TY - JOUR
T1 - Structural studies of the 1:1 addition complexes of niobium and tantalum pentachlorides with o-phenylenebis(dimethylarsine)
AU - Dewan, John C.
AU - Kepert, David L.
AU - Raston, Colin L.
AU - White, Allan H.
PY - 1975
Y1 - 1975
N2 - The addition of o-phenylenebis(dimethylarsine), 'diars.' in equimolar ratio to the pentachlorides of tantalum and niobium has yielded addition complexes shown by X-ray crystallographic structure determination to have the probable stoicheiometries [TaCl4(diars)2]+[TaCl5(OEt)] - (I), [NbCl4(diars)2]+2[NbCl 3O2]2- (II), and [NbCl4-(diars)2]+ [NbOCl4]- (III). Crystals of (I) are triclinic, space group P1, a = 12.983(4), b = 14.484(6), c = 12.359(6) Å, α = 108.04(3), β = 102.17(5), γ = 110.35(5)°, Z = 2, 2 448 observed reflections being refined to R 0.09. Crystals of (II) are monoclinic, space group C2/c or Cc, a = 20.877(4), b = 16.086(3), c = 19.458(2) Å, β = 106.25(1)°, Z = 4, 1 183 observed reflections refined to R 0.08. Crystals of (III) are triclinic, space group P1 a = 14.815(3), b = 12.273(2), c = 10.397(2) Å, α = 92.03(1), β = 103.56(2), γ = 110.80(2)°, Z = 2, 2 473 observed reflections refined to R 0.06. In all three, an eight-co-ordinate dodecahedral cation is found; mean distances: Ta-As 2.761, Ta-Cl 2.40, Nb-As 2.743, and Nb-Cl 2.426 Å. The structures were determined from diffractometer data [(I) and (III) by the heavy-atom method, (II) by direct methods].
AB - The addition of o-phenylenebis(dimethylarsine), 'diars.' in equimolar ratio to the pentachlorides of tantalum and niobium has yielded addition complexes shown by X-ray crystallographic structure determination to have the probable stoicheiometries [TaCl4(diars)2]+[TaCl5(OEt)] - (I), [NbCl4(diars)2]+2[NbCl 3O2]2- (II), and [NbCl4-(diars)2]+ [NbOCl4]- (III). Crystals of (I) are triclinic, space group P1, a = 12.983(4), b = 14.484(6), c = 12.359(6) Å, α = 108.04(3), β = 102.17(5), γ = 110.35(5)°, Z = 2, 2 448 observed reflections being refined to R 0.09. Crystals of (II) are monoclinic, space group C2/c or Cc, a = 20.877(4), b = 16.086(3), c = 19.458(2) Å, β = 106.25(1)°, Z = 4, 1 183 observed reflections refined to R 0.08. Crystals of (III) are triclinic, space group P1 a = 14.815(3), b = 12.273(2), c = 10.397(2) Å, α = 92.03(1), β = 103.56(2), γ = 110.80(2)°, Z = 2, 2 473 observed reflections refined to R 0.06. In all three, an eight-co-ordinate dodecahedral cation is found; mean distances: Ta-As 2.761, Ta-Cl 2.40, Nb-As 2.743, and Nb-Cl 2.426 Å. The structures were determined from diffractometer data [(I) and (III) by the heavy-atom method, (II) by direct methods].
UR - http://www.scopus.com/inward/record.url?scp=37049140536&partnerID=8YFLogxK
U2 - 10.1039/DT9750002031
DO - 10.1039/DT9750002031
M3 - Article
AN - SCOPUS:37049140536
SN - 1472-7773
SP - 2031
EP - 2038
JO - Journal of the Chemical Society. Dalton Transactions
JF - Journal of the Chemical Society. Dalton Transactions
IS - 20
ER -