Author:
Gruber SJ,Harris CM,Kokot E,Lenzer SL,Lockyer TN,Sinn E
Abstract
The magnetism of
various copper(II) complexes of pyridine
and quinoline N-oxides1 has been further investigated.
The compounds Cu(C5H5NO)nX2
(where n = 4 or 6, X = ClO4; n = 2, X =
Cl, Br, NCS; n = 1, X = Cl, Br, CH3COO)
and Cu(C9H7NO)nX2
where n = 4, X = ClO4; n = 2, X = Cl, Br, NO3; n = 1, X = Cl,
Br, CH3COO) have been studied. The variation of the magnetic
susceptibilities of most of these compounds is reported over a temperature
range.
The variation of the magnetic
susceptibility with temperature for the weakly paramagnetic complex Cu(C5H5NO)Cl2 is discussed in terms of the binuclear
oxygen-bridged structure previously postulated.1
The compound exhibits anti-ferromagnetic interaction between pairs of copper(II)
atoms with a singlet-triplet separation of 2.1 kcal/mole. The compounds Cu(C5H5NO)2Cl2, Cu(C5H5NO)Br2, and Cu(C9H7NO)X2
(X = Cl, Br) are more weakly paramagnetic due to a
larger singlet-triplet separation. The compound Cu(C5H5NO)2Br2 possesses a higher paramagnetic
susceptibility than those of the previous compounds, and its magnetic
properties are consistent with a dimeric structure involving a singlet- triplet
separation of 0.7 kcal/mole. The copper(II) acetate adducts, Cu(CH3COO)2,L
(L = C5H5NO or C9H7NO), possess
very similar magnetic properties to binuclear copper(II) acetate monohydrate
and presumably possess a similar structure, with the N-oxides replacing the
water molecules. These compounds exhibit singlet-triplet energies of c. 1
kcal/mole similar to values reported for a large number of copper(II)
alkanoates.
The compounds Cu(C5H5NO)2(NCS)2,
Cu(C5H5NO)4(ClO4)2,
Cu(C5H5NO)6- (ClO4)2,
Cu(C9H7NO)2X2 (X = Cl, Br, NO3), all obey the Curie-Weiss law and
possess mean magnetic moments of 1.89, 1.80, 1.93, 1.88, 1.96, and 1.88 B.M.
(corrected for θ values of -12, -7, -8, + -4, and -16�) respectively.
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