Mono(dinitrogen) and Carbon Monoxide Adducts of Bis(cyclopentadienyl) Titanium Sandwiches

The silyl-substituted titanocene complex, (η5-C5Me4SiMe2Ph)2Ti, coordinates dinitrogen upon cooling to −35 °C to yield an unprecedented example of a mono(dinitrogen) complex of a substituted bis(cyclopentadienyl) titanium compound, (η5-C5Me4SiMe2Ph)2Ti(N2). Analogous monocarbonyl derivatives, (η5-C5Me4R)2Ti(CO) (R = SiMe3, SiMe2Ph, CHMe2), have been prepared by mixing the dicarbonyl compounds with the corresponding sandwiches. Both (η5-C5Me4SiMe2Ph)2Ti(N2) and (η5-C5Me4SiMe2Ph)2Ti(CO) have been characterized by X-ray diffraction, and mixed N2−CO titanocene complexes have also been observed by in situ IR spectroscopy.