RESUMO
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)·M(OC(14)H(9))](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)·Na(µ-(t)Bu)(µ-TMP)Zn((t)Bu)] are employed, only the alkali-metal-containing species is isolated (e.g., 2 in this case). Providing a contrast, complexes 5 [(TMEDA)·Mg(OC(14)H(9))(n)Bu] and 6 [(TMEDA)·Zn(OC(14)H(9))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.
Assuntos
Antracenos/química , Compostos Organometálicos/síntese química , Zinco/química , Antracenos/síntese química , Cristalografia por Raios X , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Estrutura Molecular , Compostos Organometálicos/química , PrótonsRESUMO
The first sodium-magnesium and sodium-zinc ketimido complexes display contrasting inverse crown ring and pseudo-cubane structures respectively, while a sodium-zinc heterotrianionic alkide-alkoxide-amide adopts a third type of structure with a stepped ladder motif.
RESUMO
Benzene can be easily 1,4-dideprotonated stoichiometrically on reaction with two equivalents of a synergic mixture of tBu2Zn, NaTMP and TMEDA to give a unique 1,4-dizincated benzene product which has been characterised by X-ray crystallography and NMR spectroscopy as well as modelled theoretically by DFT computational studies; a related synergic dimagnesiation of benzene is also reported.
