Abstract:Cyclic phosphorus ylids such as 3 and 4 form coordination compounds both with main group and transition group metals. While 3 functions exclusively as a monodentate ligand, 4 can be monodentate or bidentate. In many reactions of 3 with carbonyl metals, organometallic compounds, and metal halides the cyclic structure is retained, in other cases it is opened. After reviewing the syntheses of 3,4 and a phosphirane examples of reactions with metal compounds and their products are described and discussed. Special attention is given to the formation of C-C bonds in some of the reactions.

Inhaltsu È bersicht. Die Darstellung von 1,1,3,3,5,5-Hexakis-(dimethylamino)-1,2-dihydro-3k 5 ,5k 5 -[1,3,5]triphosphininiumtetrafluoroborat (3) und 1,1,3,3,5,5-Hexakis(dimethylamino)-k 5 -[1,3,5]triphosphinantriium-tris(tetrafluoroborat) (4) aus 1,1,3,3,5,5-Hexakis-(dimethylamino)-1k 5 ,3k 5 ,5k 5 -triphosphinin (1) und HBF 4´O (C 2 H 5 ) 2 werden beschrieben. Die Strukturen von 3 und 4 werden durch ihre NMR-Spektren und Kristallstrukturanalysen belegt. Durch Hydrolyse von 4 mit konz. Salzsa È ure entsteht 1,3,5-Trioxo-1k 5 ,3k 5 ,5k 5 -[1,3,5]triphosphinan-1,3,5-triol (Cyclotrimethylentriphosphinsa Èure) (8), durch deren Neutralisierung mit NaOH ihr Natriumsalz 9. 8 und 9 sind durch ihre NMR-Spektren charakterisiert. Fu È r die Verbindungen 1'±4' und das Trianion 9 wurden quantenchemische Rechnungen durchgefu È hrt. Die Systeme 1'±4' unterscheiden sich von 1±4 dadurch, dass die Gro È ûe der Liganden am Phosphoratom von N(CH 3 ) 2 auf NH 2 reduziert wurde. Die Ziele der Rechnungen waren, Hybridisierungen und Moleku È lstrukturen, Lewis-bzw. Resonanzstrukturen und Ladungsverteilungen sowie NMR-chemische Verschiebungen zu ermitteln.Protonation of 1,1,3,3,5,5-Hexakis(dimethylamino)-k 5 -[1,3,5]triphosphinine.Abstract. Preparation of 1,1,3,3,5,5-hexakis(dimethylamino)-1,2-dihydro-3k 5 ,5k 5 -[1,3,5]triphosphininium-tetrafluoroborate (3) und 1,1,3,3,5,5-hexakis(dimethylamino)-k 5 -[1,3,5]triphosphinanetriium-tris(tetrafluoroborate) (4) from 1,1,3,3,5,5-hexakis(dimethylamino)-1k 5 ,3k 5 ,5k 5 -triphosphinine 1 and HBF 4´O (C 2 H 5 ) 2 are described. The structures of 3 und 4 are elucidated by n. m. r. and X-ray structural analyses. By hydrolysis of 4 with conc. hydrochloric acid 1,3,5-trioxo1k 5 ,3k 5 ,5k 5 -[1,3,5]triphosphinane-1,3,5-triol (cyclotrimethylene-triphosphinic acid) (8) is formed. Neutralisation with NaOH yields its sodium salt 9. 8 and 9 are characterized by their n. m. r. spectra. Quantum chemical calculations have been investigated for the compounds 1'±4' and the trianion 9. The systems 1'±4' are distinguished from 1±4 by the size of the ligands at phosphorus which is reduced from N(CH 3 ) 2 to NH 2 , respectively. The aims of the calculations are to elucidate hybridisations and molecular structures, Lewis or resonance structures, electronic charge distributions and NMR chemical shifts.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.