20145-47-5Relevant academic research and scientific papers
Regioselectivity of reactions of vinyl- and isopropenylcyclopentadienide anions with electrophilic agents. Synthesis and crystal structures of complexes [C5H4C(Me)=CH2]ZrCl3·2THF and [C5Me4CH=CH2]ZrCl3·2THF
Krut'ko,Borzov,Dolomanov,Churakov,Lemenovskii
, p. 390 - 399 (2005)
Regioselectivity of the reactions of lithium vinyl- and isopropenylcyclopentadienides C5H4C(R)=CH2 -Li+(R = H, Me) and lithium tetramethylvinylcyclopentadienide C5Me4CH=CH2 -Li+ with various electrophilic agents (Me 3SiCl, Me3SnCl, Et2PCl, 2-chloro-1, 3-dioxaphospholane, and MeI) was studied. Two new monocyclopentadienyl zirconium complexes, [C5H4C(Me) = CH2]ZrCl 3·2THF and [C5Me4CH=CH 2]ZrCl3·2THF, were synthesized. Their crystal structures were established by X-ray diffraction. The results of quantum chemical calculations for the C5H4C(R) = CH2 - (R = H, Me) and C5Me4CH=CH2 - anions by the DFT method (RMPW1PW91) with the 6-311+G(d, p) split valence basis set are in good agreement with experimental data on the regioselectivity of their reactions with electrophilic agents.
The Photoisomerization of 1,2,3,4,5-Pentamethyl-5-vinyl-1,3-cyclopentadiene
Burger, Ulrich,Etienne, Robert
, p. 2057 - 2062 (2007/10/02)
The title compound 1 is shown to give, both upon direct irradiation at 254 nm and upon acetophenone-sensitized photolysis at 300 nm, the syn-vinyl-pentamethylhousene 5, which spontaneously rearranges in a -sigmatropic process to give the bicycloheptadiene skeleton 2.Based on the photochemical behaviour of selectively deuterated starting material, the suggestion is made that the direct photolysis produces the vinylhousene skeleton by a classic electrocyclization, whereas the sensitized reaction reaches the same target via a di-?-methane rearrangement.The bicycloheptadiene derivative 2 gives pentamethylhomoprismane 3 upon prolonged irradiation at 254 nm.
