Density functional investigation and bonding analysis of pentacoordinated iron complexes with mixed cyano and carbonyl ligands.

The equilibrium structures and vibrational frequencies of the iron complexes [Fe(0)(CN)(n)(CO)(5-n)](n-) and [Fe(II)(CN)(n)(CO)(5-n)](2-n) (n = 0-5) have been calculated at the BP86 level of theory. The Fe(0) complexes adopt trigonal bipyramidal structures with the cyano ligands occupying the axial positions, whereas corresponding Fe(2+) complexes adopt square pyramidal structures with the cyano ligands in the equatorial positions. The calculated geometries and vibrational frequencies of the mixed iron Fe(0) carbonyl cyanide complexes are in a very good agreement with the available experimental data.

Vanadium(V) compounds with the bis-(hydroxylamino)-1,3,5-triazine ligand, H2bihyat: synthetic, structural, and physical studies of [V2(V)O3(bihyat)2] and of the enhanced hydrolytic stability species cis-[V(V)O2(bihyat)]-.

Reaction of the ligand 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine (H(2)bihyat) with NaV(V)O(3) in aqueous solution followed by addition of either Ph(4)PCl or C(NH(2))(3)Cl, respectively, gave the mononuclear vanadium(V) compounds Ph(4)P[V(V)O(2)(bihyat)].1.5H(2)O (1) and C(NH(2))(3)[V(V)O(2)(bihyat)] (2).