38957-97-0Relevant academic research and scientific papers
Ready Approach to Organophosphines from ArCl via Selective Cleavage of C-P Bonds by Sodium
Ye, Jingjing,Zhang, Jian-Qiu,Saga, Yuta,Onozawa, Shunya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
, p. 2682 - 2694 (2020/07/30)
The preparation, application, and reaction mechanism of sodium phosphide R2PNa and other alkali metal phosphides R2PM (M = Li and K) have been studied. R2PNa could be prepared, accurately and selectively, via the reactions of SD (sodium finely dispersed in mineral oil) with phosphinites R2POR′ and chlorophosphines R2PCl. R2PNa could also be prepared from triarylphosphines and diarylphosphines via the selective cleavage of C-P bonds. Na was superior to Li and K for these reactions. R2PNa reacted with a variety of ArCl to efficiently produce R2PAr. ArCl is superior to ArBr and ArI since they only gave low yields of the products. In addition, Ph2PNa is superior to Ph2PLi and Ph2PK since Ph2PLi did not produce the coupling product with PhCl, while Ph2PK only gave a low yield of the product. An electron-withdrawing group on the benzene ring of ArCl greatly accelerated the reactions with R2PNa, while an alkyl group reduced the reactivity. Vinyl chloride and alkyl chlorides RCl also reacted efficiently. While t-BuCl did not produce the corresponding product, admantyl halides could give the corresponding phosphine in high yields. A wide range of phosphines were prepared by this method from the corresponding chlorides. Unsymmetric phosphines could also be conveniently generated in one pot starting from Ph3P. Chiral phosphines were also obtained in good yields from the reactions of menthyl chlorides with R2PNa. Possible mechanistic pathways were given for the reductive cleavage of R3P by sodium generating R2PNa and the substitution reactions of R2PNa with ArCl generating R2PAr.
Ph2PI as a reduction/phosphination reagent: Providing easy access to phosphine oxides
Wang, Feijun,Qu, Mingliang,Chen, Feng,Xu, Qin,Shi, Min
supporting information; experimental part, p. 8580 - 8582 (2012/09/22)
The reaction of aldehydes with Ph2PI provides a facile way to the synthesis of pentavalent phosphine compounds with moderate to good yields.
Synthesis and structure of intermediates in copper-catalyzed alkylation of diphenylphosphine
Cain, Matthew F.,Hughes, Russell P.,Glueck, David S.,Golen, James A.,Moore, Curtis E.,Rheingold, Arnold L.
scheme or table, p. 7650 - 7662 (2010/11/19)
Cu(I) catalysts for alkylation of diphenylphosphine were developed. Treatment of [Cu(NCMe)4][PF6] (1) with chelating ligands gave [CuL(NCMe)][PF6] (2; L = MeC(CH2PPh2) 3 (triphos), 3; L = 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (XantPhos)). These complexes catalyzed the alkylation of PHPh2 with PhCH2Br in the presence of the base NaOSiMe3 to yield PPh2CH2Ph (4). The precursors Cu(dtbp)(X) (dtbp =2,9-di-t-butylphenanthroline, X = Cl (5) or OTf (6)), CuCl, and 1 also catalyzed this reaction, but dtbp dissociated from 5 and 6 during catalysis. Both 2 and 3 also catalyzed alkylation of PHPh2 with PhCH 2Cl/NaOSiMe3, but XantPhos dissociation was observed when 3 was used. When CH2Cl2 was used as the solvent for alkylation of PhCH2Cl with precursors 2 or 3, or of PhCH(Me)Br with 2, it was competitively alkylated to yield PPh2CH2Cl (7), which was formed exclusively using 2 in the absence of a benzyl halide. Cu(triphos)-catalyzed alkylation of PhCH(Me)Br gave mostly PPh2CHMePh (8), along with some Ph2P-PPh2 (9), which was also formed in attempted alkylation of dibromoethane with this catalyst. The phosphine complexes [Cu(triphos)(L′)][PF6] (L′ = PH2Ph (10), PH2CH2Fc (Fc = C5H4FeC 5H5, 11), PHPh2 (12), PHEt2 (13), PHCy2 (Cy = cyclo-C6H11, 14), PHMe(Is) (Is = 2,4,6-(i-Pr)3C6H2, 15), PPh2CH 2Ph (16), PPh2CH2Cl (17)), and [Cu(XantPhos)(L′)][PF6] (L′ = PHPh2 (18), PPh2CH2Ph (19)) were prepared by treatment of 2 and 3 with appropriate ligands. Similarly, treatment of dtbp complexes 5 or 6 with PHPh2 gave [Cu(dtbp)(PHPh2)(X)] (X = OTf (20a) or Cl (20b)), and reaction of PPh2CH2Ph (4) with 1 formed [Cu(PPh2CH2Ph)3][PF6] (21). Complexes 2, 3, 11-14, 16, 17, 19, and 21 were structurally characterized by X-ray crystallography. Deprotonation of diphenylphosphine complex 12 in the presence of benzyl bromide gave diphenylbenzylphosphine complex 16, while deprotonation of 12 in CD2Cl2 gave 17 containing a PPh2CD2Cl ligand. Low-temperature deprotonation of the soluble salt 12-[B(ArF)4] (ArF = 3,5-(CF 3)2C6H3) in THF-d8 gave the phosphido complex Cu(triphos)(PPh2) (22). Thermally unstable 22 was characterized by NMR spectroscopy and, in comparison to 12, by density functional theory (DFT) calculations, which showed it contained a polarized Cu-P bond. The ligand substitution step required for catalytic turnover was observed on treatment of 16 or 17 with PHPh2 to yield equilibrium mixtures containing 12 and the tertiary phosphines 4 or 7; equilibrium constants for these reactions were 8(2) and 7(2), favoring complexation of the smaller secondary phosphine in both cases. These observations are consistent with a proposed mechanism for catalytic P-C bond formation involving deprotonation of the cationic diphenylphosphine complex [Cu(triphos)(PHPh2)][PF 6] (12) by NaOSiMe3 to yield the phosphido complex Cu(triphos)(PPh2) (22). Nucleophilic attack on the substrate (benzyl halide or CH2Cl2) then yields the tertiary phosphine complex [Cu(triphos)(PPh2CH2X)][PF6] (X = Ph (16) or Cl (17)), and ligand substitution with PHPh2 regenerates 12.
COMPOUNDS COMPRISING PHOSPHORUS-CONTAINING METAL COMPLEXES
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Page 23-24, (2010/11/30)
Compounds comprising phosphorus-containing metal complexes can be used in electroluminescent devices and have an emission maximum closer to the blue region of the visible light spectrum. The complexes can be used within an organic active layer in electron
