functionalized tertiary phosphines o-Ph 2 PCH 2 N(H)C 6 H 4 (OH) (I) and o-Ph 2 PCH 2 N(H)C 6 H 4 (CH 2 OH) (II) are reported. Oxidation with aqueous H 2 O 2 gave the corresponding phosphine oxides o-Ph 2 P(O)CH 2 N(H)C 6 H 4 (OH) (III) and o-Ph 2 P(O)CH 2 N(H)C 6 H 4 (CH 2 OH) (IV) ( 31 P NMR evidence only). The ligating ability of I, II and, in several cases, the known ligand 2,3-Ph 2 PCH 2 N(H)C 5 H 3 N(OH) (V), was investigated with a range of late transition-metal precursors. Accordingly, reaction of 2 equiv of I (or II) with [MCl 2 (cod)] (M = Pd or Pt, cod = cycloocta-1,5-diene) gave the corresponding dichloro metal(II) complexes [MCl 2 (I) 2 ] (M = Pd 1; M = Pt 2) and [MCl 2 (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(CH 3 ) 2 (cod)] gave the neutral complex [Pt(CH 3 ) 2 (II) 2 ] (5) whose X-ray structure confirmed a cis disposition of "hybrid" ligands. In contrast, reaction of I with [Pt(CH 3 ) 2 (cod)] gave initially [Pt(CH 3 ) 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{C 5 (CH 3 ) 5 }} 2 ] with I (or II) proceeds smoothly and gave the mononuclear complexes [RuCl 2 (p-cymene)I] (7), [RuCl 2 (p-cymene)II] (8), [RhCl 2 {C 5 (CH 3 ) 5 }I] (9), and [RhCl 2 {C 5 (CH 3 ) 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···Cl coord 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-C 6 H 4 CH 2 N(CH 3 ) 2 , C,N-C 10 H 6 N(CH 3 ) 2 , C,N-C 6 H 4 N=NC 6 H 5 ] with V (or I) gave the neutral complexes [PdCl(C~N)V] (13-15) (or [PdCl(C 9 H 12 N)I] (16)), respectively. Chloride abstraction from 13 (or 15) with Ag[BF 4 ] gave the cationic complexes [Pd(C~N)V][BF 4 ] (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.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.001 |
| 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) | 0.001 | 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".