Recent Advances in Metallaaromatic Chemistry

Metallaaromatics can be broadly defined as aromatic compounds in which one of the ring atoms is a transition metal. The metallabenzenes are one important class of these compounds that has undergone extensive study recently. Closely related species such as fused‐ring metallabenzenes, heterometallabenzenes, π‐coordinated metallabenzenes and metallabenzynes have also attracted considerable attention. Although many metallaaromatics can be considered as metalla‐analogues of classic organic aromatic compounds, this is not always the case. Recent seminal studies have shown that metallapentalenes and metallapentalynes, which are metalla‐analogues of the anti‐aromatic compounds pentalene and pentalyne, are in fact aromatic and highly stable. Very unusual spiro‐metallaaromatic compounds have also recently been isolated. In this concepts article, key features of all these intriguing metallaaromatic compounds are discussed with reference to the structural, spectroscopic, reactivity and theoretical studies that have been undertaken. These compounds continue to generate much interest, not only because of the contributions they make to fundamental chemical understanding, but also because of the promise of possible practical applications. New aromatics with a metallic ring: Aromatic compounds in which one of the ring atoms is a transition metal are attracting growing interest. Recent developments in this field of metallaaromatic chemistry include the isolation and study of metalla‐pentalenes, metallapentalynes, metallaanthracenes and spiro‐metallaaromatic compounds. These and other recent advances are discussed within the context of established metallaaromatics.