Alkali/coinage metals – organolithium, organocuprate chemistry

This chapter describes the most interesting recent advances in group 1 and 11 organometallic chemistry. The focus throughout will be on compounds and complexes that contain at least one carbon–metal bond and which appeared in 2013. Section 1 discusses compounds and complexes of the alkali metals, looking firstly at organolithiums and then at higher alkali metal systems. Highlights include the development of new spectroscopic methods for evaluating mean molecular size in solution, the combination of alkali metals with less polarising metals in so-called synergic bases and attempts to use these systems catalytically with respect to at least one metal. Interesting advances have also been reported in the synthesis of stable alumoles and their corresponding dianions. Compounds of the coinage metals – copper, silver and gold – are considered in Section 2 of the review, with discussion being broken down by metal and starting with copper. Work on the direct activation of fluoroform continued in 2013, with CuCF₃ successfully being stabilized by the addition of a crown ether. Meanwhile, in a structural vein, the carbonyl π-complexation of lithiocuprates has been reported. Highlights of higher group 11 chemistry include the observation of post-synthetic photolytic modifications to the structures of molecular squares based on olefin-bridged bis(nhc) ligands and silver and gold centres, with UV-irradiation initiating a [2+2] cycloaddition reaction to yield cyclobutane-bridged tetrakis(nhc) complexes. Mixed-metal systems of group 11 are also discussed as appropriate.