| Abstrakt: |
The iridium(III) complexes containing (2-aminoethyl)dimethylphosphine (edmp) or (2-aminoethyl)diphenylphosphine (edpp) were prepared. Crystal structures of fac-[Ir(edmp)3]Cl3·5H2O (2), trans(Cl,Cl),cis(P,P)-[IrCl2(edpp)2]BF4(3), and ?(lel3)- and ?(ob3)-[Ir(R,R-chxn)3](NO3)3·3H2O (4and 5; chxn = trans-1,2-cyclohexanediamine) were determined by single-crystal X-ray diffraction. Crystal data and final Rvalues are: for 2, FW = 703.7, triclinic, , a= 11.718(2), b= 13.199(1), c= 9.482(1) Å, a= 91.44(1), ß= 105.86(1), ?= 90.53(1)°, V= 1410.0(2) Å3, Dx= 1.66 Mg m-3, and Z= 2, R= 0.039 for 5410 reflections. For 3, FW = 808.5, triclinic, , a= 11.465(1), b= 13.694(1), c= 10.049(1) Å, a= 94.764(6), ß= 92.197(8), ?= 102.807(8)°, V= 1530.5(2) Å3, Dx= 1.75 Mg m-3, and Z= 2, R= 0.035 for 5978 reflections. For 4, FW = 774.9, hexagonal, P63, a= 13.005(1), c= 10.221(2) Å, V= 1497.1(3) Å3, Dm= 1.71(2), Dx= 1.72 Mg m-3, and Z= 2, R= 0.020 for 1063 reflections. For 5, hexagonal, FW = 774.9, P63, a= 13.359(1), c= 9.848(2) Å, V= 1522.0(3) Å3, Dm= 1.70(2), Dx= 1.69Mg m-3, and Z= 2, R= 0.015 for 1105 reflections. The average Ir–N bond length of 2.167(6) Å in 2is longer by 0.077(6) Å than those in 4and 5. The structural data of the corresponding cobalt(III) and rhodium(III) complexes show that the order of the strength of the trans influence of the –PMe2group in edmp is CoIII< IrIII< RhIII. In 3, the elongation of the metal–nitrogen bond length by the trans influence of the –PPh2group in edpp is smaller than that of the –PMe2group in 2, and the elongation is nearly the same as those in the corresponding cobalt(III) and rhodium(III) complexes. The absorption spectra of the two series of complexes, fac-[M(edmp)3]3+and trans(Cl,Cl),cis(P,P)-[MCl2(edpp)2]+(M = CoIII, RhIII, and IrIII) are compared and Shimura’s spectrochemical parameters for iridium(III) are discussed. |
