Crystal structure and electronic and magnetic properties of hexacyanoosmate (III)
Inorganic chemistry, 2006•ACS Publications
The [OsIII (CN) 6] 3-anion is prepared by chemical oxidation in aqueous solution and
isolated as yellow prisms of [Ph4P] 3 [OsIII (CN) 6]⊙ 6H2O (1). This species crystallizes in
the triclinic space group P 1̄ with cell parameters a= 13.7609 (11) Å, b= 16.2275 (13) Å, c=
17.0895 (14) Å, α= 91.4040 (10)°, β= 109.3600 (10)°, γ= 102.3970 (10)°, V= 3497.4 (5) Å3,
and Z= 2. The slightly distorted octahedral moiety displays Os− C and C− N bond lengths
that average 2.058 and 1.146 Å, respectively. Spin− orbit-coupling splitting of the ground …
isolated as yellow prisms of [Ph4P] 3 [OsIII (CN) 6]⊙ 6H2O (1). This species crystallizes in
the triclinic space group P 1̄ with cell parameters a= 13.7609 (11) Å, b= 16.2275 (13) Å, c=
17.0895 (14) Å, α= 91.4040 (10)°, β= 109.3600 (10)°, γ= 102.3970 (10)°, V= 3497.4 (5) Å3,
and Z= 2. The slightly distorted octahedral moiety displays Os− C and C− N bond lengths
that average 2.058 and 1.146 Å, respectively. Spin− orbit-coupling splitting of the ground …
The [OsIII(CN)6]3- anion is prepared by chemical oxidation in aqueous solution and isolated as yellow prisms of [Ph4P]3[OsIII(CN)6]·6H2O (1). This species crystallizes in the triclinic space group P1̄ with cell parameters a = 13.7609(11) Å, b = 16.2275(13) Å, c = 17.0895(14) Å, α = 91.4040(10)°, β = 109.3600(10)°, γ = 102.3970(10)°, V = 3497.4(5) Å3, and Z = 2. The slightly distorted octahedral moiety displays Os−C and C−N bond lengths that average 2.058 and 1.146 Å, respectively. Spin−orbit-coupling splitting of the ground-state term dominates the NIR region of the electronic spectrum and the magnetic behavior of 1. The experimental information points to higher spin delocalization over the coordinated cyanides than in [FeIII(CN)6]3-.
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