Ethenyl anions

The question of configurational stability has been investigated first for vinylidene carbenoids and, more recently, for alkylcarbenoids. Vinyl anions are usually considered to be configurationally stable" ° the calculated inversion barrier of the ethenyl anion 10 (R = H) is about 35 kcal mol (equation 4)" . Concerning lithioalkenes, this configurational stability has been confirmed experimentally for a-hydrogen, a-alkyl and a-aryl substituted derivatives . The inversion of vinylidene lithium carbenoids was already... 

The crystal structure of [Fe(C5H4R)2][Ni(mnt)2] ([Fe(C5R)2]+ = l,l -bis[2-(4-(methylthio)-( )-ethenyl]ferrocenium) is based on segregated chains of cations and anions. The stacks of anions are isolated by the cations and consist of a packing of dimers. In this compound yT decreases cooling, which indicating the presence of dominant AF interactions [66]. 

Figure 2.30 Representation of the asymmetric unit of [Nd(L )4(H20)][(TTF—CH=CH—Py+)] 2-The radical cation donors are drawn as balls and sticks the paramagnetic anionic coordination complexes of Nd(III) are drawn as capped sticks [23d], (Reprinted with permission from F. Pointillart, O. Maury, Y. Fe Gal, S. Golhen, O. Cador and F. Ouahab, 4-(2-Tetrathiafulvalenyl-ethenyl)pyridine (TTF—CH=CH—py) radical cation salts containing poly(P-diketonate) rare earth complexes synthesis, crystal structure, photoluminescent and magnetic properties, Inorganic Chemistry, 48, 7421-7429, 2009. 2009 American Chemical Society.)...

ETHENYL-4-METHOXYCYCLOBUTENE-l,2-DIONE. This procedure also provides a convenient method for the preparation of DIMETHYL SQUARATE, an important intermediate. The synthesis of (lR, 6S, 7S )-4-(tert-BUTYLDIMETHYLSILOXY)-6-(TRIMETHYLSILYL)BICYCLO-[5.4.0JUNDEC-4-EN-2-ONE is representative of a general protocol for the construction of cycloheptenones by a [3 + 4] annulation. The method features the addition of a lithium enolate to an acryloyl silane to give a 1,2-adduct that undergoes a novel sequence of a concerted Brook rearrange-ment/cyclopropanation and an anionic oxy-Cope rearrangement. 

Introduction of arylsulfonylmethyl substituents into nitroheteroaromatic rings is of great practical value because these sulfones are versatile intermediates in organic synthesis. Nitrobenzyl aryl sulfones and their heterocyclic analogues can easily be transformed into the corresponding ethenyl derivatives by a simple alkylation with simultaneous elimination of arylsulfinate anion [125]. Diethyl methylenemalonate substituent can be introduced in the positimi 4- of 5-nitroimidazole via the VNS reaction of 5-nitroimidazole with the carbanion of chloromethyl phenyl sulfone [112, 124], followed by condensation of the obtained 4-(phenylsulfonyl)methyl derivative with diethyl bromomalonate or diethyl ketomalonate (Scheme 33) [126]. 

The IR spectroscopic pattern of l-methyl-4-[2-(4-hydroxyphenyl)ethenyl)]pyri-dinium] hydrogensquarate in the solid state is significantly complicated because of the presence of hydrogensquarate anions being characterized by a series of absorption peaks within the whole 1800 to 400 cm" region. In this and other similar cases, Raman spectroscopy (Figure 6.12) supports the interpretation of the vibrational characteristics and structural analysis. 

---