Photochemical decomposition of (diphenyl)bis(η5-cyclopentadienyl) titanium, (diphenyl)bis(η5-pentamethylcyclopentadienyl) titanium and the zirconium analogs

Add time:07/23/2019    Source:sciencedirect.com

Qualitative investigations of the mechanisms of photochemical decomposition of diphenylpermethyltitanocene and zirconocene have been made. Reductive elimination as well as homolytic cleavage of metal-carbon 0-bonds are the two major pathways for photodecomposition of the diphenylpermethylmetallocenes. When benzene-d6 was used as the solvent for photolysis of diphenylpermethyltitanocene, biphenyl-d0 and biphenyl-d5 were found in a ratio of 36/1, indicating that reductive elimination was the much more favorable process. But in the case of diphenylpermethylzirconocene, biphenyl-d0 and biphenyl-d5 were found in a ratio of 1/3, indicating that the homolytic photocleavage of the 0-bonds was predominant.In the presence of carbon monoxide, moderately large amount of the dicarbonylpermethylmetallocenes were found, suggesting that the permethylmetallocenes were the intermediates. The discovery of pentamethylcyclopentadiene and 2,3,4,5-tetramethylfulvene in the recovered solvent indicated further photodecomposition of permethylmetallocene. Consequently another intermediate, [(C5Me4CH2)M], is proposed. An oligomeric material was found to be the major metal containing product after the photolyses.

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