Neues aus der Chemie des Berylliums

<jats:title>Abstract</jats:title><jats:p><jats:bold>Recent Advances in the Chemistry of Beryllium</jats:bold></jats:p><jats:p>A review of recent results in coordination chemistry of beryllium halides is given. In accordance with the editors' objective, this Research Report is not a complete review of the literature in this field, but the important literature close to it is considered. The following subjects are presented:</jats:p><jats:p>(i) Syntheses and structural characterizations of tetraphenylphosphonium salts of [BeCl<jats:sub>4</jats:sub>]<jats:sup>2−</jats:sup>, [Be<jats:sub>2</jats:sub>Cl<jats:sub>6</jats:sub>]<jats:sup>2−</jats:sup>, and the unique [Be<jats:sub>2</jats:sub>F<jats:sub>6</jats:sub>]<jats:sup>2−</jats:sup> ion, which are soluble in organic solvents like dichloromethane or acetonitrile. (Ph<jats:sub>4</jats:sub>P)<jats:sub>2</jats:sub>[Be<jats:sub>2</jats:sub>F<jats:sub>6</jats:sub>]·2CH<jats:sub>3</jats:sub>CN is also extensively studied by IR spectroscopy and quantum chemical calculations (DFT).</jats:p><jats:p>(ii) Application of (Ph<jats:sub>4</jats:sub>)<jats:sub>2</jats:sub>[Be<jats:sub>2</jats:sub>Cl<jats:sub>6</jats:sub>] to prepare donor acceptor complexes with <jats:italic>N</jats:italic>‐donor ligands D to give complexes [BeCl<jats:sub>3</jats:sub>(D)]<jats:sup>−</jats:sup> which are isoelectronical with the corresponding boron compounds [BCl<jats:sub>3</jats:sub>(D)], including quantum chemical calculations.</jats:p><jats:p>(iii) Molecular complexes of the type [BeCl<jats:sub>2</jats:sub>(D)<jats:sub>2</jats:sub>] with D = phosphorane imines HNPR<jats:sub>3</jats:sub> or Me<jats:sub>3</jats:sub>SiNPR<jats:sub>3</jats:sub>.</jats:p><jats:p>(iv) Phosphoraneiminato complexes of beryllium, among these the first example [BeCl(μ‐NPEt<jats:sub>3</jats:sub>)]<jats:sub>4</jats:sub> with a Be<jats:sub>4</jats:sub>N<jats:sub>4</jats:sub> heterocubane skeleton.</jats:p><jats:p>(v) Azido complexes of several types, including the unique examples with adamantane‐like structure [Be<jats:sub>4</jats:sub>X<jats:sub>4</jats:sub>(μ‐N<jats:sub>3</jats:sub>)<jats:sub>6</jats:sub>]<jats:sup>2−</jats:sup> with X = Cl, Br.</jats:p><jats:p>(vi) Monocationic complexes [BeCl(12‐crown‐4)]<jats:sup>+</jats:sup>[SbCl<jats:sub>4</jats:sub>]<jats:sup>−</jats:sup> and [BeCl(PMDETA)]<jats:sup>+</jats:sup>Cl<jats:sup>−</jats:sup> (PMDETA = pentamethyl‐diethylenetriamine).</jats:p><jats:p>(vii) Dicationic complexes with <jats:italic>O</jats:italic>‐donor ligands H<jats:sub>2</jats:sub>O and OSMe<jats:sub>2</jats:sub>. [Be(OH<jats:sub>2</jats:sub>)<jats:sub>4</jats:sub>]Cl<jats:sub>2</jats:sub>, [Be(OSMe<jats:sub>2</jats:sub>)<jats:sub>4</jats:sub>]Cl<jats:sub>2</jats:sub>, and mixed ligand complexes like [Be(OH<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>(OSMe<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>]Cl<jats:sub>2</jats:sub>.</jats:p><jats:p>(viii) Molecular and anionic oxo‐complexes, particularly with μ‐OSiMe<jats:sub>3</jats:sub> groups, among these the tetramethyl‐trioxosilanato complex (Ph<jats:sub>4</jats:sub>P)<jats:sub>2</jats:sub>[Be<jats:sub>4</jats:sub>(μ‐Cl)<jats:sub>2</jats:sub>Cl<jats:sub>4</jats:sub>(OSiMe<jats:sub>2</jats:sub>OSiMe<jats:sub>2</jats:sub>O)<jats:sub>2</jats:sub>].</jats:p>