181864-73-3Relevant academic research and scientific papers
Synthesis and Identification of Aryl and Alkyl Gem-Dilithium Phosphido-Boranes: A Boost to the Chemistry of Phosphandiides
Guang, Jie,Duwald, Romain,Maddaluno, Jacques,Oulyadi, Hassan,Lakhdar, Sami,Gaumont, Annie-Claude,Harrison-Marchand, Anne
, p. 6717 - 6721 (2018)
The synthesis and identification of unprecedented gem-dianionic phosphorus compounds, that is, gem-dilithium phosphido-boranes Li2[RP?BH3], with R=Ph or Cy, are reported in THF solution. These were obtained by double deprotonation of the corresponding primary phosphine-borane precursors RPH2?BH3. Their in-depth structural study, based on multinuclear (1H, 6Li, 7Li, 11B, 13C, 31P) mono- and bi-dimensional NMR analyses, indicates a strong influence of the phosphorus substituent on the structure of the gem-dianionic phosphorus structure; a monomeric arrangement was obtained when R=phenyl, whereas a cyclic oligomer was observed for R=cyclohexyl. These compounds represent a new type of useful reagent, and their access paves the way for the concept of “RP synthons” (i.e., RP2? phosphandiides), likely to be the most flexible precursors of a variety of phosphorus targets.
Synthesis of water-soluble, aliphatic phosphines and their application to well-defined ruthenium olefin metathesis catalysts
Mohr, Bernhard,Lynn, David M.,Grubbs, Robert H.
, p. 4317 - 4325 (2008/10/08)
Water-soluble aliphatic phosphines Cy2P(CH2)2N(CH3)3 +Cl- (14), Cy2P[4-(N,N-dimethyl-piperidinium)]+Cl- (15), Cy2P(CH2)2SO3-Na + (16), and CyP[(CH2)2N(CH3)3+Cl -]2 (17) (Cy = cyclohexyl) were prepared from air-stable, borane-protected precursors. Spectroscopic investigations of corresponding Pd(PR3)2Cl2 complexes were used to estimate the steric parameters of these new phosphines. Spectroscopic investigation of Ni(CO)3PR3 complexes of the new phosphines indicated that phosphines bearing quaternary amine functionalities were less electron donating than tricyclohexylphosphine, while the presence of a sulfonate group increased phosphine electron donation. Cationic phosphines 14 and 15 were used to synthesize water-soluble ruthenium carbene complexes of the type (Cy2PR)2Cl2Ru=CHPh. These complexes initiate the ring-opening metathesis polymerization (ROMP) of functionalized 7-oxanorbornenes in water, methanol, and aqueous emulsions.
