139010-70-1Relevant academic research and scientific papers
Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9
Brennessel, William W.,Kucera, Benjamin E.,Young, Victor G.,Ellis, John E.
, p. 1118 - 1127 (2019/07/24)
Structures and spectroscopic characterization of the divalent complexes cisdibromidotetrakis( 2,6-dimethylphenyl isocyanide)iron(II) dichloromethane 0.771-solvate, [FeBr2(C9H9N)4]-0.771CH2Cl2 or cis-FeBr2(CNXyl)4-0.771CH2Cl2 (Xyl = 2,6-dimethylphenyl), trans-dibromidotetrakis(2,6-dimethylphenyl isocyanide)-iron(II), [FeBr2(C9H9N)4] or trans-FeBr2(CNXyl)4, trans-dibromidotetrakis(2,6-dimethylphenyl isocyanide)cobalt(II), [CoBr2(C9H9N)4] or trans-CoBr2(CNXyl)4, and trans-dibromidobis(2,6-dimethylphenyl isocyanide)nickel(II), [NiBr2(C9H9N)2] or trans-NiBr2(CNXyl)2, are presented. Additionally, crystals grown from a cold diethyl ether solution of zero-valent Fe(CNXyl)5 produced a structure containing a cocrystallization of mononuclear Fe(CNXyl)5 and the previously unknown dinuclear [Fe(CNXyl)3]2(-2-CNXyl)3, namely pentakis(2,6-dimethylphenyl isocyanide)iron(0) tris(-2-2,6-dimethylphenyl isocyanide)bis[tris(2,6-dimethylphenyl isocyanide)iron(0)], [Fe(C9H9N)5][Fe2(C9H9N)9]. The (M)C- N-C(Xyl) angles of the isocyanide ligand are nearly linear for the metals in the +2 oxidation state, for which the ligands function essentially as pure donors. The -CN stretching frequencies for these divalent metal isocyanides are at or above that of the free ligand. Relative to FeII, in the structure containing iron in the formally zero-valent oxidation state, the Fe-C bond lengths have shortened, the C N bond lengths have elongated, the (M)C-N-C(Xyl) angles of the terminal CNXyl ligands are more bent, and the -CN stretching frequencies have shifted to lower energies, all indicative of substantial M(d-).- backbonding.
Nickel(II) Isocyanide complexes as ethylene polymerization catalysts
Tanabiki, Masao,Tsuchiya, Kazuhiro,Kumanomido, Yasuaki,Matsubara, Kouki,Motoyama, Yukihiro,Nagashima, Hideo
, p. 3976 - 3981 (2008/10/09)
Isocyanide complexes of nickel, NiBr2(CNAr)2, are found to be active catalysts for polymerization of ethylene in the presence of methylaluminoxane (MAO). The catalytic activity and properties of polyethylene formed vary with substitu
Four- and Five-Coordinated Nickel(II) Isocyanide Complexes and Donor-Acceptor Complexes Containing Nickel and Mercury
Yamamoto, Yasuhiro,Ehara, Kazuko,Takahashi, Katsuo,Yamazaki, Hiroshi
, p. 3376 - 3383 (2007/10/02)
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(RCN)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) Angstroem, α = β = γ = 90.0 deg, V = 3477.7(6) Angstroem3, 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 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: P1/ (triclinic); a = 12.709(3), b = 16.145(3), c = 12.614(3) Angstroem, α = 96.11(2), β = 107.67(2), γ = 73.11(2) deg, V = 2359.5(10) Angstroem3, 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.
