55552-24-4Relevant articles and documents
Adaptive Behavior of a Ditopic Phosphine Ligand
Renard, Nicolas,Brenner, Eric,Matt, Dominique,Gourlaouen, Christophe
, p. 2996 - 3004 (2019)
Synthetic, structural and computational studies have been performed to investigate ligand interchange in the fluxional chelate complex [RhCl3{Ph2PACH2C(OA)OEt-κ2POA}{Ph2PBCH2C(OB)OEt-κP}], which contains two hybrid phosphine-ester ligands, one acting as P,O chelator, the other as a P-monodentate ligand. The observed ligand exchange may occur according to two pathways which both involve four elementary movements: a) oxygen dissociation with formation of a lacunary octahedral RhCl3P2 intermediate; b) migration of the Cl atom trans to PA towards the position trans to PB; c) rotations of the phosphine moieties about the Rh–P bonds, these occurring either concomitantly with the Cl displacement or in a separate step; d) coordination of an oxygen atom of the second phosphine. The two pathways thus differ by conformational changes within two distinct steps. In each pathway the rate-limiting step is the one involving a movement of the two phosphines, which generates steric frictions between the two PPh2 groups. The calculated theoretical energetic spans of both pathways (ΔG≠ ≈ 17 kcal mol–1) is close to the energy barrier obtained from a variable temperature NMR study carried out in C2D2Cl4 (ΔG≠ = 15.5 kcal mol–1). While one of the pathways leads to an isomer with a Rh-bound ethoxy O atom, the other results in the isomer having the metal coordinated to the adjacent C=O group. Exchange between the two O atoms of the coordinated ester group occurs readily (ΔGTS = 12.5 kcal mol–1).
Photoinduced Coupling Reaction of Diphenyl(2,4,6-trimethylbenzoyl)phosphine Oxide with Interelement Compounds: Application to the Synthesis of Thio- or Selenophosphinates
Sato, Yuki,Kawaguchi, Shin-Ichi,Nomoto, Akihiro,Ogawa, Akiya
, p. 3558 - 3567 (2017/08/16)
Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TMDPO) is a radical initiator widely used in the field of macromolecular chemistry, but not often applied in synthetic organic chemistry. We have focused on the use of TMDPO as a phosphorus source in reactions with different E - E compounds, where E - E represents a heteroatom-heteroatom bond, under photoirradiation. Interestingly, the cross-coupling reaction between TMDPO and disulfides or diselenides successfully affords thio- or selenophosphinates and thio- or selenoesters, respectively. The synthesis of series of thio- and selenophosphinates by this photoinduced cross-coupling reaction is demonstrated.
CsOH-promoted P-alkylation: A convenient and highly efficient synthesis of tertiary phosphines
Honaker, Matthew T.,Sandefur, Benjamin J.,Hargett, James L.,McDaniel, Alicia L.,Salvatore, Ralph Nicholas
, p. 8373 - 7377 (2007/10/03)
A mild and efficient method for the synthesis of tertiary phosphines and ditertiary phosphines has been developed. In the presence of cesium hydroxide, molecular sieves and DMF at room temperature, various secondary phosphines and alkyl bromides were examined, and the results have demonstrated that this methodology offers a general synthetic procedure to produce tertiary phosphines in moderate to high yields. Optically active tertiary phosphine synthesis is also described.
