The thermal induced reactions of bis((eta)('5)-cyclopentadienyl)diphenyltitanium with several unsymmetrical acetylenes have been investigated. Acetylenes which vary widely in electronic and or steric properties were used to gain further insight in the thermolyses of bis((eta)('5)-cyclopentadienyl)diphenyltitanium with acetylenes. Analysis of the resulting isomeric benzotitanoles by ('1)H-NMR and chemical degradation techniques indicated that steric effects rather than electronic controlled the finial outcome of the reaction. Bis((eta)('5)-cyclopentadienyl) Group 4B diaryls {Cp(,2)MR(,2) (M = Ti, Zr, Hf) (R = C(,6)H(,5), p-CH(,3)C(,6)H(,4))} are photo-reactive. Unlike the thermal degradation of these materials the major organic product was the biaryl. Deuteration experiments indicated solvent participation during the photo-induced decomposition. An EPR study of the Group 4B diaryl metallocene derivatives indicated that a primary photo-process is homolytic cleavage of the metal-carbon linkage. Paramagnetic species, indicated by their EPR signals, and free organic radicals observed as a radical trap adduct were produced. These species can activate the carbon-hydrogen bonds of benzene and catalyzed the H/D exchange between molecular deuterium and benzene. The metal carbonyl compounds, Cp(,2)M(CO)(,2) (M = Ti, Zr, Hf), Ind(,2)M(CO)(,2) (M = Ti, Zr), Cp''CpM(CO)(,2) (M = Ti, zr, Hf) and Cp''(,2)M(CO)(,2) (M = Ti, Zr, Hf) were prepared in good yields under mild conditions (1 atm., 25(DEGREES)C) via the reductive carbonylation of the corresponding metallocene dichlorides complexes using mercuric chloride activated magnesium metal as a reducing agent.

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