Application of n-Bu4NHF2 as a fluorinating agent for the preparation of fluoroanions: Synthesis and crystal structure of the anions [t-BuPO3AlF2](2)(2-), [PhPO3AlF2](2)(2-), and [(O-i-Pr)(3)Ti(mu-F)(2)(mu-O-i-Pr)Ti(O-i-Pr)(3)](-)

Abstract

The first phosphonate anions of aluminum-containing fluorine and an anionic bridged fluoroalkoxy derivative of titanium have been realized using n-Bu4NHF2 as a fluorinating agent in organometallic synthesis. Reactions of RPO3AlMe [R = Ph (1), t-Bu] with n-Bu4NHF2 yield organic-soluble compounds of the type n-Bu4NRPO3AlF2 [R = Ph (2), t-Bu (3)], whereas the reaction of Ti(O-i-Pr)(4) with n-Bu4NHF2 results in the formation of [n-Bu4N][(O-i-Pr)(3)Ti(mu-F)(2)(mu-O-i-Pr)Ti(O-i-Pr)(3)] (4). These compounds have been obtained in high yields and have been adequately characterized through spectroscopic techniques and X-ray diffraction studies.