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Kiessling, Tilmann G. and Suenkel, Karlheinz (2018): Metalation Studies on Titanocene Dithiolates. In: Inorganics, Vol. 6, No. 3, 85 [PDF, 1MB]

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Titanocene bis-arylthiolates [(C5H4X)(C5H4Y)Ti(SC6H4R)(2)] (X,Y = H, Cl;R = H, Me) can be prepared from the corresponding titanocene dichlorides by reacting with the thiols in the presence of DABCO as a base. They react with n-butyl lithium to give unstable Ti(III) radical anions. While the unsubstituted thiolates (X = Y = R = H) react with lithium Di-isopropylamide by decomposing to dimeric fulvalene-bridged and thiolate-bridged Ti(III) compounds, the ring-chlorinated compounds can be deprotonated with LDA and give appropriate electrophiles di-substituted and tri-substituted titanocene dithiolates.

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