Conformationally locked pentadentate macrocycles containing the 1,10-phenanthroline unit. Synthesis and crystal structure of 5-oxa-2,8-dithia[9](2,9)-1,10-phenanthrolinophane (L) and its coordination properties to Ni-II, Pd-II, Pt-II, Rh-III and Ru-II
M. Arca et al., Conformationally locked pentadentate macrocycles containing the 1,10-phenanthroline unit. Synthesis and crystal structure of 5-oxa-2,8-dithia[9](2,9)-1,10-phenanthrolinophane (L) and its coordination properties to Ni-II, Pd-II, Pt-II, Rh-III and Ru-II, J CHEM S DA, (8), 2001, pp. 1180-1188
Citations number
42
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
The complexation of the new mixed thia-aza-oxa macrocycle 5-oxa-2,8-dithia[
9](2,9)-1,10-phenanthrolinophane (L) containing the 1,10-phenanthroline uni
t with Ni-II, Pd-II, Pt-II, Rh-III and Ru-II has been investigated. The res
ults have been compared with those obtained with the structurally related l
igand 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane (L'). The most stable
conformations of both ligands have been calculated in order to understand t
heir change upon metal complexation and for L good agreement has been found
with the conformations observed in the crystal structure of L .1/2H(2)O. T
he single-crystal structures of [Ni(L)Cl]BF4 and [Ru(L)(PPh3)][PF6](2).1/4M
eCN reveal a N2S2O coordination sphere about Ni-II and Ru-II, with the macr
ocyclic ligand in a folded conformation and with the sixth coordination sit
e taken up by Cl- or PPh3, respectively. For [Pd(L)][BF4](2) an [N2S2 + O]
coordination is observed, with the O-donor interacting weakly with the meta
l centre at the apical position of a square-based coordination sphere. C-13
and H-1 NMR spectroscopic studies indicate that the complexes are not flux
ional in solution, with the ligand imposing the same coordination sphere as
observed in the solid state. C-13 NMR spectroscopy has also helped in eluc
idating the stereochemistry of [Rh(L)Cl-2]BF4 for which no suitable crystal
s could be grown: the two Cl- ligands are mutually trans with the N2S2 dono
r set of the macrocyclic ligand occupying the equatorial positions of an oc
tahedral coordination sphere and with the O-donor atom left un-coordinated.
The redox properties of all the complexes in MeCN have been studied.