Copper dusters

Reinhard, D., Hall, B.D., Berthoud, P., Valkealahti, S. and Monot, R. (1998) Unsupported nanometer-sized copper dusters smdied by electron diffraction and molecular dynamics. Physical Review B, 58, 4917-26. 

Fig. 19.30 Molecular structure of copper complex of D-penknUamme. The ICu Cu pefl(cillajnrnate) 2CI ion (a) the central cluster of Cu and ligating atoms only, (b) the entire ion with the centra] duster oriented as In (a). From Biricer. P. J. M. W. L. Freeman. H. C. Chem. Commtm. 1976.312. Reproduced with permission.)...

The central feature of the mechanism is the 3-cuprio(III) enolate Cpop, of an open dimeric nature as shown by comparison of theory with experimentation involving NMR and KIEs [80 81]. This species serves as the direct precursor to the product (Scheme 10.5 top box). In this critical CPop complex copper/olefin (soft/soft) and a lithium/carbonyl (hard/hard) interactions are present The open complex may be formed directly by way of an open cluster (bottom left of Scheme 10.5)j or by complexation of a dosed duster with the enone (CPd). Experiments have shown that the enone/lithium complex (top left of Scheme 10.11) is a deadend spedes [60 74]. 

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