Reactions of activated organonickel σ-complexes with elemental (white) phosphorus

The reactivity of organonickel σ-complexes of the type [NiBr(Ar)(bpy)] (Ar is 2,4,6-tri-methylphenyl (Mes) or 2,4,6-triisopropylphenyl (Tipp); bpy is 2,2′-bipyridine) toward elemental (white) phosphorus was studied. For the reaction to occur, the complexes must be activated by removal of the bromide anion from the coordination sphere of nickel. This can be achieved either in the presence of halogen scavengers or by electrochemical reduction. The arylphosphinic acids ArP(O)(OH)H formed by hydrolysis of organic nickel phosphides are the major reaction products of the overall process. © 2013 Springer Science+Business Media New York

Synthesis, structure and electrochemical properties of the organonickel complex [NiBr(Mes)(phen)] (Mes = 2,4,6-trimethylphenyl, phen = 1,10-phenanthroline)

The organonickel complex [NiBr(Mes)(phen)] (1) (Mes = 2,4,6- trimethylphenyl, phen = 1,10-phenanthroline) was synthesized by oxidative addition of MesBr to nickel(0) complexes, obtained from [Ni(COD)2] (COD = 1,5-cyclooctadiene) and phen, or electrochemically generated from [NiBr2(phen)], and by ligand exchange reaction from [NiBr(Mes)(PPh3)2]. The electrochemical properties of [NiBr(Mes)(phen)] were investigated by cyclic voltammetry and in situ EPR spectroelectrochemistry. The cathodic reduction of 1 resulted in formation of the neutral radical complex [Ni(Mes)(phen-)] with a 1,10-phenanthroline radical anion bound to a nickel(II) centre. The electrochemical generation of the free 1,10-phenanthroline radical anion from 1,10-phenanthroline is also described. © 2013 Elsevier B.V. All rights reserved

Reactions of activated organonickel σ-complexes with elemental (white) phosphorus

The reactivity of organonickel σ-complexes of the type [NiBr(Ar)(bpy)] (Ar is 2,4,6-tri-methylphenyl (Mes) or 2,4,6-triisopropylphenyl (Tipp); bpy is 2,2′-bipyridine) toward elemental (white) phosphorus was studied. For the reaction to occur, the complexes must be activated by removal of the bromide anion from the coordination sphere of nickel. This can be achieved either in the presence of halogen scavengers or by electrochemical reduction. The arylphosphinic acids ArP(O)(OH)H formed by hydrolysis of organic nickel phosphides are the major reaction products of the overall process. © 2013 Springer Science+Business Media New York

Synthesis, structure and electrochemical properties of the organonickel complex [NiBr(Mes)(phen)] (Mes = 2,4,6-trimethylphenyl, phen = 1,10-phenanthroline)

The organonickel complex [NiBr(Mes)(phen)] (1) (Mes = 2,4,6- trimethylphenyl, phen = 1,10-phenanthroline) was synthesized by oxidative addition of MesBr to nickel(0) complexes, obtained from [Ni(COD)2] (COD = 1,5-cyclooctadiene) and phen, or electrochemically generated from [NiBr2(phen)], and by ligand exchange reaction from [NiBr(Mes)(PPh3)2]. The electrochemical properties of [NiBr(Mes)(phen)] were investigated by cyclic voltammetry and in situ EPR spectroelectrochemistry. The cathodic reduction of 1 resulted in formation of the neutral radical complex [Ni(Mes)(phen-)] with a 1,10-phenanthroline radical anion bound to a nickel(II) centre. The electrochemical generation of the free 1,10-phenanthroline radical anion from 1,10-phenanthroline is also described. © 2013 Elsevier B.V. All rights reserved

Synthesis, structure and electrochemical properties of the organonickel complex [NiBr(Mes)(phen)] (Mes = 2,4,6-trimethylphenyl, phen = 1,10-phenanthroline)

The organonickel complex [NiBr(Mes)(phen)] (1) (Mes = 2,4,6- trimethylphenyl, phen = 1,10-phenanthroline) was synthesized by oxidative addition of MesBr to nickel(0) complexes, obtained from [Ni(COD)2] (COD = 1,5-cyclooctadiene) and phen, or electrochemically generated from [NiBr2(phen)], and by ligand exchange reaction from [NiBr(Mes)(PPh3)2]. The electrochemical properties of [NiBr(Mes)(phen)] were investigated by cyclic voltammetry and in situ EPR spectroelectrochemistry. The cathodic reduction of 1 resulted in formation of the neutral radical complex [Ni(Mes)(phen-)] with a 1,10-phenanthroline radical anion bound to a nickel(II) centre. The electrochemical generation of the free 1,10-phenanthroline radical anion from 1,10-phenanthroline is also described. © 2013 Elsevier B.V. All rights reserved

Synthesis, structure and electrochemical properties of the organonickel complex [NiBr(Mes)(phen)] (Mes = 2,4,6-trimethylphenyl, phen = 1,10-phenanthroline)

The organonickel complex [NiBr(Mes)(phen)] (1) (Mes = 2,4,6- trimethylphenyl, phen = 1,10-phenanthroline) was synthesized by oxidative addition of MesBr to nickel(0) complexes, obtained from [Ni(COD)2] (COD = 1,5-cyclooctadiene) and phen, or electrochemically generated from [NiBr2(phen)], and by ligand exchange reaction from [NiBr(Mes)(PPh3)2]. The electrochemical properties of [NiBr(Mes)(phen)] were investigated by cyclic voltammetry and in situ EPR spectroelectrochemistry. The cathodic reduction of 1 resulted in formation of the neutral radical complex [Ni(Mes)(phen-)] with a 1,10-phenanthroline radical anion bound to a nickel(II) centre. The electrochemical generation of the free 1,10-phenanthroline radical anion from 1,10-phenanthroline is also described. © 2013 Elsevier B.V. All rights reserved