Abstract
Abstract Reaction of NiI2(RNC)2 (1) (a: R=2,6-Me2C6H3; b; 4-Br-2,6-Me2C6H2; c: 2,4-t-Bu2-6-MeC6H2: d: 2,4,6-t-Bu3C6H2 with RNC or PPh3 gave NiI2(RNC)3 (2) or NiI2(PPh3) (RNC)2 (3) (a: R=2,6-Me2C6H3; b: 2,6-Me2-4-BrC6H2). An X-ray analysis of (3a) showed that the complex has a trigonal bipyramidal structure; crystal data: Space group Pna21; a=21.577(2), b=9.440(1), c=17.075(1) Å, α=β=γ=90.0°, V=3477.7(6) Å3, R=0.0444. The bromide and chloride complexes, NiX2(2,6-Me2C6H3NC)2 (1e: X=Cl; 1f: X=Br) did not produce five-coordinated species. When complexes (1a, 1b, 1e, or 1f) were treated with Hg in the presence of isocyanide, the donor–acceptor complexes [Ni(RNC)4HgX2]2 (X=I, Br, or Cl) (4) were formed. An X-ray analysis of (4b) (R=4-Br-2,6-Me2C6H2) was undertaken; crystal data: Space group: Pl (triclinic); a=12.709(3), b=16.145(3), c=12.614(3) Å, α=96.11(2), β=107.67(2), γ=73.11(2)°, V=2359.5(10) Å3, R=0.0686. The complex is a donor-acceptor complex containing the Ni–Hg bond and has a dimeric structure bridged by two I atoms. The configuration around Ni is the trigonal bipyramid and around Hg, distorted tetrahedron.
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