Catalytic dehydrocoupling of H3B·NMe2H using the in situ system Cp2Zr(Cl)(µ-Me3SiC3SiMe3)Zr(Cl)Cp2 (1)/MeLi was studied as a model for previously reported dehydropolymerisation of H3B·NMeH2. NMR and UV-Vis spectroscopic monitoring of the precatalyst...
We
describe reactions of the dilithioallene precursor Li2(Me3SiC3SiMe3) (1)
with Cp2HfCl2, which depending on the stoichiometric
ratio furnishes either a highly sensitive dinuclear allenediide bridged
hafnocene dichloride complex (2-Hf) or a chemically robust
dihafnacyclooctatetraene (3-Hf). Both complexes were
fully characterized, and their formation was analyzed by in
situ NMR spectroscopy. Other than that described before for
the Zr analogues, the generation of both isolated complexes occurs
via a Li containing, yet structurally elusive, metallocene intermediate.
Mono- and dinuclear zirconocene amide complexes were tested as catalysts for the dehydropolymerisation of phenylsilane. The dinuclear complex is surprisingly stable, producing mixtures of polysilanes and cyclic oligomers.
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