Structural elucidation of homometallic anthracenolates synthesised via deprotonative metallation of anthrone

Five novel neutral homometallic complexes which contain the anthracen-9-olate anion have been prepared and characterised by treating anthrone with an organometallic base to induce aromatisation. Three of these complexes [(donor)center dot M(OC14H9)](2) (2-4) are dimeric and contain sodium, lithium and potassium respectively. For 2 and 3 the donor is N,N,N',N'-tetramethylethylenediamine (TMEDA) whilst for 4 it is N, N, N', N '', N ''-pentamethyldiethylenetriamine (PMDETA). When bimetallic reagents such as [(TMEDA)center dot Na(mu-Bu-t)(mu-TMP)Zn(Bu-t)] are employed, only the alkali-metal-containing species is isolated (e.g., 2 in this case). Providing a contrast, complexes 5 [(TMEDA)center dot Mg(OC14H9)Bu-n] and 6 [(TMEDA)center dot Zn(OC14H9)Et] are monomeric. The alkali metal complexes were prepared by reacting anthrone with one molar equivalent of either n-butylsodium, n-butyllithium or (trimethylsilyl)methylpotassium in the presence of the required donor solvent. For 5 and 6, equimolar quantities of di-n-butylmagnesium and diethylzinc, respectively, were reacted with anthrone in the presence of TMEDA. The solid-state structures and the arene solution structures of 2-6 have been determined by X-ray crystallography and NMR spectroscopy respectively.