18789-77-0Relevant academic research and scientific papers
DARSTELLUNG UND REAKTIONEN EINIGER LITHIUMPHOSPHINOFORMIATE R2PCOOLi UND RHPCOOLi - AB INITIO-RECHNUNGEN IM SYSTEM H2PCOOH-PH3/CO2
Diemert, K.,Hahn, T.,Kuchen, W.,Tommes, P.
, p. 65 - 76 (2007/10/02)
The preparation of lithiumphosphinoformates R2PCOOLi 1 (R = Ph, c-Hexyl, i-Pr, Et) and RHPCOOLi 2 (R = Ph, c-Hexyl) from R2PLi or RHPLi and CO2 is described.In the latter reaction RP(COOLi)2 3 and RPH2 are formed in addition to 2.In protic media 1-3 are rapidly decomposed with decarboxylation and formation of R2PH and RPH2, respectively.Reactions of 1 with MeI, (MeO)2SO2, Me3SiCl and CS2 are similar to those of Ph2PCOONa and no significant influence of R was detected.With (MeO)2SO2 mixtures of 2 and 3 gave esters RHPCOOMe and RP(COOMe)2 while with Me3SiClRHPCOOSiMe3 was obtained as the sole product.Ab initio MO calculations (GAUSSIAN 90 system of programs; HF/3-21G*, HF/6-31G** and MP2/6-31G** basis sets) showed the phosphinoformic acid to be less stable than its decomposition products, from which it is separated by a high barrier of isomerization.Therefore the acid should be stable in the rarefied gas phase.Key words: Li-Phosphinoformates; R2PCOOLi; RHPCOOLi; RP(COOLi)2; ab initio MO calculations; H2PCOOH-PH3/CO2.
ZUR KENNTNIS DES NATRIUMDIPHENYLPHOSPHINOFORMIATS Ph2PCOONa
Diemert, Klaus,Hahn, Thomas,Kuchen, Wilhelm
, p. 287 - 294 (2007/10/02)
Ph2PCOONa 2, prepared from Ph2PNa and CO2, is readily hydrolyzed in protic media with formation of Ph2PH and CO2.Hydrolysis is much slower in NaOH and small quantities of Ph2P(O)O- and HCOO- are additionally formed.Reactions of 2 with RI in stoichiometrical amounts gave tertiary phosphines Ph2PR (R=Me, Et) while the phosphonium compound I resulted from 2 and MeI in excess.Ph2PCOOMe, Ph2PCOOSiMe3 or Ph2PCSSNa were obtained from 2 and (MeO)2SO2, Me3SiCl or CS2.Ph2P(O)ONa and Ph2P(S)SNa were isolated when 2 was reacted with O2 or S8 in benzene.
