Orbitals secondary interaction

A common interpretation of the interaction of chalcogens with nucleophiles considers donation of electron density from a lone pair on the donor atom into the o- (E-X) orbital (Figure 15.1). As the degree of covalency increases, a hypervalent three-centre four-electron bond is formed. Real systems fall somewhere between secondary interactions and hypervalent (three centre - four electron) bonds. The two extremes can be distinguished by the correlation of X-E and E D distances.In the hypervalent case both bond distances decrease simultaneously, whereas in the secondary bond the distances are anticorrelated. This concept has been applied in a study of selenoquinones 15.17 (R = Ph, Me) with short Se 0 contacts,for... 

Such secondary bonds are formed by donation from the lone pair of a nucleophile into the a orbital of a covalent bond ( n —> a attack ). Weak covalent bonds (implying low-energy a levels) are easier attacked by n - a overlap, leading to unsymmetric or symmetric 3c le bonds, than strong bonds this is why supramolecular arrays, due to secondary interactions or 3c-4e bonds, play a particular role in the chemistry of the heavier main group elements. 

Variations to the cis addition have been found in the transtition state in some cases and a mixture of products has been reported. Two possible stereochemical variations have been reported because of endo and exo addition. Thus in the dimerisation of butadiene Hoffmann and Woodward have shown that besides the primary orbital interactions between C, and C4 of the diene and Cj and C2 of the dienophile, there are also secondary interactions (shown by dotted lines and also called endo addition) between C-2 of the dieno and C-3 of the dienophile. Such orientations are only possible in endo orientation and this will stabilize the transition state. 

The perpendicular orientation of the alkene in such complexes is favored because it maximizes the overlap of the bond with the LUMO (dx2 — y2, Figure 13.7) and minimizes 4e repulsive interactions with the HOMO (ndz2). The in-plane orientation is not expected to be strongly disfavored, however, because of the secondary interaction between the orbital and the dxy orbital. The rotational barrier of ethylene in Zeise s anion was theoretically estimated to be 55 kj/mol [282], within the range 42-63 kj/mol measured by NMR for related complexes [286]. 

Figure B3.7. (a) Four-electron, two-orbital interaction diagram for the N lone pairs, nn (b) secondary interactions with the in-phase combinations of the C—C a and a orbitals which reverse the order of the HOMO and HOMO-1. The orbitals symmetries are specified in D h-...

Figure B7.1. a) 1-Trifluoromethylperfluorocyclobutyl carbanion. (b) The group antibonding orbitals of the CF3 group, (c) Orbital interaction diagram showing the dominant interaction between erf and tic and the secondary interaction of nc with erf (dashed line).

With this model, we need only apply the method already used to derive the selection rules for electrocyclic reactions (p. 53). From the Coulson equations, we can deduce that in the in conrotatory cyclization of pentadiene, the MO generates a destabilizing C5-C4 secondary interaction, a stabilizing and Fg a destabilizing interaction. The absolute values of these contributions rise steadily because the terminal coefficients increase from Fg to Fg. Therefore, the sign of their sum is given by the HOMO contribution. If R is an attractor, the HOMO is Fg and rotation inwards is favored. If R is a donor, the HOMO is 4T and rotation inwards is disfavored. As the Coulson equations are valid only for polyenes, these conclusions are correct insofar as R can be modeled by a carbon 2p orbital. It follows that the Rondan-Houk theory works better for conjugative than for saturated substituents. 

Just as there are secondary interactions in cycloadditions, so too are there ancillary orbital-symmetry effects in sigmatropic reactions. In process (79), Jones and Jones (1967) find no products of [1,3] hydrogen or methyl shifts, e.g. 1,4,7-trimethylheptatriene, which ostensibly (Table 5) are photochemically allowed. They point out that in the first... 

Fukui and Fujimoto (1966a) suggest that an overlap or bond-order criterion is another way in which secondary interactions may be examined. If benzene is assumed to be a crude model for the transition state of the [3,3] sigmatropic reaction, it is easy to show that P for the three orbitals is 2(p z +pz + p ) = — 0 33. The negative bond order indicates repulsion. Therefore, the concerted [3,3] sigmatropic reaction prefers the chair transition state in which atoms 2 and 5 are as far apart as possible. 

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