Picture of person typing on laptop with programming code visible on the laptop screen

World class computing and information science 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 researchers from the Department of Computer & Information Sciences involved in mathematically structured programming, similarity and metric search, computer security, software systems, combinatronics and digital health.

The Department also includes the iSchool Research Group, which performs leading research into socio-technical phenomena and topics such as information retrieval and information seeking behaviour.

Explore

Alkali-metal-mediated manganation: a method for directly attaching manganese(II) centers to aromatic frameworks

Mulvey, R.E. and Garcia-Alvarez, J. and Kennedy, A.R. and Klett, J. (2007) Alkali-metal-mediated manganation: a method for directly attaching manganese(II) centers to aromatic frameworks. Angewandte Chemie, 46 (7). pp. 1105-1108. ISSN 0044-8249

Full text not available in this repository. Request a copy from the Strathclyde author

Abstract

A keystone methodology in synthetic chemistry, metalation (metal-hydrogen exchange) reactions of aromatic compounds are usually the domain of highly reactive polar organometallics such as alkyllithium compounds, LICKOR (alkyllithium compounds cocomplexed with potassium tertbutoxide) superbases, or lithium amides.[1] Strictly these reactions are lithiations (or potassiations) as the incoming lithium atom (or potassium atom) takes the place of the outgoing hydrogen atom. The lower-polarity metals magnesium, zinc, and aluminum generally form slow-reacting metalating agents which are ineffective towards aromatic compounds. Therefore, to attach these less reactive metals directly to an aromatic scaffold, the lithiated aromatic compound must be synthesized beforehand and then an additional metathetical reaction often involving a metal halide (for example, RMgX, ZnX2, or R2AlX) has to be carried out. The presence of the ionic halide often limits the range of solvents available for such reactions with hydrocarbons and arenes, which are generally ruled out in favor of polar substitutes (commonly ether or THF). Recently, however, it has been shown that pairing lithium (or another alkali metal) with one of these inferior multivalent metals in the same organometallic molecule (an '-ate' formulation), can generate 'synergic', mixed-metal reagents capable of directly magnesiating,[2,3] zincating,[3] or aluminating[4] aromatic substrates, thus circumventing the need for a subsequent metathesis. In addition to this new inorganic (metal) perspective, these synergic reagents can open up new organic horizons by promoting unusual regioselective deprotonations (for example, meta-orientated in the cases of toluene[5] and N,Ndimethylaniline[ 6]) or special polydeprotonations (for example, 2,6-twofold in the case of naphthalene[7] and 1,1',3,3'- fourfold in the cases of ferrocene and its Group 8 homologues[ 8]).