Abstract: | The water‐soluble phosphine ligands, 1,3,5‐triaza‐7‐phosphatricyclo[3.3.1.13,7]decane (tpa) and 1‐alkyl‐1‐azonia‐3,5‐diaza‐7‐phosphatricyclo[3.3.1.13,7]decane iodides (Rtpa+I−), with alkyl=methyl(mtpa+I−), ethyl (etpa+I−) and n‐propyl, (ptpa+I−), and mtpa+Cl− react with [Rh2Cl2(CO)4] giving the rhodium(I) complexes [RhCl(CO)(tpa)2], [RhI(CO)(Rtpa+I−)2], [RhCl‐(CO)(mtpa+Cl−)3] and [RhI(CO)(Rtpa+I−)3]. The properties and reactivities of the complexes have been investigated using 1H and 31PNMR and IR spectroscopies. The five‐coordinate complexes in solutions show dynamic properties. The complexes are catalysts of the water‐gas shift reaction, the hydrogenation of CC and CO bonds, the hydroformylation of alkenes and the isomerization of unsaturated compounds. Copyright © 1999 John Wiley & Sons, Ltd. |