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Poster Presentations
Day 1, June 22（Sun.）
Room P (Maesato East, Foyer, Ocean Wing)
- 1P-PM-43
Gas-Phase Photoelectron Spectroscopy and Reactivity of the Phenylacetylide PhCC- and Copper Bis(phenylacetylide) [Cu(CCPh)2]- Anions
(1unimelb, 2PNNL)
oHoward Ma1, Wenjin Cao2, Yufei Xie1, Xue-Bin Wang2, Richard O'hair1
The introduction of mixed organocuprate reagents [Cu(R1)(R2)]-, where R1 = alkyl and R2 = acetylide, by E. J. Corey represented a breakthrough in the development of C-C bond coupling reactions. In contrast to homocuprates [Cu(R)2]- which only effectively transfers a single R group to an electrophilic substrate, these mixed-ligand cuprates allowed for the selective transfer of a desired ligand (R1) and the acetylide (R2) serves as a non-transferable 'dummy' ligand. Thereby preventing the valuable R group from being wasted. Seminal theoretical studies by E. Nakamura have shown that the reactivity of dialkylcuprates, e.g., [Cu(Me)2]-, can be understood on the basis of frontier molecular orbital (FMO) theory. Inspired by Nakamura's work, this MO approach was adopted by O'Hair and co-workers to rationalize the gas-phase reactivities of dialkylcuprates with various electrophiles. However, despite the prevalence of copper acetylides as intermediates in numerous organic transformations, studies featuring coordinated acetylides (R2) are rarer. Thus, in order to better understand these mixed organocuprates, [Cu(R1)(R2)]-, here we present a combined experimental and theoretical study on the fundamental reactivity of a 'dummy ligand', in its bare (PhCC-) and coordinated ([Cu(CCPh)2]-) forms, via negative ion photoelectron spectroscopy (NIPES), ion-molecule reactions (IMR), Density Functional Theory (DFT) calculations.