TY - JOUR
T1 - EPR study of (η5-cyclopentadienyl)nickel(I) complexes with P-and N-donor ligands and 1,5-cyclooctadiene
AU - Saraev, V. V.
AU - Kraikivskii, P. B.
AU - Zelinskii, S. N.
AU - Vil'ms, A. I.
AU - Matveev, D. A.
AU - Yunda, A. Yu
AU - Fedonina, A. A.
AU - Lammertsma, K.
PY - 2006/6
Y1 - 2006/6
N2 - 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).
AB - 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).
UR - http://www.scopus.com/inward/record.url?scp=33745300373&partnerID=8YFLogxK
U2 - 10.1134/S1070328406060029
DO - 10.1134/S1070328406060029
M3 - Article
AN - SCOPUS:33745300373
SN - 1070-3284
VL - 32
SP - 397
EP - 401
JO - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya
JF - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya
IS - 6
ER -