“…Its results, which showed the structure to be (III) or more clearly shown in (IV) and Fig. 2, were reported in a preliminary communication (Birnbaum, Altman, Maymon & Ginsburg, 1970). In this structure as well as in others in which an irontricarbonyl group is complexed to a cyclic substituted butadiene (e.g.…”
This symmetrical 12-oxa[4.4.3]propella-2,4,7,9-tetraene bis-irontricarbonyl complex, C~sHI207Fe2, m.p.200-204°C, crystallizes in the monoclinic space group C2/c with eight half-molecules in a unit cell of dimensions a=20.791 (3), b=7.173 (1), c= 12"625 (2) A; fl= 111"42 (2) °. The densities are: Dx= 1.713 g.cm -3, D,,= 1.709 g.cm -3. The structure was determined by the heavy-atom method from data collected at room temperature on a four-circle diffractometer using the 0/20 scan technique. It was refined by the least-squares method to R = 4"5 % for 1323 observed reflexions. Each iron atom is complexed to a butadiene group of four planar carbon atoms of the ligand with the following C-C bond lengths, 1-413 (6), 1.401 (6), 1.422 (6) A,.161
“…Its results, which showed the structure to be (III) or more clearly shown in (IV) and Fig. 2, were reported in a preliminary communication (Birnbaum, Altman, Maymon & Ginsburg, 1970). In this structure as well as in others in which an irontricarbonyl group is complexed to a cyclic substituted butadiene (e.g.…”
This symmetrical 12-oxa[4.4.3]propella-2,4,7,9-tetraene bis-irontricarbonyl complex, C~sHI207Fe2, m.p.200-204°C, crystallizes in the monoclinic space group C2/c with eight half-molecules in a unit cell of dimensions a=20.791 (3), b=7.173 (1), c= 12"625 (2) A; fl= 111"42 (2) °. The densities are: Dx= 1.713 g.cm -3, D,,= 1.709 g.cm -3. The structure was determined by the heavy-atom method from data collected at room temperature on a four-circle diffractometer using the 0/20 scan technique. It was refined by the least-squares method to R = 4"5 % for 1323 observed reflexions. Each iron atom is complexed to a butadiene group of four planar carbon atoms of the ligand with the following C-C bond lengths, 1-413 (6), 1.401 (6), 1.422 (6) A,.161
“…'1ore secondar orbital effects a Reactions of propellanes with organametallic reagents Since the ether ~ (X=O) reacts with Fe(CO)s to give 63 exclusively in high yield (27) it immediately seems reasonable to attribute this specificity to a secondary orbital interaction. This stereospecificity is all the more impressive in view of the complex mixture of products obtained from ~ with Fe 2 (C0) 9 , in which the non-discriminating species attacking the substrate in Fe(C0)4.…”
-The use of different propellane substrates indicates for a number of chemical reactions that either repulsive steric interactions of the reactants or attractive interactions of the secondary orbital type control the configuration of the product.The structure of propellanes is such that the three constituent rings divide space into three distinct sectors. It is therefore possible to use suitably constructed propellanes in the study of stereospecific and regiospecific reactions. Thus, if we have a propellane comprising three different rings as indicated by the descriptors a, b, c in its Newman projection A we may observe attack of ring a by a reagent operating within the sector defined by rings a änd b or within the sector defined by rings a and c, and analogously we may observe attack of ring b or ring c in the alternatively possible sectors.Wehave reported on the employment of propellanes as stereochemical models in simpler cases, i.e. in compounds of type! having c2v symmetry (1,2).
A 8Wehave shown that in many propellanes having c 2 symmetry attack occurs exclusively, or almost so, from the direction ~-to the hetero~ring as shown in !• whilst in other cases of such compounds attack occurs mainly from the direction anti-to the hetero-ring as shown in 2.
Diels-Alder ReactionThe oxidation state of the substrates attacked from the ~-direction doesn't appear to matter when additional relatives are attacked in the same type of reaction. Thus, not only 1 but also related compounds containing only one cyclohexadiene ring (e.g. l·~·~ are attacked fromthe ~-direction in the Diels-Alder reaction with the very reactive dienophiles of the cisazo type ~· Thus far mainly such adducts of azo-dienophiles have been studied because t~ permit ready chemical proof of the configurations of the ~-and bis-Diels-Alder adducts
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