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p-Chloro binuclear rhodium( I) complexes trap the bidentate PIII-NIII tautomers of bicyclic phosphoranes containing a P-H bond to give monomeric rhodium(1) complexes, two of which [(5a) and (5b)l have been characterised by X-ray crystallography.(1) b3( 2 ) Jt THE bicyclic phosphoranes (1) formally arise from oxidative addition of the N-H or 0-H groups of the intermediates (2), (3), or (4) to the P I 1 1 atom [reaction (l)]. However, neither (2) nor the equilibrium between (1) and (2), (3), or (4) have been observed spectroscopically. The presence of two donor atoms in the potentially bidentate ligand (2) prompted us to study the co-ordination chemistry

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In den bicyclischen Phosphoranen (II) wird in Gegenwart von Mo‐ oder W‐hexacarbonyl, dimerem Chlorodicarbonyl‐Rh oder Chloro‐bis‐[ethylen]‐Rh die P‐N‐Bindung gespalten.