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- W1965254908 abstract "The titanocene vinylidene intermediate [Cp*2TiCCH2] (6) (Cp*: C5(CH3)5), formed by ethene or methane elimination from Cp*2TiCH2CH2CCH2 (5) and Cp*2Ti(CHCH2)(CH3) (7), respectively, reacts with 1,3-diynes RC⋮C-C⋮CR (R = Me (13a), Ph (13b), SiMe3 (13c), CMe3 (13d)) by a [2 + 2]-cycloaddition, giving metallacyclobutenes Cp*2TiC(C⋮CR)CRCCH2 (9a−d). Using the unsymmetrical 1,3-diyne RC⋮CC⋮CR1 (R = CMe3, R1 = SiMe3 (13e)), a 9:1 mixture of the metallacyclobutenes Cp*2TiC(C⋮CR)CR1CCH2 (9e) and Cp*2TiC(C⋮CR1)CRCCH2 (9e‘) is formed. In all cases, exclusive formation of one regioisomer exhibiting the C⋮CR substituent in the α-position of the metallacycle is observed. The regioselectivity of the formation of 9 is attributed to the polarity of the C⋮C bond as well as the stereochemical conditions, proven by ab initio calculations at the Hartree−Fock (HF) level of theory with the 3-21G(*) standard basis set and molecular modeling. The X-ray structure of 9c is presented. Subsequent reactions of 9 with an excess of the titanocene intermediate 6, to form binuclear metallacycles, are not observed." @default.
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- W1965254908 date "1996-10-29" @default.
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- W1965254908 title "Regioselective Reactions of 1,3-Diynes with the Titanocene Vinylidene Fragment [Cp*<sub>2</sub>TiCCH<sub>2</sub>]. Crystal and Molecular Structure of Cp*<sub>2</sub>TiC(C⋮CSiMe<sub>3</sub>)C(SiMe<sub>3</sub>)CCH<sub>2</sub>" @default.
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- W1965254908 doi "https://doi.org/10.1021/om960591v" @default.
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