New rhodium(I) water‐soluble complexes with 1‐alkyl‐1‐azonia‐3,5‐diaza‐7‐phospha‐adamantane iodides and their catalytic activity

The water‐soluble phosphine ligands, 1,3,5‐triaza‐7‐phosphatricyclo3.3.1.1^3,7]decane (tpa) and 1‐alkyl‐1‐azonia‐3,5‐diaza‐7‐phosphatricyclo3.3.1.1^3,7]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 C?C and C?O bonds, the hydroformylation of alkenes and the isomerization of unsaturated compounds. Copyright © 1999 John Wiley & Sons, Ltd.