A new class of cyclopentadiene-bis(oxazoline) compounds and their piano-stool-type organometallic complexes have been prepared as catalysts for hydroamination of aminoalkenes. The two compounds MeC(Ox Me2 ) 2 C 5 H 5 (Bo M CpH; Ox Me2 = 4,4-dimethyl-2-oxazoline) and MeC-(Ox Me2 ) 2 C 5 Me 4 H (Bo M Cp tet H) are synthesized from C 5 R 4 HI (R = H, Me) and MeC(Ox Me2 ) 2 Li. These cyclopentadienebis(oxazolines) are converted into ligands that support a variety of metal centers in piano-stool-type geometries, and here we report the preparation of Mg, Tl, Ti, and Zr compounds. Bo M CpH and Bo M Cp tet H react with MgMe 2 (O 2 C 4 H 8 ) 2 to give the magnesium methyl complexes {Bo M Cp}MgMe and {Bo M Cp tet }MgMe. Bo M CpH and Bo M Cp tet H are converted to Bo M CpTl and Bo M Cp tet Tl by reaction with TlOEt. The thallium derivatives react with TiCl 3 (THF) 3 to provide [{Bo M Cp}TiCl(μ-Cl)] 2 and [{Bo M Cp tet }TiCl(μ-Cl)] 2 , the former of which is crystallographically characterized as a dimeric species. Bo M CpH and Zr(NMe 2 ) 4 react to eliminate dimethylamine and afford {Bo M Cp}Zr(NMe 2 ) 3 , which is crystallographically characterized as a monomeric four-legged piano-stool compound. {Bo M Cp}Zr(NMe 2 ) 3 , {Bo M Cp}MgMe, and {Bo M Cp tet }MgMe are efficient catalysts for the hydroamination/cyclization of aminoalkenes under mild conditions.