By Bryan L. Connelly
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Alternatively, if one considers the hydroxylamido group to be a monodentate ligand, then the complex is a distorted, six-coordinate octahedral complex. 89 Dimethylation of the hydroxylamine unit has no observable effects on the lengths of the V-OH2O, V-OR2NO, V-Npy, and the hydroxylamine N-O bonds. 028(3) Å, respectively; such an increase would be anticipated based on the extra steric bulk of the two methyl groups. 105 Comparing the bond lengths of the hydroxylamido derivative complexes with those of the parent dipicolinato complexes (Tables 4 and 5) showed several differences.
H2O. (Reproduced by permission from reference 81). 24 A. Alvin Holder, C. Lesley Lewis-Alleyne, Don vanDerveer et al. Table 5. 5H2O and other known seven-coordinate dipicolinato-vanadium(V) complexes with ternary peroxo or hydroxylamido ligands. H2O is shown. [VO2(dipicOH)]- exists as a discrete mononuclear unit with the vanadium atom in a distorted trigonal bipyramidal coordination environment. The pyridine nitrogen atom (N1) and two oxygen atoms (O1, O2) of the VO2 group coordinate to the vanadium center and occupy the distorted equatorial plane, while two carboxylate oxygen atoms occupy the axial positions.
An exception to this pattern is observed when the H-acceptor is a carboxylate group bound in coordination mode b. The two H2O molecules (O(30) and O(20)) link two complexes through hydrogen bonds. 51(5) Å (O(20)••••••H(1)). All hydrogen atoms except those of the disordered water oxygen atom O40 were found in the electron density map at the expected orientation. Figure 25. 3H2O. (Reproduced by permission from reference 56). 56 The two dipic2- ligands are deprotonated in the complex. Both dipic2- ligands are coordinated in a tridentate manner to one cobalt atom; one of the two dipic2- groups also acts as a bridging ligand to the pentaaquo-Co(II) unit.