Boreen Michael A, Bogart Justin A, Carroll Patrick J, Schelter Eric J
P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
Inorg Chem. 2015 Oct 5;54(19):9588-93. doi: 10.1021/acs.inorgchem.5b01687. Epub 2015 Sep 23.
The tripodal nitroxide ligand (2-(t)BuNO)C6H4CH2)3N (TriNOx(3-)) binds the Ti(IV) cation and prevents inner-sphere coordination of chloride in the complex [Ti(TriNOx)]Cl (1). The ligand undergoes an η(2)-NO to κ(1)-O rearrangement to enable a fluoride ion to bind in the related complex Ti(TriNOx)F (2). Computational and reactivity studies demonstrated that the ligand rearrangement contributed to the enthalpy change in the transfer of a fluoride anion.
三脚架型氮氧化物配体(2-(叔丁基)NO)C6H4CH2)3N(三氮氧(3-))与Ti(IV)阳离子结合，并阻止配合物[Ti(三氮氧)]Cl(1)中氯离子的内球配位。该配体发生η(2)-NO到κ(1)-O的重排，以使氟离子能在相关配合物Ti(三氮氧)F(2)中结合。计算和反应性研究表明，配体重排有助于氟阴离子转移过程中的焓变。
