Solid state reactions cyclometallation

The solution and solid state structural features of the optically pure [Rh(TpMenth)(CO)2] have been reported, TpMenth being found in both k2- and k3-coordination modes. The optically active TpMenth and XpMementh are able to control the stereoselectivity of the C-H bond activation by their coordinated rhodium center. Irradiation of [Rh(TpMenth)(CO)2] under N2 resulted in the generation of an 85 15 mixture of diastereomeric alkyl hydrides due to intramolecular cyclometalation reaction involving the methyl substituents on the ligand isopropyl group (Fig. 3.51).240... 

Cyclometallation reactions that occur in solution are very well documented and such reactions often involve dehydrohalogenation. A solid state orthometallation reaction that occurs via dehydrohalogenation S has been reported. Scheme 12.13 ... 

For complexes with P-donor ligands, metallation often occurs in solution with elimination of an alkane and such reactions also occur in the solid state. For example, the solid state cyclometallation of [PtMe2 PMe2(l-naphthyl) 2l has been investigated. When heated to 200 C, the complex evolved methane (monitored by IR spectroscopy) and gave a product cyclometallated in the 8 (peri) position, containing a stable five-membered... 

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