Journal of the Chemical Society, Dalton Transactions p. 1001 - 1010 (1988)
Update date:2022-08-30
Topics:
Nelson, Jane
Murphy, Brian P.
Drew, Michael G. B.
Yates, Paul C.
Nelson, S. Martin
Template condensation products of 1,5-diaminopentane and 1,6-diaminohexane with 2,6-diacetylpyridine on Pb(NCS)2 have been transmetallated with CoII and CuII to yield homobinuclear complexes of the 24- and 26-membered macrocycles, L1 and L2 respectively.In the dicobalt(II) complex of the smaller macrocycle, L1, a thermally populated spin equilibrium exists lying well to the low-spin side at 93 K.E.s.r. spectra indicate the complex has an equatorially compressed tetragonal geometry.The dicobalt(II) complex of the larger macrocycle, L2, is effectively high-spin, down to 93 K.Dicopper(II) complexes of L1 display a weak antiferromagnetic interaction, absent in analogous complexes of L2.Heterobinuclear complexes a.b.) mass spectra.An X-ray crystallographic structure determination on the heterobinuclear complex PbMnL1(NCS)4 reveals a Pb-Mn distance of 4.857(2) Angstroem and confirms that the metal centres are bridged by two 1,3-μ-NCS-bridges, as inferred from i.r. spectroscopy for the other thiocyanato complexes studied.However, the X-ray structure shows that in this case the thiocyanate bridges present both S-donors to Pb and both N-donors to Mn.
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