Pyrolysis of metallocene complexes (ηC 5 H 4 R) 2 MR: An organometallic route to metal carbide (MC) materials (M = Ti, Zr, Hf)

The following compounds were prepared and their pyrolysis in a stream of argon was studied: (η 5 ‐C 5 H 5 ) 2 Ti(CCC 6 H 5 ) 2 , (η 5 ‐C 5 H 4 SiMe 3 ) 2 ‐Ti(SH) 2 , [(η 5 ‐C 5 H 5 )Ti(μ‐CH 2 )] 2 , (η 5 ‐C 5 H 5 ) 2 ZrR 2 ‐(RCH 2 , CH 2 C 6 H 5 , N(CH 3 ) 2 ), (η 5 ‐C 5 H 4 CH 3 ) 2 ‐Zr(CCC 6 H 5 ) 2 , [(η 5 ‐C 5 H 4 SiMe 3 ) 2 Zr(μ‐S)] 2 , [(η 5 ‐C 5 H 4 SiMe 3 ) 2 Hf(μ‐S)] 2 and (η 5 ‐C 5 H 4 SiMe 3 ) 2 Hf‐(CCC 6 H 5 ) 2 . The products of bulk pyrolysis of these materials were formed in 20–40% yield, based on the charged sample weight, and consisted mainly of titanium carbide together with small amounts of amorphous carbon.