PROPERTIES AND CRYSTAL-STRUCTURE OF A 4-CO-ORDINATE NICKEL(I) COMPLEXWITH THE MACROTRICYCLE 1,3,6,8,12,15-HEXAAZATRICYCLO[L3.3.1.1 (8,12)]ICOSANE

Citation
Mp. Suh et al., PROPERTIES AND CRYSTAL-STRUCTURE OF A 4-CO-ORDINATE NICKEL(I) COMPLEXWITH THE MACROTRICYCLE 1,3,6,8,12,15-HEXAAZATRICYCLO[L3.3.1.1 (8,12)]ICOSANE, Journal of the Chemical Society. Dalton transactions, (10), 1995, pp. 1577-1581
Citations number
33
Categorie Soggetti
Chemistry Inorganic & Nuclear
ISSN journal
03009246
Issue
10
Year of publication
1995
Pages
1577 - 1581
Database
ISI
SICI code
0300-9246(1995):10<1577:PACOA4>2.0.ZU;2-G
Abstract
The four-co-ordinate nickel(I) macrocyclic complex R,R,S,S-[NiL]ClO4 ( L = 6.8,12,15-hexaazatri-cyclo[13.3.1.1(8.12)]icosane) has been synthe sized by the reduction of the corresponding nickel(II) complex R,R,S,S ,-[Nil][ClO4](2) . 0.5H(2)O with sodium amalgam in MeCN under nitrogen . It absorbs at 589 (epsilon = 620) and 355 nm (epsilon = 3020 dm(3) m ol(-1) cm(-1)). The EPR powder spectrum shows the anisotropic axial g values of g(parallel to) = 2.272 and g(perpendicular to) = 2.074. The complex crystallizes in the orthorhombic space group P2(1)2(1)2(1) wit h a = 8.681(2), b = 11.358(2), c = 19.146(4) Angstrom and Z = 4. The s tructure was solved by the heavy-atom method and refined anisotropical ly to R = 0.0363 and R' = 0.0379 for 1551 observed reflections [I > 3 sigma(I)] measured with Mo-K alpha radiation. It reveals a tetrahedral ly distorted square-planar geometry having two sets of Ni-N bond dista nces, three at 1.978(3) (average) and one at 1.878(4) Angstrom, withou t any noticeable expansion of the macrocyclic hole.