Spectroscopy and photochemical reactivity of cyclooctadiene platinum complexes

The spectroscopic and photochemical properties of a series of 1,5-cycloocta diene platinum complexes of the type [(COD)Pt(R)(2)] (R = alkyl, alkynyl, o r aryl) were examined. The observed photoreactivity is wavelength dependent and observed reaction rates correlate with the donor-strength of the R gro up. For strongly donating substituents like adamantylmethyl, benzyl or iso- propyl rates were increased by factors of about 100 for a given model react ion compared to the dimethyl derivative. The products were determined by NM R spectroscopy. Different reaction pathways were found depending on the sub stituents R. Theoretical calculations (DFT) on the electronic structure rev ealed the character of optical transitions and excited states. (C) 2001 Els evier Science B.V. All rights reserved.