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Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
Published on: November 27, 2015
trans-Bis(N,N-diethyl-ethylenediamine)-nickel(II) dibromide
Skylar J Ferrara1, Joel T Mague, James P Donahue
1Department of Chemistry, Tulane University, 6400 Freret Street, New Orleans, Louisiana 70118-5698, USA.
Abstract:
The structure of the title compound, [Ni(C(6)H(16)N(2))(2)]Br(2) or [Ni(Et(2)en)(2)]Br(2) (Et(2)en is asymmetric N,N-diethyl-ethylene-diamine), containing an Ni(II) atom (site symmetry ) in square-planar NiN(4) coordination, is described and contrasted with related structures containing Ni(II) in octa-hedral coordination with axial X(-) ligands (X(-) = variable anions). The dialkyl-ated N atom has an appreciably longer bond length to the Ni(II) atom [1.9666 (13) Å] than does the unsubstituted N atom [1.9202 (14) Å]. The Ni-N bond lengths in [Ni(Et(2)en)(2)]Br(2) are significantly shorter than corresponding values in tetra-gonally distorted [Ni(Et(2)en)(2)X(2)] compounds (X = (-)O(2)CCF(3), OH(2), or (-)NCS), which have a triplet ground state. The electronic configuration in these axially ligated [Ni(Et(2)en)(2)X(2)] compounds populates the metal-based d(x) (2) (-y) (2) orbital, which is Ni-N anti-bonding in character. Each Et(2)en ligand in each [Ni(Et(2)en)(2)](2+) cation forms a pair of N-H⋯Br hydrogen bonds to the Br(-) anions, one above and below the NiN(4) square plane. Thus, a ribbon of alternating Br(-) pairs and [Ni(Et(2)en)(2)](2+) cations that are canted at 65° relative to one another is formed by hydrogen bonds.
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