STRUCTURAL AND REACTION CHEMISTRY OF TUNGSTENOCENE BORYL COMPLEXES

The structural and reaction chemistry of Cp(2)W(H)(Bcat) (cat = O2C6H4 ) (1) and Cp(2)W-(Bcat')(2) (cat' = O2C6H3-t-Bu or O2C6H2-t-Bu(2)) (2a ,b) is reported. Compound 1 was prepared by reaction of the anion [Cp( 2)WH](-) with ClBcat, and 2a,b were prepared by oxidative addition of cat'BBcat' by photochemical or thermal generation of tungstenocene. Th e X-ray structures of 1 and 2a are reported, and they display geometri es indicating d pi-p pi interaction. The reaction chemistry of these c ompounds with small molecules involves protonation by alcohols, water- catalyzed protonation by amines, halogenation of the hydride in 1, and resistance toward formation of Lewis acid-base complexes. In addition , 1 undergoes photochemically induced reductive elimination of HBcat. Remarkably, generation of tungstenocene in the presence of cat'BBcat' in benzene solvent led to the formation of 2 rather than oxidative add ition of the solvent.