Preparation and characterization of iridium(III) Complexes Containing (2-Aminoethyl)dimethylphosphine (edmp) or (2-Aminoethyl)diphenylphosphine (edpp). Structures of/ac-[Ir(edmp)₃]Cl₃-5H₂0 and trans(Cl,Cl),cis(P,P)-[IrCl₂ (edpp)₂]BF₄ and Comparisons of Their properties with those of the cobalt (III) and Rhodium(III) Analogs

The iridium(III) complexes containing (2-Aminoethyl)dimethylphosphine (edmp) or (2-Aminoethyl)diphen-ylphosphine (edpp) were prepared. Crystal structures of/ac-[Ir(edmp)₃]Cl3∗5H₂0 (2), trans(Cl,Cl),cis(P,P)-[IrCl₂ (edpp)₂]BF₄ (3), and A(lel₃)-and δ (o₃)-[Ir(P,chxn)₃](N0₃)₃-3H₂0 (4 and 5; chxn= trans-1,2-cyclo-hexanediamine) were determined by single-crystal X-ray diffraction. Crystal data and final R values are: for 2, FW=703.7, triclinic, PT, a = 11.718(2), b = 13.199(1), c = 9.482(l) Aα=91.44(l), β=105.86(1), γ = 90.53(1)°, 7 = 1410.0(2) A3, Dx = l.ffi Mgm^-3, and Z = 2, # = 0.039 for 5410 reflections. For 3, FW=808.5, triclinic, Pi, a = 11.465(l), 6 = 13.694(1), c=10.049(l) Aα=94.764(6), β=92.197(8), γ=102.807(8)°, 7 = 1530.5(2) A³, Dx = 1.75 Mgm"3, and Z = 2, fl=0.035 for 5978 reflections. For 4, FW=774.9, hexagonal, P63, a = 13.005(l), c=10.221(2) A, 7 = 1497.1(3) A3, Dm = 1.71(2), DX = 1.12 Mgm"3, and Z=2, .R=0.020 for 1063 reflections. For 5, hexagonal, FW=774.9, P63, a=13.359(l), c=9.848(2) A, 7=1522.0(3) A³, <m = 1.70(2), >= 1.69 Mgm"3, and Z = 2, i?=0.015 for 1105 reflections. The average Ir-N bond length of 2.167(6) A in 2 is longer by 0.077(6) A than those in 4 and 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-PMe2 group in edmp is ConiIrniRhin. In 3, the elongation of the metal-nitrogen bond length by the trans influence of the-PPh2 group in edpp is smaller than that of the-PMe2 group 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)₃J³⁺ and trans(C7,C7),czs(P,P)-[MCl₂ (edpp)₂]+ (M = Coin, RhIH, and Ir111) are compared and Shimura's spectrochemical parameters for iridium(III) are discussed.