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• W1985415489 abstract "The insertion of unactivated acetylenes into the metal-hydride bonds of (η5-C5Me5)2MH2 (M = Zr, Hf) proceeds rapidly at low temperature to form mono- and/or bisinsertion products, dependent on the steric bulk of the acetylene substituents. 2-Butyne and t-butylacetylene react to form (η5-C5Me5)2M(H)(C(Me)CHMe) and (η5-C5Me5)2M(H)(CHCHCMe3) (M = Zr, Hf). Propyne and 1-butyne react to form (η5-C5Me5)2M(CHCHCH3)2 (M = Zr, Hf) and (η5-C5Me5)2Zr(CHCHCH2CH3)2. Phenylacetylene yields both (η5-C5Me5)2M(H)(CHCHPh) and (η5-C5Me5)2M(CHCHPh)2 (M = Zr, Hf). To extend the study of the unsaturated carbon ligands, the bis(propynyl) complexes (η5-C5Me5)2M(CCCH3)2 (M = Zr, Hf) are prepared by treating (η5-C5Me5)2MCl2 with LiCCCH3. The reactivity of many of these complexes with carbon monoxide and dihydrogen is surveyed. The mono(2-butenyl)zirconium complex (η5-C5Me5)2Zr(H)(C(Me)CHMe) rearranges, forming the crotyl-hydride species (η5-C5Me5)2Zr(H)(η3-C4H7) or, in the presence of 2-butyne, the zirconacyclopentene (η5-C5Me5)2-ZrCH2CH(CH2CH3)C(CH3)C(CH3). The hafnium analog (η5-C5Me5)2Hf-(H)(C(Me)CHMe) also rearranges, although more slowly and less cleanly, to the analogous crotyl-hydride hafnium species. The bis(propenyl) and bis(butenyl)zirconium complexes also rearrange, forming zirconacyclopentenes (η5-C5Me5)2ZrCH2CH(R)CHCR and (η5-C5Me5)2ZrCH2CH(R)C(R)CH (R = CH3, CH2CH3). The bis(propenyl)hafnium complex is stable to rearrangement. Mechanistic and kinetic studies of these transformations demonstrate the occurrence of an unusual β-hydrogen elimination from an sp2-hybridized carbon." @default.
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• W1985415489 date "1985-01-01" @default.
• W1985415489 modified "2023-10-16" @default.
• W1985415489 title "Synthesis and reactivity of alkenyl and alkynyl derivatives of permethylzirconocene and permethylhafnocene. Rearrangement of alkenyl derivatives involving β-H elimination from an sp2-hybridized carbon" @default.
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• W1985415489 doi "https://doi.org/10.1016/0022-328x(85)87025-x" @default.
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