Publisher： John Wiley & Sons Inc
E-ISSN： 1521-3749|44-2313|12‐13|2047-2050
ISSN： 0044-2313
Source： ZAAC-JOURNAL OF INORGANIC AND GENERAL CHEMISTRY (ELECTRONIC), Vol.44-2313, Iss.12‐13, 2015-10, pp. : 2047-2050
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Abstract
Abstract The reactivity of the bis‐oxygen substituted alkyne bis(tert‐butoxy)acetylene (3) towards titanocene‐ and zirconocene complexes of btmsa [btmsa = bis(trimethylsilyl)acetylene] was investigated. Those metallocenes with unsubstituted Cp ligands (Cp = η5‐cyclopentadienyl) afforded metallacyclopropenes by alkyne replacement, but only in low yields. The metallocenes bearing the sterically more demanding Cp* ligands (Cp* = η5‐pentamethylcyclopentadienyl) do not engage in replacement reactions with the alkyne 3. If titanocene monochloride is present in the reaction mixture of Cp2Ti(η2‐btmsa) with the alkyne 3, a rather unusual Calkyne–O bond cleavage occurs. The so‐formed acetylide moiety bridges two titanocene centres with an end‐on σ coordination to one of them and a π‐side‐on one to the other. This complex was investigated by X‐ray crystallography and temperature dependent NMR spectroscopy, revealing an unusual behavior.
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