Lead electron pairs

The next simplest loop would contain at least one reaction in which three electron pairs are re-paired. Inspection of the possible combinations of two four-electron reactions and one six-electron reaction starting with CHDN reveals that they all lead to phase preseiwing i p loops that do not contain a conical intersection. It is therefore necessary to examine loops in which one leg results in a two electron-pair exchange, and the other two legs involve three elechon-pair exchanges fip loops). As will be discussed in Section VI, all reported products (except the helicopter-type elimination of H2) can be understood on the basis of four-electron loops. We therefore proceed to discuss the unique helicopter... 

The transformation of ethylene to the carbene requires the re-pairing of three electron pairs. It is a phase-preserving reaction, so that the loop is an ip one. The sp -hybridized carbon atom formed upon H transfer is a chiral center consequently, there are two equivalent loops, and thus conical intersections, leading to two enantiomers. 

The positive bromine which leads to bromonium ion intermediates is softer and also has unshared electron pairs which can permit a total of four electrons to participate in the bridged bromonium ion intermediate. This would be expected to lead to a more strongly bridged and more stable species than is possible in the case of the proton. The bromonium ion can be represented as having two covalent bonds to bromine and is electrophilic but not electron-deficient. 

The hypothesis that electron-pair donation from the a atom will stabilize this transition state leads to the difficulty that the attacking atom must carry more bonds than conventional valence bond symbolism admits. Despite this problem, the general idea is expressed by 7 and its relationship to 6 by resonance. It is possible that transition state stabilization can be obtained in this way by rehybridization of the entire molecule. Klopman et al. suggest that the a effect arises from... 

The chemistry of Lewis acid-base adducts (electron-pair donor-acceptor complexes) has stimulated the development of measures of the Lewis basicity of solvents. Jensen and Persson have reviewed these. Gutmann defined the donor number (DN) as the negative of the enthalpy change (in kcal moL ) for the interaction of an electron-pair donor with SbCls in a dilute solution in dichloroethane. DN has been widely used to correlate complexing data, but side reactions can lead to inaccurate DN values for some solvents. Maria and Gal measured the enthalpy change of this reaction... 

Processes such as bond dissociation which require the separation of an electron pair and for which restricted calculations thus lead to incorrect products (even though there is an even number of electrons). 

These questions can often be answered with the aid of a set of rules regarding the properties of electron-pair bonds derived from the quantum mechanics, and of a semi-quantitative method of treatment of bond eigenfunctions leading to information on the strengths and relative orientation of bonds2). The rules are the following. 

It is interesting to note, as pointed out to me by Mr. J. L. Hoard, that these considerations lead to an explanation of the stability of trivalent cobalt in electron-pair bond complexes as compared to ionic compounds. The formation of complexes does not change the equilibrium between bivalent and trivalent iron very much, as is seen from the electrode potentials, while a great change is produced in the equilibrium between bivalent and trivalent cobalt. 

The foregoing discussion leads to the conclusion that static deformations as well as phonons should be stabilized for superconducting metals by the change in effective radius associated with unsynchronized resonance of electron-pair bonds. Deformation from cubic to tetragonal symmetry, presumably the result of this interaction, has been reported for VsSi at temperatures below 21 K26- 27 and for Nb2Sn at temperatures below 43°K.28... 

In—W bond. Use of Ph3Al leads to a complex in which the oxygen atom of a carbonyl ligand is the site of electron pair basicity in a WC=OAl link. Solutions of [n-Bu4N][Ph3GaCpW(CO)3] in CH2CI2 contain, in addition to free [CpW(CO)3], two isomeric complexes a metal-metal-bonded species and a C- and O-bonded adduct of the type found in the Ph3Al case. 

Ligands that reduce the activity of Hg(II) more than that of Hg(I) lead to disproportionation products when added to a solution containing Hg2 ions. Because the smaller Hg ion is a better electron-pair acceptor acid than the larger Hgj ion, the number of Hg(I) complexes may be limited, but many complexes of Hg(I) are formed by reactions of Hg, with ligands containing donor atoms from groups VB and VIB. Polyethers and polyesters are good solvents for these reactions, ... 

The nucleophile OH uses its lone pair electrons to attack the alkyl halide carbon 180° away from the departing halogen. This leads to a transition state with a partially formed C-O bond and a partially broken C-X bond. The stereochemistry is inverted as the C-O bond fully forms, and the halide ion departs with the electron pair from the former C-X bond. 

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