EPR study of (η5-cyclopentadienyl)nickel(I) complexes with P-and N-Donor ligands and 1,5-cyclooctadiene

EPR study of (η5-cyclopentadienyl)nickel(I) complexes with P-and N-Donor ligands and... Mononuclear (η5-cyclopentadienyl)nickel(I) complexes with triphenylphosphine, triethylphosphite, 2,2’-bipyridyl, and 1,5-cyclooctadiene formed in the course of reduction of nickelocene were studied by EPR method. Monocyclopentadienyl Ni(I) complexes of the composition CpNiL2 were shown to form during nickelocene reduction irrespective of the method applied (the use of organometallic compound, alkali metal, thermal conditions) in the presence of stabilizing ligands L (L = PPh3, P(OEt)3, Bipy/2, COD/2) and in the course of contradisproportionation reaction between nickelocene and the corresponding NiL4 complex. It was found that in the structure of these CpNiL2 complexes (L = PPh3, P(OEt)3, Bipy/2), the main molecular axis is perpendicular to the L-Ni-L plane and these complexes should be considered as derivatives of trigonal structures of D 3h symmetry distorted by Cp ligand. In CpNi(COD) complex, the main axis passes through the Cpring center and this complex should be treated as a derivative of pentagonal structure of C 5v symmetry distorted by COD ligand. Nonequivalence of 31P nuclei results from vibronic interaction effect in tricoordinate structures in pseudodegenerate electron state (Jahn-Teller effect). http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Russian Journal of Coordination Chemistry Springer Journals

EPR study of (η5-cyclopentadienyl)nickel(I) complexes with P-and N-Donor ligands and 1,5-cyclooctadiene

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Publisher
Nauka/Interperiodica
Copyright
Copyright © 2006 by Pleiades Publishing, Inc.
Subject
Chemistry; Inorganic Chemistry; Physical Chemistry
ISSN
1070-3284
eISSN
1608-3318
D.O.I.
10.1134/S1070328406060029
Publisher site
See Article on Publisher Site

Abstract

Mononuclear (η5-cyclopentadienyl)nickel(I) complexes with triphenylphosphine, triethylphosphite, 2,2’-bipyridyl, and 1,5-cyclooctadiene formed in the course of reduction of nickelocene were studied by EPR method. Monocyclopentadienyl Ni(I) complexes of the composition CpNiL2 were shown to form during nickelocene reduction irrespective of the method applied (the use of organometallic compound, alkali metal, thermal conditions) in the presence of stabilizing ligands L (L = PPh3, P(OEt)3, Bipy/2, COD/2) and in the course of contradisproportionation reaction between nickelocene and the corresponding NiL4 complex. It was found that in the structure of these CpNiL2 complexes (L = PPh3, P(OEt)3, Bipy/2), the main molecular axis is perpendicular to the L-Ni-L plane and these complexes should be considered as derivatives of trigonal structures of D 3h symmetry distorted by Cp ligand. In CpNi(COD) complex, the main axis passes through the Cpring center and this complex should be treated as a derivative of pentagonal structure of C 5v symmetry distorted by COD ligand. Nonequivalence of 31P nuclei results from vibronic interaction effect in tricoordinate structures in pseudodegenerate electron state (Jahn-Teller effect).

Journal

Russian Journal of Coordination ChemistrySpringer Journals

Published: Jun 15, 2006

References

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