- Synthesis, Crystal and Electronic Structures of a Thiophosphinoyl- and Amino-Substituted Metallated Ylide
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α-Metallated ylides have revealed themselves to be versatile reagents for the introduction of ylide groups. Herein, we report the synthesis of the thiophosphinoyl and piperidyl (Pip) substituted α-metallated ylide [Ph2(Pip)P=C?P(S)Ph2]M (M=Li, Na, K) through a four-step synthetic procedure starting from diphenylmethylphosphine sulfide. Metallation of the ylide intermediate was successfully accomplished with different alkali metal bases delivering the lithium, sodium and potassium salts, the latter isolable in high yields. Structure analyses of the lithium and potassium compounds in the solid state with and without crown ether revealed different aggregates (monomer, dimer and hexamer) with the metals coordinated by the thiophosphoryl moiety and ylidic carbon atom. Although the piperidyl group does not coordinate to the metal, it significantly contributes to the stability of the yldiide by charge delocalization through negative hyperconjugation.
- J?rges, Mike,Kroll, Alexander,Kelling, Leif,Gauld, Richard,Mallick, Bert,Huber, Stefan M.,Gessner, Viktoria H.
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p. 1089 - 1094
(2021/09/29)
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- Mixed (P=S/P=O)-stabilized geminal dianion: Facile diastereoselective intramolecular C-H activations by a related ruthenium-carbene complex
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A new unsymmetrical geminal dianion that contained both a phosphine oxide moiety and a phosphine sulfide moiety has been synthesized. Its reactivity towards RuII was explored, which led to the formation of a highly reactive carbene complex that evolved at room temperature to yield a kinetic orthometalated RuII complex through C-H activation of the phenyl group of the phosphine oxide moiety. This insertion was found to be thermally reversible and a second C-H insertion occurred at a phenyl group of the phosphine sulfide moiety to form the thermodynamic orthometalated Ru II complex in a diastereospecific manner. DFT calculations fully rationalized the experimental findings in terms of the relative energies of the kinetic and thermodynamic products and allowed the mechanism of this process to be fully understood.
- Heuclin, Hadrien,Le Goff, Xavier F.,Mezailles, Nicolas
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p. 16136 - 16144
(2013/02/23)
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- New method for synthesis of methylenebis(diarylphosphine) monoxides
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Synthesis of methylenebis(diphenyl- and methylenebis(di-p-tolylphosphine) monoxides, via the reaction of diarylphosphines with formic acid in presence of concentrated hydrochloric acid is described. Methylenebis(diphenylphosphine) monoxide is oxidized with hydrogen peroxide and sulfur into the corresponding methylenebis(diphenylphosphine) dioxide and methylenebis(diphenylphosphine) monoxide monosulfide. Attempts to carry out this reaction with butylphenyl- and dibutylphosphines failed.
- Bondarenko,Rudomino,Tsvetkov
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p. 125 - 126
(2007/10/02)
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