Don J. Chandler

THE JAHN-TELLER EFFECT IN A TRIGONAL BIPYRAMIDAL Ni(III) COMPLEX; SYNTHESIS AND X-RAY CRYSTAL STRUCTURE OF trans-NiI3 (PMe3)2

Abstract Reaction of [Ni(μ-t-Bu2As)(PMe3)2]2, with I2(Ni:I = 1:2) in toluene yields the black, crystalline Ni(III) complex trans-Nil3(PMe3)2, (1), (38%). The coordination geometry about Ni is a distorted trigonal bipyramid with a distortion which can be attributed to a Jahn-Teller effect. One Ni-I bond (2.530(1)A) is shorter than the other two (both 2.551(1)A). Crystal data.(1). C6H18I3NiP2, M = 591.6, orthorhombic, space group Pnma. a = 10.197(3), b = 11.155(8) c = 14.213(3)A, U = 1616.7(5)A3, Dc = 2.43 g cm−3, Z = 4. λ(MoK α) = 0.71073 A (graphite monochromator). μ(MoK α) = 70.4 cm−1. Refinement of 1168 reflection I > 3 ·(I)σ out of 1667 unique observed reflections (2.0° < 2° < 50.0°) gave R and Rw values of 0.046 and 0.066, respectively. The Ni-P distances are 2.246(2) A and 2.253(2) A.

SYNTHESIS AND STRUCTURE OF A HETEROBIMETALLIC Fe-Ni PHOSPHIDO BRIDGED COMPLEX; X-RAY CRYSTAL STRUCTURE OF (PMe3)(CO)3Fe(μ-t-Bu2P)Ni(PMe3)Cl, (Fe-Ni)

Abstract Reaction of Fe(CO)3(t-Bu2PH)(t-Bu2PLi) with NiCl2(PMe3)2 gives the heterobimetallic ditertbutyl-phosphido bridged complex (PMe3)(CO)3Fe(μ-t-Bu2P)Ni(PMe3)Cl, (Fe-Ni), (1), (55%). The Fe atom bears three terminal CO groups and a PMe3 ligand in a roughly trigonal-bipyramidal geometry. The Fe-PMe3 ligand is trans to the μ-t-Bu2P group. The Ni atom is roughly planar with the Cl atom trans to the μ-t-Bu2P unit. Crystal data: (1) C17H36ClFeNiO3P3, M = 531.4 monoclinic, space group P21/c (No. 14), a = 17.363 (1) A, b = 11.383 (2) A, c = 13.308 (2) A, β = 104.60 (1)°, U = 2545.1 (5) A3, Dc = 1.387 g cm−3, Z = 4, μ(MoKα = 16.2 cm−1. Refinement of 1979 reflections (I > 3[sgrave](I)) out of 3537 unique observed reflections (2° < 2θ < 46°) gave R and R w values of 0.062 and 0.070 respectively. Data/parameter ratio 8.4, hydrogen atoms not located, λ(MoKx) = 0.71073 A, (graphite monochromator); methods: MULTAN, difference Fourier, full-matrix least squares; all non-hydrogen atoms anisotropic.

The First Structurally Characterized Trithionantimonite Transition Metal Complex, (CO)5W(μ-SBt)Sb(SBut)2, Exhibiting a Novel Mode of Coordination for the Trithioantimonite Ligand Sb(t-BuS)3

Abstract Reaction of Sb(SBut)3 with W(CO)6 in THF gives (CO)5W(μ-SBut)Sb(SBut)2. (1). The structure of (1) was been determined by single crystal X-ray diffraction methods. Crystal data for (1): C17H27O5S3SbW. M = 713.2, monoclinic, space group P21/n (No. 1014), a = 9.892(2), b = 17.489(4), c = 15.014(3) A, Z = 4, U = 2597.1 (5) A3, Dc = 1.824 g cm−3, λ(MoKα) = 0.71073 A. graphite monochromator, μ = 58.22 cm−1. Methods: Multan, difference Fourier, full-matrix least-squares. Refinement of 3083 reflections (I > 3σ(I)) out of 4732 unique observed reflections (2° < 2° < 50°) gives current R and Rw values of 0.043 and 0.047, respectively. All nonhydrogen atoms were refined with anisotropic thermal parameters; hydrogen atoms were not located Data/parameter ratio = 12.6, shift to error ratio = 0.39, highest peak in final difference Fourier = 0.66 eA−3. Data were collected on an Enraf-Nonius CAD-4 diffractometer at 23 ± 2°C. The Sb(SBut)3 ligand binds to W via S giving the W atom an octahedral coordination geometr...