Syntheses, structures and spectroscopic properties of mixed-ligand chromium(III) complexes containing 1,2-bis(dimethylphosphino)-ethane, 1,3-bis(dimethylphosphino)propane or 1,1,1-tris(dimethylphosphinomethyl)ethane

TY - JOUR

T1 - Syntheses, structures and spectroscopic properties of mixed-ligand chromium(III) complexes containing 1,2-bis(dimethylphosphino)-ethane, 1,3-bis(dimethylphosphino)propane or 1,1,1-tris(dimethylphosphinomethyl)ethane

AU - Suzuki, Takayoshi

AU - Kashiwabara, Kazuo

AU - Usami, Tsutomu

AU - Imamura, Takeshi

AU - Kiki, Masakazu

AU - Fujita, Junnosuke

AU - Kaizaki, Sumio

PY - 2001/6

Y1 - 2001/6

N2 - Mixed-ligand chromium(III) complexes containing di- or tridentate phosphines, trans-[CrX 2(dmpe) 2] + (X = Cl, Br, I, CN, NCS or N 3; dmpe = Me 2P(CH 2) 2PMe 2), trans-[CrX′ 2(dmpp) 2] + (X′ = Cl, Br or I; dmpp = Me 2P(CH 2) 3PMe 2), [CrX″ 3(tdmme)] (X″ = Cl, Br, CN or NCS; tdmme = MeC(CH 2PMe 2) 3) and [CrCl 2(tdmme)(PMe 3)] +, have been prepared and their structures and spectroscopic properties have been investigated. The single-crystal X-ray analyses of trans-[CrI 2(dmpp) 2]I (6) and [Cr(CN) 3(tdmme)]·2H 2O (16·2H 2O) have also been reported. The Cr-P bond length in 6 (2.5147(6) Å) is longer than those in trans-[CrCl 2(dmpe) 2]BPh 4 (av 2.445 Å) and in 16·2H 2O (av 2.455 Å). In the UV-vis absorption spectra of trans-[Cr(Cl or Br) 2(dmpe or dmpp) 2] +, an intense (ε > 1000 dm 3 mol -1 cm -1) absorption envelope is observed at 20000-30000 cm -1, in addition to the 4B 1 → a 4E d-d transition band at ∼ 17000 cm -1 (ε = 44-65 dm 3 mol -1 cm -1). The envelope consists of three d-d transition components: 4B 1 → 4A 2, 4B 2 and b 4E, similar to the corresponding H 2N(CH 2) 2NH 2 (= en) complexes. The magnetic circular dichroism (MCD) spectra of these didentate phosphine complexes show a spin-forbidden d-d transition ( 4B 1 → 2E, 2B 2) component at ∼ 19000 cm -1. The ligand-field and Racah parameters, Δ(d), Δ(e), Δ(t 2) and B, of the complexes are estimated. It is found that the ligand-field and repulsion parameters of the dmpp complexes are almost the same as those of the corresponding en complexes. For the dmpe complexes, while Δ(d) is just slightly smaller than those of the dmpp and en complexes, the tetragonal symmetry parameters, Δ(e) and Δ(t 2), are much reduced. The ligand-field perturbation energies of phosphines are estimated as Δ dmpp = 21830 > Δ tdmme = 20920 > Δ dmpe = 20620 cm -1, the order of which is strange, since the Cr-P bond lengths in the complexes increase in the order of dmpp > tdmme > dmpe. Furthermore, the interelectronic repulsion parameter B of [Cr(Cl or Br) 3(tdmme)] estimated from the 4A 2 → 4T 1 transition energy (B 35) is remarkably much smaller than the parameter estimated from the spin-forbidden 4A 2 → 2T 2 transition energy (B 55).

AB - Mixed-ligand chromium(III) complexes containing di- or tridentate phosphines, trans-[CrX 2(dmpe) 2] + (X = Cl, Br, I, CN, NCS or N 3; dmpe = Me 2P(CH 2) 2PMe 2), trans-[CrX′ 2(dmpp) 2] + (X′ = Cl, Br or I; dmpp = Me 2P(CH 2) 3PMe 2), [CrX″ 3(tdmme)] (X″ = Cl, Br, CN or NCS; tdmme = MeC(CH 2PMe 2) 3) and [CrCl 2(tdmme)(PMe 3)] +, have been prepared and their structures and spectroscopic properties have been investigated. The single-crystal X-ray analyses of trans-[CrI 2(dmpp) 2]I (6) and [Cr(CN) 3(tdmme)]·2H 2O (16·2H 2O) have also been reported. The Cr-P bond length in 6 (2.5147(6) Å) is longer than those in trans-[CrCl 2(dmpe) 2]BPh 4 (av 2.445 Å) and in 16·2H 2O (av 2.455 Å). In the UV-vis absorption spectra of trans-[Cr(Cl or Br) 2(dmpe or dmpp) 2] +, an intense (ε > 1000 dm 3 mol -1 cm -1) absorption envelope is observed at 20000-30000 cm -1, in addition to the 4B 1 → a 4E d-d transition band at ∼ 17000 cm -1 (ε = 44-65 dm 3 mol -1 cm -1). The envelope consists of three d-d transition components: 4B 1 → 4A 2, 4B 2 and b 4E, similar to the corresponding H 2N(CH 2) 2NH 2 (= en) complexes. The magnetic circular dichroism (MCD) spectra of these didentate phosphine complexes show a spin-forbidden d-d transition ( 4B 1 → 2E, 2B 2) component at ∼ 19000 cm -1. The ligand-field and Racah parameters, Δ(d), Δ(e), Δ(t 2) and B, of the complexes are estimated. It is found that the ligand-field and repulsion parameters of the dmpp complexes are almost the same as those of the corresponding en complexes. For the dmpe complexes, while Δ(d) is just slightly smaller than those of the dmpp and en complexes, the tetragonal symmetry parameters, Δ(e) and Δ(t 2), are much reduced. The ligand-field perturbation energies of phosphines are estimated as Δ dmpp = 21830 > Δ tdmme = 20920 > Δ dmpe = 20620 cm -1, the order of which is strange, since the Cr-P bond lengths in the complexes increase in the order of dmpp > tdmme > dmpe. Furthermore, the interelectronic repulsion parameter B of [Cr(Cl or Br) 3(tdmme)] estimated from the 4A 2 → 4T 1 transition energy (B 35) is remarkably much smaller than the parameter estimated from the spin-forbidden 4A 2 → 2T 2 transition energy (B 55).

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U2 - 10.1246/bcsj.74.1055

DO - 10.1246/bcsj.74.1055

M3 - Article

AN - SCOPUS:0034928813

VL - 74

SP - 1055

EP - 1064

JO - Bulletin of the Chemical Society of Japan

JF - Bulletin of the Chemical Society of Japan

SN - 0009-2673

IS - 6

ER -