A possible reaction route for Ir(H)(Cl) 2 (P-i-Pr 3 ) 3 (4) is proposed. The complexes [HP-i-Pr 3 ] 2 [IrCl 6 ] (1), [HP-i-Pr 3 ] 2 [Ir 2 Cl 8 (P-i-Pr 3 )] (2) and [HP-i-Pr 3 ][Ir 2 Cl 7 (P-i-Pr 3 ) 2 ] (3) were investigated. It is shown that 1,2 and 3 are possible intermediates in the synthesis of 4. Crystallographic data are as follows: for 1 (at 298 K), a=9.314(1), b=15.415(2), c=10.073(1) 9, β=95.38(1) o , space group P2 1 /n; for 2 (at 298 K), a=16.382(4), b=13.968(2), c=18.616(3) 9, β=93.62(2) o , space group P2 1 /c; for 3 (at 298 K), a=11.564(3), b=12.436(3),c =28.873(7) 9, β=92.40(2) o , space group P2 1 /c.