Preparation and Crystal Structures of a Series of Titanium(III) 9-BBN Hydroborate Complexes Containing Ti···H Agostic Interactions

9-BBN hydroborate complexes Ti{(μ-H)2BC8H14}3(THF)2 (1), Ti{(μ-H)2BC8H14}3(OEt2) (2), and [K(OEt2)4]-[Ti{(μ-H)2BC8H14}4] (4) were formed from the reaction of TiCl4 with K[H2BC8H14] in diethyl ether or THF.
Ti{(μ-H)2BC8H14}3(PhNH2) (3) was isolated from the reaction of 2 with aniline in diethyl ether. In the formation of
these complexes, Ti(IV) is reduced to Ti(III). The coordinated diethyl ether in 2 can be displaced by the stronger
bases THF and aniline, to form 1 and 3, respectively. All of the compounds were characterized by single-crystal
X-ray diffraction analysis. In complex 1, which contains two coordinated THF ligands, the titanium possesses a 17
electron configuration and there is no evidence for agostic interaction. Complexes 2 and 3 contain only one coordinated
ether or aniline ligand, and the titanium possesses a 15 electron configuration. In these compounds, a C−H hydrogen
on an α carbon on the BC8H14 unit of a 9-BBN hydroborate ligand forms an agostic interaction with the titanium.
Criteria for assessing the existence of agostic interactions are discussed. As the potassium salt, the anion of
complex 4 is more stable than the complexes 1−3. Organometallic anions of the type [ML4]- for titanium(III) are
rare.