β‑H Abstraction/1,3‑CH Bond Addition
as a Mechanism for the Activation of CH Bonds at Early Transition
Metal Centers
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Abstract
This
article describes the generalization of an overlooked mechanism
for CH bond activation at early transition metal centers, namely 1,3‑CH
bond addition at an η<sup>2</sup>-alkene intermediate. The X-ray-characterized
[Cp<sub>2</sub>Zr(<i>c</i>-C<sub>3</sub>H<sub>5</sub>)<sub>2</sub>] eliminates cyclopropane by a β‑H abstraction
reaction to generate the transient η<sup>2</sup>-cyclopropene
[Cp<sub>2</sub>Zr(η<sup>2</sup>-<i>c</i>-C<sub>3</sub>H<sub>4</sub>)] intermediate <b>A</b>. <b>A</b> rapidly
cleaves the CH bond of furan and thiophene to give the furyl and thienyl
complexes [Cp<sub>2</sub>Zr(<i>c</i>-C<sub>3</sub>H<sub>5</sub>)(2-C<sub>4</sub>H<sub>3</sub>X)] (X = O, S), respectively.
Benzene is less cleanly activated. Mechanistic investigations including
kinetic studies, isotope labeling, and DFT computation of the reaction
profile all confirm that rapid stereospecific 1,3‑CH
bond addition across the Zr(η<sup>2</sup>-alkene) bond of <b>A</b> follows the rate-determining β‑H abstraction
reaction. DFT computations also suggest that an α‑CC
agostic rotamer of [Cp<sub>2</sub>Zr(<i>c</i>-C<sub>3</sub>H<sub>5</sub>)<sub>2</sub>] assists the β‑H abstraction
of cyclopropane. The nature of the α‑CC agostic
interaction is discussed in the light of an NBO analysis