Thomas Hahn

Reactions of coordinated ligands: VIII. Phosphinoformic acids RR′PCOOH (R, R′ = organyl, H), the still unknown P-analogues of carbaminic acids, stabilized as ligands in complexes (CO)5MPRR′COOH (M Cr, W)

Abstract Metal carbonyl complexes containing phosphinoformic acids, including the parent compound H2PCOOH, have been made by the following route: (CO)5MPRR′H → (CO)5MPRR′Li → (CO)5MPRR′COOLi → (CO)5MPRR′COOSiMe3 → (CO)5MPRR′COOH (R = organyl, H; M  Cr, W). While the uncoordinated silyl esters RR′PCOOSiMe3 spontaneously decompose to RR′PH, CO2 and Me3SiOH in protic media the last step in the sequence above can be safely brought about by silica gel. So far only chromatography on silica gel has been found to provide the mild conditions necessary to avoid decarboxylation of the ligated esters during protolysis. Some reactions of (CO)5MPRR′COOLi are reported and compared with those of the free ligands RR′PCOOLi. The structures of the complexes have been confirmed by spectroscopic methods (IR, MS, 1H-, 13P-, 13C-NMR).

ZUR KENNTNIS DES NATRIUMDIPHENYLPHOSPHINOFORMIATS Ph2PCOONa1

Abstract Ph 2 PCOONa 2, hergestellt dutch Reaktion von Ph2PNa mit CO2, wird in protischen Medien rasch unter Bildung von Ph2PH and CO2 hydrolysiert. Die Hydrolyse verlauft in Natronlauge sehr viel langsamer and es bilden sich zusatzlich geringe Mengen Ph2P(O)O− und HCOO−, Aus 2 and stochiometrischen Mengen RI bilden sich tertiare Phosphine Ph2PR (R[dbnd]Me, Et) wahrend mit uberschussigem MeI das Phosphoniumsalz [Ph2PMe2]I erhalten wird. Ph2PCOOMe, Ph2PCOOSiMe3 bzw. Ph2PCSSNa wurden durch Umsetzung von 2 mit (MeO)2SO2, Me3SiCl bzw. CS2 synthetisiert. Ph2P(O)ONa and Ph2P(S)SNa entstanden bei der Reaktion von 2 mit O2 oder S8 in Benzol. Concerning Sodiumdiphenylphosphinoformiate Ph2PCOONa1. Ph2PCOONa 2, prepared from Ph2PNa and CO2, is readily hydrolyzed in protic media with formation of Ph 2 PH 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[dbnd]Me, Et) while ...

DARSTELLUNG UND REAKTIONEN EINIGER LITHIUMPHOSPHINOFORMIATE R2PCOOLi UND RHPCOOLi—AB INITIO-RECHNUNGEN IM SYSTEM H2PCOOH—PH3/CO2

Abstract The preparation of lithiumphosphinoformates R2PCOOLi 1 (R = Ph, c-Hexyl, i-Pr, Et) and RHPCOOLi 2 (R = Ph, c-Hexyl) from R2PLi or RPHLi 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 McI, (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 Me3SiCl RHPCOOSiMe3 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. Die Darstellung der Lithiumphosphinoformiate R2PCOOLi 1 (R = Ph, c-Hex, i-Pr, Et)...

The inorganic–organic hybrid material triethyl­enetetra­mmonium hexa­chlorido­rhodate(III) chloride

Single crystals of the new title compound [systematic name: 1,4,7,10-tetrazoniadecane hexachloridorhodate(III) chloride], [H3N(CH2)2NH2(CH2)2NH2(CH2)2NH3][RhCl6]Cl, were obtained from the corresponding amine and rhodium trichloride in hydrochloric acid solution by slow crystallization under diffusion-controlled conditions at room temperature. Its solid-state structure is defined by a three-dimensional framework of numerous electrostatic-supported N—H⋯Cl hydrogen bonds between the ionic components of the compound. Within this framework, layered arrangements of the complex ions on one hand and of the protonated amines and chloride ions on the other hand, can be recognized. The octahedral hexachloridorhodate(III) anion resides on a symmetry site, while the triethylenetetrammonium cation and the chloride ion both reside on twofold axes.

Reactions of Sodiumdiphenylphosphinoformiat

Abstract Sodiumdiphenylphosphinoformiat 1, can easily be of Ph2PNa with CO2 [1]. Some reactions of 1 have reinvestigated by us.