(Apy)Cu(PPh3)22BF42 (I; apy = azo-2,2'-pyridine) and (apy)Co(hfacac)2 (II; Hhfacac = hexafluoroacetylacetone) were prepd. from Cu(PPh3)4BF4 or Cu(hfacac)2, resp., and apy. The crystal structures of I and (apy)Mo(CO)4 (III) were detd. I and III are monoclinic, space groups P21/c and C2/c, Z = 4, R = 0.042 and 0.078, resp. Edge-sharing of 2 a-iminoazo 5-membered chelate rings in dinuclear complexes of the S-frame ligand apy give rise to short distances between coplanar mol.-bridged metal centers. An intramol. Cu-Cu distance of 493.7 pm was found for (μ,η4-apy)Cu(PPh3)222+ in the crystal with BF4- anions. Despite such relatively short metal-metal distances II does not exhibit unusual magnetic coupling between the high-spin d7 centers. III contains a not completely coplanar apy ligand; the free pyridyl group is rotated in such a fashion as to minimize steric repulsion and possibly coordinate weakly to the metal. on SciFinder(R)
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