Metallation-boration sequence

The use of other crosslinking metals developed simultaneously with the use of antimony, chromium, and boron(borate). Tiner, et al.(242) introduced titanium (IV) crosslinkers in 1975 as ammonium tetralactonate or bis(triethanolamine)bis(isopropyl)titanium(IV). Upon contact with water soluble titanium (IV) derivatives ordinarily form orthotitanic acid, Ti(0H)4, which rapidly forms oligimeric metatitanic acid, [Ti(0H)2] and titanium dioxide. Electron donors such as the hydroxyl groupsxof polysaccharides, if properly oriented, can participate in the sequence of titania reactions and a crosslinked gel network results. Various titanium metal crosslinkers remain in common use today. More will be said about titanium crosslinked gels later. 

Speculation is made about why epi-inositol flips into the triaxial form to form a tridentate complex with borate, but complexes without flipping with metal ions. The distances between the three axial oxygen atoms are similar to those between the three oxygen atoms in the ax-eq-ax sequence. However, in the triaxial borate complexes (3) the bonds are tetrahedral if one were formed at the ax-eq-ax oxygen atoms, the bonds would be considerably distorted. However, the angles have much less effect on complex formation with cations which does not involve covalent bonds. 

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