Cyclometallated complexes thermal reactions

Thermal reactivity of those cyclometallated complexes which are interesting for photochemistry has not been widely and systematically studied so far. Two types of such reactions can be distinguished. 

Ishii A, Yamaguchi Y, Nakata N (2010) Thermal reaction of a (hydrido)(selenolato)platinnm (II) complex having a dibenzobarrelenyl group leading to three cyclometalations. Dalton Trans... 

Many types of aromatic substrate are known to undergo a cyclometallation reaction when exposed to alkylpentacar-bonylmanganese complexes under thermal conditions. It is well established that the treatment of ligand appended arenes with alkylmanganesepentacarbonyl complexes can lead to the formation of [C,Y] heterochelates of Mn(CO)4 (Y being a two-electron donor ligand) (Equation 6). For instance, aromatic compounds such as W,W-dimethylbenzyl-amine, alkyl benzyl thioethers, 2-phenylpyridine, acetophenone, benzaldehyde, and diazobenzene can be readily... 

Pt(II) and Pd(II) form planar, bis-cyclometallated species only through exchange with another metal, for example, Li. The former undergoes facile thermal, or photochemically induced, oxidative addition reactions, yielding bis-cyclometallated Pt(IV) complexes. 

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