Journal of the American Chemical Society p. 10041 - 10046 (1995)
Update date:2022-08-17
Topics:
Baranger, Anne M.
Hanna, Tracy A.
Bergman, Robert G.
The early-late heterobimetallic complex Cp2Zr(μ-N-t-Bu)IrCp* (1) has been found to undergo oxygen and sulfur abstraction reactions. Imido complex 1 reacts with Me3P=S, S8, H2S, and thiiranes to form the bridging sulfido complex 2 (Cp2Zr(μ-N-t-Bu)(μ-S)IrCp*). The structure of complex 2 was confirmed by an X-ray diffraction study. The addition of cis-2-butene sulfide to imido complex 1 gave only 2 and cis-2-butene. Similarly, the addition of trans-2-butene sulfide resulted only in the formation of trans-2-butene. These results argue against mechanisms for sulfur abstraction that involve ring-opened intermediates. Imido complex 1 was found to react with pyridine N-oxide, nitrous oxide, and styrene oxide to form the bridging oxo complex 4 (Cp2Zr(μ-N-t-Bu)(μ-O)IrCp*), but it was unreactive toward cis-2-butene oxide or triphenylphosphine oxide. A competition study revealed that cis-2-butene sulfide, trans-2-butene sulfide, 2-methylpropene sulfide, propene sulfide, and ethylene sulfide reacted with complex 1 at very similar rates. We believe that this weak selectivity is a result of inherently very rapid - perhaps even diffusion-controlled - rates of reaction for the sulfur atom abstraction. It may be that low activation barriers are an inherent property of cooperative two-metal atom transfer reactions.
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