15629-46-6Relevant articles and documents
Halogen Photoelimination from Monomeric Nickel(III) Complexes Enabled by the Secondary Coordination Sphere
Hwang, Seung Jun,Anderson, Bryce L.,Powers, David C.,Maher, Andrew G.,Hadt, Ryan G.,Nocera, Daniel G.
, p. 4766 - 4774 (2015/10/28)
Endothermic halogen elimination reactions, in which molecular halogen photoproducts are generated in the absence of chemical traps, are rare. Inspired by the proclivity of mononuclear Ni(III) complexes to participate in challenging bond-forming reactions in organometallic chemistry, we targeted Ni(III) trihalide complexes as platforms to explore halogen photoelimination. A suite of Ni(III) trihalide complexes supported by bidentate phosphine ligands has been synthesized and characterized. Multinuclear NMR, EPR, and electronic absorption spectroscopies, as well as single-crystal X-ray diffraction, have been utilized to characterize this suite of complexes as distorted square pyramidal, S = 1/2 mononuclear Ni(III) complexes. All complexes participate in clean halogen photoelimination in solution and in the solid state. Evolved halogen has been characterized by mass spectrometry and quantified chemically. Energy storage via halogen elimination was established by solution-phase calorimetry measurements; in all cases, halogen elimination is substantially endothermic. Time-resolved photochemical experiments have revealed a relatively long-lived photointermediate, which we assign to be a Ni(II) complex in which the photoextruded chlorine radical interacts with a ligand-based aryl group. Computational studies suggest that the observed intermediate arises from a dissociative LMCT excited state. The participation of secondary coordination sphere interactions to suppress back-reactions is an attractive design element in the development of energy-storing halogen photoelimination involving first-row transition metal complexes.
Ditertiary phosphine complexes of nickel. Spectral, magnetic, and proton resonance studies. A planar-tetrahedral equilibrium
Van Hecke, Gerald R.,Horrocks Jr., William DeW.
, p. 1968 - 1974 (2008/10/08)
A number of complexes of nickel in oxidation states 0, II, and III with the ditertiary phosphines (C6H5)2P(CH2)nP(C 6H5)2 (n = 1, 2, or 3) are reported and studied by spectral and magnetic methods. In solution in organic solvents complexes of the type Ni[(C6H5)2P(CH2)nP(C 6H5)2]X2 where X = Br or I and n = 2 remain diamagnetic. The analogous complexes with n = 3 show a square-planar (diamagnetic)-tetrahedral (paramagnetic) equilibrium in solution. Isotropic proton magnetic resonance shifts were observed in these systems and thermodynamic parameters for the equilibrium were obtained from the temperature dependences of these shifts. The epr spectrum of polycrystalline Ni[(C6H5)2P(CH2)3P(C 6H5)2]Br3 shows an isotropic signal at g = 2.218.
