Bond pairs

The shapes of covalent compounds are determined by the tendency for bonding pairs to be as far apart as possible whilst lone pairs have a greater effect than bonding pairs (VSEPR theory). 

A simple example would be in a study of a diatomic molecule that in a Hartree-Fock calculation has a bonded cr orbital as the highest occupied MO (HOMO) and a a lowest unoccupied MO (LUMO). A CASSCF calculation would then use the two a electrons and set up four CSFs with single and double excitations from the HOMO into the a orbital. This allows the bond dissociation to be described correctly, with different amounts of the neutral atoms, ion pair, and bonded pair controlled by the Cl coefficients, with the optimal shapes of the orbitals also being found. For more complicated systems... 

The shapes indicated in Table 2.8 are only exact in cases in which all the electron pairs are equivalent, i.e. they are all bonding pairs. 

Methane, CH4, for example, has a central carbon atom bonded to four hydrogen atoms and the shape is a regular tetrahedron with a H—C—H bond angle of 109°28, exactly that calculated. Electrons in a lone pair , a pair of electrons not used in bonding, occupy a larger fraction of space adjacent to their parent atom since they are under the influence of one nucleus, unlike bonding pairs of electrons which are under the influence of two nuclei. Thus, whenever a lone pair is present some distortion of the essential shape occurs. 

In this case we have three bonding pairs and one lone pair. The essential shape is, therefore, tetrahedral but this is distorted due to the presence of the lone pair of electrons, the H—N—H bond angle beine 107 ... 

When the ammonium ion NH is formed the lone pair becomes a bonding pair and the shape becomes a regular tetrahedron. 

The tetrahedral geometry of methane is often explained with the valence shell electron pair repulsion (VSEPR) model The VSEPR model rests on the idea that an electron pair either a bonded pair or an unshared pair associated with a particular atom will be as far away from the atom s other electron pairs as possible Thus a tetrahedral geomehy permits the four bonds of methane to be maximally separated and is charac terized by H—C—H angles of 109 5° a value referred to as the tetrahedral angle... 

Water (H2O) 105 H V. 0— / Oxygen has two bonded pairs + two unshared pairs Tetrahedral Bent <4... 

Ammonia (NH3) 107 H / Nitrogen has three bonded pairs + one unshared pair Tetrahedral Trigonal pyramidal ... 

Boron trifluoride (BF3) F 20. B- F F Boron has three bonded pairs Trigonal planar Trigonal planar ... 

Carbon dioxide (CO2) /80 0=C=0 Carbon has two double bonds which are counted as two bonded pairs Linear Linear ... 

Bonded pair bonded pair > Unshared pair bonded pair > Unshared pair unshared pair Least repulsive Most repulsive... 

Boron trifluoride is a trigonal planar molecule There are six electrons two for each B—F bond associated with the valence shell of boron These three bonded pairs are farthest apart when they are coplanar with F—B—F bond angles of 120°... 

For the general case of R = any alkyl group how many bonded pairs of electrons are involved in stabilizing RjC by hyperconjugation How many in RzCH"" In RCNz"" ... 

One proposed approach (75) to modeling the phase behavior for hydrogen bonding pairs uses the following expression for the free energy of mixing (eq. 7). 

This initial assignment is, of course, not at equilibrium. In particular, the expected velocity correlation between neighboring atoms is not guaranteed, and most likely it is nonexistent (i.e., in general, neighboring atoms, such as bonded pairs, are expected to... 

Disconnection of non-building-block rings which are embedded in a skeleton and also centrally located, either by breaking one bond or a pair of bonds. The one-bond disconnections which are of value are (a) bonds between C and N, O or S and (b) bonds leading to a totally symmetrical, locally symmetrical, or linear skeleton. The bond-pair disconnections which are most effective in simplification are those which generate two structures of roughly equal complexity. 

Among the most logical disconnections of the carbocyclic rings of 272 (or the other precursors shown extending to 278) is that involving the strategic C(4)-C(5), C(6)-0 bond pair in 272 - 278. 

The highest priority ring disconnective T-goals for 272 are those which disconnect a cocyclic 5,5-fusion bond and offexendo bond pair. The internal ketene-olefin cycloaddition in tactical combination with the Baeyer-Villiger transform is well suited to the double disconnection of such a cyclopentane-y-lactone ring pair. 

Topological Strategy. The use of a particular bond, pair of bonds, set of bonds, or subunit as eligible for disconnection to guide retrosynthetic analysis conversely the designation of bonds or cyclic subunits as ineligible for disconnection (i.e. to be preserved). 

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