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, H-1-, P-31-, C-13-NMR).

The preparation of lithiumphosphinoformates R(2)PCOOLi 1 (R = Ph, c-Hexyl, i-Pr, Et) and RHPCOOLi 2 (R = Ph, c-Hexyl) from R(2)PLi or RPHLi and CO2 is described. In the latter reaction RP(COOLi)(2) 3 and RPH(2) are formed in addition to 2. In protic media 1-3 are rapidly decomposed with decarboxylation and formation of R(2)PH and RPH(2), respectively. Reactions of 1 with Mel, (MeO)(2)SO2, Me(3)SiCl and CS2 are similar to those of Ph(2)PCOONa and no significant influence of R was detected. With (MeO)(2)SO2 mixtures of 2 and 3 gave esters RHPCOOMe and RP(COOMe)(2) while with Me(3)SiCl RHPCOOSiMe(3) 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.

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ChemInformVolume 21, Issue 49 Organoelement Compounds ChemInform Abstract: Reactions of Sodium Diphenylphosphinoformate. K. DIEMERT, K. DIEMERT Inst. Anorg. Chem. Strukturchem., Heinrich-Heine-Univ., D-40225 Duesseldorf, GermanySearch for more papers by this authorT. HAHN, T. HAHN Inst. Anorg. Chem. Strukturchem., Heinrich-Heine-Univ., D-40225 Duesseldorf, GermanySearch for more papers by this authorW. KUCHEN, W. KUCHEN Inst. Anorg. Chem. Strukturchem., Heinrich-Heine-Univ., D-40225 Duesseldorf, GermanySearch for more papers by this author K. DIEMERT, K. DIEMERT Inst. Anorg. Chem. Strukturchem., Heinrich-Heine-Univ., D-40225 Duesseldorf, GermanySearch for more papers by this authorT. HAHN, T. HAHN Inst. Anorg. Chem. Strukturchem., Heinrich-Heine-Univ., D-40225 Duesseldorf, GermanySearch for more papers by this authorW. KUCHEN, W. KUCHEN Inst. Anorg. Chem. Strukturchem., Heinrich-Heine-Univ., D-40225 Duesseldorf, GermanySearch for more papers by this author First published: December 4, 1990 https://doi.org/10.1002/chin.199049220AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume21, Issue49December 4, 1990 RelatedInformation

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