Abstract
Bis(decamethyltitanocene) oxide, [(Cp-2*Ti)(2)O] (1; Cp* = eta(5)-C5Me5) has been obtained as a yellow crystalline solid after reacting equimolar amounts of the hydride [Cp-2*TiH] and the hydroxide [Cp-2*Ti(OH)]. The solid-state structure of I revealed a linear Ti-O-Ti arrangement and a mutual, nearly perpendicular orientation of the bent-sandwich titanocene moieties; the length of both Ti-O bonds amounted to 1.9080(3) angstrom.
A unique structural feature was a close-to-eclipsed conformation of the cyclopentadienyl ligands, attributed to the high steric congestion of 1. The molecule in toluene glass exhibited a triplet state EPR spectrum of rhombic symmetry, having zero field splitting D = 0.02159 cm(-1) and E = 0.00230 cm(-1).
The H-1 NMR spectrum of I in toluene-d(8) displays a paramagnetic resonance at delta 4.3 ppm (Delta nu(1/2) approximate to 270 Hz). Compound 1 reacts with 1 molar equiv of water to give [Cp-2*Ti(OH)].
In CD2Cl2, 1 is oxidized to yield the major product [(Cp*TiCl2)(2)O] and minor product [{Cp*Ti(Cl)O}(3)].