Bond, order Lewis

The cluster calculations for Li+, Na+, and K+ ions in six-membered windows (S,. and Sn sites) were performed by Beran (104). It was concluded that in this series the properties of a zeolite framework (charge distribution, bond orders, Lewis acidity or basicity as characterized by LUMO and HOMO energies) only slightly depend on the type of cation. The decrease of water adsorption heats in this sequence was explained by the assumption that the strength of the water-cation interaction correlates with the strength of the interaction between a cation and lattice oxygen atoms. 

Why is the bond order (Lewis) for ethene given as "2" in Table 1 ... 

Based on the resonance hybrid model of Figure 1, why is the C-C bond order (Lewis) 1.5 Explain your analysis. 

Nitrones are a rather polarized 1,3-dipoles so that the transition structure of their cydoaddition reactions to alkenes activated by an electron-withdrawing substituent would involve some asynchronous nature with respect to the newly forming bonds, especially so in the Lewis acid-catalyzed reactions. Therefore, the transition structures for the catalyzed nitrone cydoaddition reactions were estimated on the basis of ab-initio calculations using the 3-21G basis set. A model reaction indudes the interaction between CH2=NH(0) and acrolein in the presence or absence of BH3 as an acid catalyst (Scheme 7.30). Both the catalyzed and uncatalyzed reactions have only one transition state in each case, indicating that the reactions are both concerted. However, the synchronous nature between the newly forming 01-C5 and C3-C4 bonds in the transition structure TS-J of the catalyzed reaction is rather different from that in the uncatalyzed reaction TS-K. For example, the bond lengths and bond orders in the uncatalyzed reaction are 1.93 A and 0.37 for the 01-C5 bond and 2.47 A and 0.19 for the C3-C4 bond, while those in... 

A single shared pair of electrons is called a single bond. Two electron pairs shared between two atoms constitute a double bond, and three shared electron pairs constitute a triple bond. A double bond, such as C 0, is written C=0 in a Lewis structure. Similarly, a triple bond, such as C C, is written G C. Double and triple bonds are collectively called multiple bonds. The bond order is the number of bonds that link a specific pair of atoms. The bond order in H, is 1 in the group C=0, it is 2 and, for O C in a molecule such as ethyne, C2H2, the bond order is 3. 

At first sight, the molecular orbital description of N2 looks quite different from the Lewis description ( N=N ). However, it is, in fact, very closely related. We can see their similarity by defining the bond order (b) in molecular orbital theory as the net number of bonds, allowing for the cancellation of bonds by antibonds ... 

SOLUTION The Lewis structure of F2 is F— F , and so we anticipate that its bond order is L. To calculate the hond order formally, we proceed as in Toolbox 3.2. 

The red arrows indicate the direction of the shift of electron density away from the O—H bond. The Lewis structures shown are the ones with the most favorable formal charges, but it is unlikely that the bond orders are as high as these structures suggest. 

The boranes are electron-deficient compounds (Section 3.8) we cannot write valid Lewis structures for them, because too few electrons are available. For instance, there are 8 atoms in diborane, so we need at least 7 bonds however, there are only 12 valence electrons, and so we can form at most 6 electron-pair bonds. In molecular orbital theory, these electron pairs are regarded as delocalized over the entire molecule, and their bonding power is shared by several atoms. In diborane, for instance, a single electron pair is delocalized over a B—H—B unit. It binds all three atoms together with bond order of 4 for each of the B—H bridging bonds. The molecule has two such bridging three-center bonds (9). 

Bond paths are observed between bonded atoms in a molecule and only between these atoms. They are usually consistent with the bonds as defined by the Lewis structure and by experiment. There are, however, differences. There is only a single bond path between atoms that are multiply bonded in a Lewis structure because the electron density is always a maximum along the internuclear axis even in a Lewis multiple bond. The value of pb does, however, increase with increasing Lewis bond order, as is shown by the values for ethane (0.249 au), ethene (0.356 au), and ethyne (0.427 au), which indicate, as expected, an increasing amount of electron density in the bonding region. 

Bond paths are normally found in cases in which there is a bond as defined by Lewis. There is only one bond path for a multiple bond irrespective of the bond order. The bond order is, however, reflected in the value of pbcp. Bond paths are also found in molecules for which a single Lewis structure cannot be written. 

The very large perturbing influence of C and 0 bonding on the CO bond order led us to explore the influence of Lewis acid and proton acid promoted reactions of metal carbonyl complexes. 

Based on Lewis theory, one would expect C2 to have the greater bond energy due to the formation of quadruple bond, CasC vs. Li—Li. The molecular orbital diagrams and bond orders are as follows. 

In practice, the NBO program labels an electron pair as a lone pair (LP) on center B whenever cb 2 > 0.95, i.e., when more than 95% of the electron density is concentrated on B, with only a weak (<5%) delocalization tail on A. Although this numerical threshold produces an apparent discontinuity in program output for the best single NBO Lewis structure, the multi-resonance NRT description depicts smooth variations of bond order from uF(lon) = 1 (pure ionic one-center) to bu 10n) = 0 (covalent two-center). This properly reflects the fact that the ionic-covalent transition is physically a smooth, continuous variation of electron-density distribution, rather than abrupt hopping from one distinct bond type to another. 

Recall that such Lewis-like diagrams are intended to convey only the localized electron-pair assignments about the central hexavalent metal atom, not the molecular shape.) Here Os(CH2)2 typifies allene-like bonding, while HW(CH2)(CH), W(CH)2, and W(CH2)3 represent cases of higher central-atom bond order that are unachievable with main-group elements. 

As in main-group chemistry, hypovalent hydrides of the transition series have pronounced tendencies to form bridging tau bonds. In addition to H4TaTaH4, the multiply bonded species HTaTaH features two symmetrically bridging hydrides. Despite the complexity introduced by such tau bonds, the Ta-Ta interaction clearly has high bond order, as simple Lewis-like structures prescribe. 

Figure 4.23 graphically displays the metal-metal bond lengths (cf. Table 4.15) and their dependences on the formal bond order of the Lewis-like formula. These plots all show the expected decrease of mm with increasing bond order, but with somewhat different rates of decrease for different metal atoms. Thus, the multiplebonding of the Lewis-like picture readily accounts for the variations of metal-metal bond length in these hydrides. 

Figure 4.23 Variations of metal-metal bond length with nominal formal bond order (the number of bonds in the natural Lewis structure) in duodectet-rule-conforming dinuclear hydrides H MMH (see Table 4.15).

In summary, the Lewis-like model seems to predict the composition, qualitative molecular shape, and general forms of hybrids and bond functions accurately for a wide variety of main-group derivatives of transition metals. The sd-hybridization and duodectet-rule concepts for d-block elements therefore appear to offer an extended zeroth-order Lewis-like model of covalent bonding that spans main-group and transition-metal chemistry in a satisfactorily unified manner. 

No. Lewis base/acid Charge Energy (kcal mol 1) 2b ah (< ) Bond orders ... 

Further synergistic enhancement of amide resonance and H-bonding occurs when both monomers can participate in two complementary H-bonds, once as a Lewis base and once as a Lewis acid. Such concerted (cooperative) pairs of H-bonds occur in the cyclic formamide dimer, as illustrated in Fig. 5.20. In this case the strength of each H-bond is further enhanced (to 6.61 kcalmol-1, about 4.7 times that of the prototype (5.31c)), the bond orders ben and bco are further shifted (to 1.384 and 1.655, respectively), and the bond lengths undergo further shifts in the... 

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