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Title: Synthesis, characterization and properties of nickel(II)pseudohalide complexes of types [Ni(pap)2(X)2], [Ni(pap)2(X)]2(Y)2 and [Ni(pap)(N3)2]n [pap=2-(phenylazo)pyridine; X=N3ˉ, NCSˉ, NCOˉ; Y=ClO4ˉ, PF6ˉ]
Authors: Rahaman, Sk. Hafijur
Ghosh, Rajarshi
Sarkar, Sajal Kumar
Ghosh, Barindra Kumar
Issue Date: Dec-2005
Publisher: NISCAIR-CSIR, India
IPC Code: Int. Cl.7 C07F15/04
Abstract: Three different types of nickel(II)pseudohalide compounds, viz. red-brown [Ni(pap)2(X)2] [pap=2-(phenylazo)pyridine; X=N3ˉ, 1; NCSˉ, 2; NCOˉ 3], greenish-brown [Ni(pap)2(X)]2(Y)2  (X= N3ˉ , Y=ClO4ˉ, 4; X= N3ˉ  , Y=PF6ˉ , 5; X=NCOˉ, Y=ClO4ˉ, 6; X= NCOˉ, Y= PF6ˉ, 7) and brownish-green, [Ni(pap)(N3)2]n (8) have been prepared and characterised on the basis of microanalytical, spectroscopic, magnetic, electrochemical and other physicochemical properties. In IR, v(N=N) stretching frequency is observed at considerably lower frequencies (-1370 cm-1) than the free ligand value (1425 cm-1) indicating substantial Ni (II)→ pap π-back bonding and in electronic spectra, the MLCT bands show characteristic lower energy shifts in going from mono- to polynuclear compounds via dinuclear ones. Room temperature magnetic measurements show uniformly two-electron paramagnetism for each nickel(II) ion in these complexes. Electrochemical electron transfer study reveals nearly- reversible responses corresponding to NiIII/NiII couple in acetonitrile solutions. On the negative side of SCE, multiple ligand reductions pertaining to azo reductions are observable.
Page(s): 2474-2479
ISSN: 0975-0975(Online); 0376-4710(Print)
Appears in Collections:IJC-A Vol.44A(12) [December 2005]

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