Picture of smart phone in human hand

World leading smartphone and mobile technology research at Strathclyde...

The Strathprints institutional repository is a digital archive of University of Strathclyde's Open Access research outputs. Strathprints provides access to thousands of Open Access research papers by University of Strathclyde researchers, including by Strathclyde researchers from the Department of Computer & Information Sciences involved in researching exciting new applications for mobile and smartphone technology. But the transformative application of mobile technologies is also the focus of research within disciplines as diverse as Electronic & Electrical Engineering, Marketing, Human Resource Management and Biomedical Enginering, among others.

Explore Strathclyde's Open Access research on smartphone technology now...

Opening the black box of mixed-metal TMP metallating reagents : direct cadmation or lithium-cadmium transmetallation?

Armstrong, David R. and Kennedy, Alan and Mulvey, Robert E. and Parkinson, John A. and Robertson, Stuart D. (2012) Opening the black box of mixed-metal TMP metallating reagents : direct cadmation or lithium-cadmium transmetallation? Chemical Science, 3 (9). pp. 2700-2707. ISSN 2041-6520

[img]
Preview
PDF
c2sc20392h.pdf - Final Published Version

Download (679kB) | Preview

Abstract

Designed to remove some of the mystery surrounding mixed-metal TMP (2,2,6,6-tetramethylpiperidide) metallating reagents, this study examines in detail "LiCd(TMP)(3)'' in its own right. Previously established as an excellent "cadmating'' (Cd-H exchange) reagent towards a wide variety of aromatic substrates, "LiCd(TMP)(3)'' has been investigated by H-1, C-13 and Cd-113 NMR studies as well as by DOSY NMR spectroscopy. This evidence puts a question mark against its ate formulation implying it exists in THF solution as two independent homometallic amides. Exploring the reactivity of "LiCd(TMP)(3)'' with anisole as a test substrate, both experimentally by NMR studies and theoretically by DFT studies suggests a two-step lithiation/transmetallation process in which the initially formed ortho-lithiated species undergoes a reaction with Cd(TMP)(2) to form new Cd-C and Li-N bonds. For completeness, the homometallic cadmium component Cd(TMP)(2) has been comprehensively characterised for the first time including a crystal structure determination revealing a near-linear N-Cd-N arrangement.