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Synthesis and characterization of new one-carbon-bridged titanocene and zirconocene derivatives

1995; Elsevier BV; Volume: 485; Issue: 1-2 Linguagem: Inglês

10.1016/0022-328x(94)24764-a

1872-8561

Ricardo Fierro, Marvin D. Rausch, Georg S. Herrman, Helmut G. Alt,

Radioactive element chemistry and processing

Abstract A variety of new chiral one-carbon-bridged metallocene derivatives of titanium and zirconium has been prepared. Addition of the anions of cyclopentadiene, indene and fluorene to 6-t-butylfulvene produced the ligands t-BuCH(C5H5)R (R=C5H5,8;C9H7,9;C13H9,10). The reaction of the ligands8–10 with n-BuLi produced the corresponding bis-anions, which were reacted with titanium or zirconium tetrachloride at low temperature (−78°C), to produce the complexes t-BuCH(η5-C5H4)(R)MCl2 (R = η5-C5H4,M=Ti,11;R= η5-C5H4,M=Zr,12,R= η5-C9H6,M=T,14;R= η5-C9H6,M=Zr,15;R= η5-C13H8,M=Zr,16). The chlorine atoms in complexes11 and16 can be easily replaced by methyl groups producing the corresponding dimethyl derivatives13 and17.