TY - JOUR
T1 - 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
AU - Suzuki, Takayoshi
AU - Rude, Mette
AU - Simonsen, Kim P.
AU - Morooka, Mitsuo
AU - Tanaka, Hitoshi
AU - Ohba, Shigeru
AU - Galsbol, Frode
AU - Fujita, Junnosuke
N1 - Publisher Copyright:
© 1994 The Chemical Society of Japan.
PY - 1994
Y1 - 1994
N2 - 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, = 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.
AB - 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, = 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.
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U2 - 10.1246/bcsj.67.1013
DO - 10.1246/bcsj.67.1013
M3 - Article
AN - SCOPUS:84969856032
SN - 0009-2673
VL - 67
SP - 1013
EP - 1023
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
IS - 4
ER -