15 BENT'S RULE AND ENERGETICS OF HYBRIDISATION: BENT RULE Bent rule may be stated as follows: “More electronegative constituents ‘prefer’ hybrid orbitals having less s character and more electropositive substituents 'prefer’ hybrid orbitals having more s character." An example of Bent rule is provided by the fluoromethanes. In CHF; the F-C-F bond angle is less than 109.5°, indicating less than 25% s character, but the H-C-H bond angle is larger and C-H bond has more s character. The bond angle in the other fluoromethanes yield similar results. The tendency of more electronegative substituents to seek out the low electronegative pxdx? apical orbital in TBP structures is often termed “apicophilicity". It is well illustrated in a series of oxysulfuranes of the type> prepared by Martin and Co-workers. These, as well as related phosphoranes provide interesting insight into certain molecular rearrangements. Bent's rule is also consistent with and may provide alternative rationalization for Gillespie's VSEPR model. Thus the Bent's rule prediction that highly electronegative constituents will ‘attract’ p character and reduce bond angles is compatible with the reduction in regular 24 Scanned bv CamScanner ‘Seenned with CamScamervolume of the bonding pair when held tightly by an electronegative substituents. Strong, s-rich covalent bonds require a larger volume in space to bond. Thus double bonded oxygen, despite the high electro negativity of oxygen, seeks s-rich orbitals because of the shortness and better overlap of the double bond. Again, the explanation, whether in purely s-character terms (bent's rule) or in larger angular volume for a double bond (VSEPR), predicts the correct structure. The mechanism operating behind Bent’s rule is not completely clear. One factor favouring increased p character in electronegative substituents is the decreased bond angles of p orbitals and the decreased steric requirements of electronegative substituents. There may also be an optimum strategy of bonding for a molecule in which the character is concentrated in those bond in which the electronegativity difference is small and covalent bonding is important. The p character, if any, is then directed towards bonds to electronegative groups. The latter will result in greater ionic bonding in a situation in which covalent bonding would be low anyway because of electronegativity difference. Some light may be thrown on the workings of Bent's rule by observations of apparent exceptions to it. The rate exceptions to broadly useful rules are unfortunate with respect to the universal applications of those rules. They also have the annoying tendency to be confusing to someone who is encountering the rule for the first time, On the other hand, any such exception or apparent exception is a boon to the research since it almost always provides insight into the mechanism operating behind the rule. 25 Scanned by CamScanner ‘Seenned with CamScamerConsider the cyclic bromophosphate ester. cH,8r “y pee, op Se The phosphorus atom is in an approximately tetrahedral environment using four o bonds of approximately sp character. We should expect the more electronegative oxygen atoms to bond to s-poor orbitals on the phosphorus and the two oxygen atoms in the ring do attract hybridizations of about 20%s. The most electropositive constituent on the phosphorus is the bromine atom and Bent's rule would predict an s-rich orbital, but instead it draws another s-poor orbital on the phosphorus atom is that involved in 6 bond to the exocyelic oxygen. This orbital has nearly 40% s-character, The oxygen atom ought to be about as electronegative as the other two, so why the difference? The answer probably lies in the overlap aspect. 1. The large bromine atom has diffuse orbitals that overlap poorly with the relatively small phosphorus atom. Thus, even though the bromine is less electronegative than the oxygen, it probably does not form as strong a covalent bond. 2. The presence of a x bond shortens the exocyclic double bond and increases the overlap of the o orbitals. If molecules respond to increase in overlap by rehybridization in order to profit from it, the increased s-character then becomes reasonable. From this point of view, Bent's rule might be rewarded. The p character tends to concentrate in orbitals with weak covalently (from either electro negativity or overlap considerations), and s-character tends to 26 Scanned by CamScanner ‘Seenned with CamScamerconcentrate in orbitals with strong covalently matched electro negativities and good overlap. Some quantitative support for the above qualitative arguments comes from average bond energies of phosphours, bromine and oxygen. P-Br 264 KJ Mot! P-0 335 KJ Mol* P=0 544 KJ Mol" Bent's rule is a useful tool in inorganic and organic chemistry. For example, it has been used to supplement the VSPER interpretation of the structures of various non-metal fluorides, and should be applicable to a wide range of question on molecular structure. Energetics of Hybridisation: According to hybridisation model, bond directions are determined by a set of hybrid orbitals on the central atom which are used to form bonds to the ligand atoms and to hold unshared pairs. Thus AB» molecules are linear due to the use of linear sp hybrid orbitals. AB, molecule should be equilaterally triangular, while AB2E molecule should be angular, due to use of trigonal sp* hybrids. ABs, AB3E and AB;E, molecule should be tetrahedral, pyramidal and angular, respectively, because here sp’ hybrid orbitals are used. These cases are, of course, very familiar and involve no more than an octet of electrons. For the ABs, AB,E, AB3E and ABE; molecules the hybrid must now include orbitals in their formation. The hybrid orbitals used must be of the sp'dz’ leading to TBP geometry and Sp’dx’-y” leading to SP geometry. There is no way to predict with certainty which set is preferred, and doubtless that difference between them connot be great, since we 7 Scanned by CamScanner ‘Seenned with CamScamerknow experimentally that ABs molecules nearly all have TBP structures, the same arrangement is assumed for the AB4E cases, and so on. Even this adhoc assumption does not solve all difficulties, since the position preferred by lone pairs must be decided and there is no simple physical model here (as there was in the VSEPR approach) to guide us. A preference by lone pairs for equatorial positions has to be assumed. With these assumptions, a consistent correlation of all structures in this five- electron-pair class is possible. For ABs molecule, octahedral sp*d* hybrids are used. For AB,E2 molecule; there is nothing in the directed valence theory itself to show whether the Ione pairs should be cis or trans. The assumption that they must be trans leads to consistent results. The most fundamental problem with the hybridisation model is that in all cases in which there are more than four electron pairs in the valence shell of the central atom, it is necessary to postulate that at least one d orbital becomes fully involved in the bonding. There are both experimental and theoretical reasons for believing that this is too drastic an assumpiton, Some recent MO calculations and other theoretical considerations suggest that although the valence shell d orbitals make a significant contribution to the bonding in many cases, they never play as full a part as do the valence shell p orbitals. Fairly directed experimental evidence in the form of nuclear quadruple resonance studies of the 1 Cl; and ICI? ions shows that in these species, d-orbitals participation is very small. This participations is probably greater in species with more electronegative ligand atoms such as PFs, SFs and Te (OH), but not of equal importance with the contribution of the s and p orbitals. 28 Scanned by CamScanner ‘Seenned with CamScamerPerhaps it is surprising that by going to the opposite extreme, namely by omitting all consideration of d orbitals, but still adhering to the concept of directed orbitals it is again possible to rationalize many of the principal features of the structures of main group. E Estp® = [2(-1806)}+[3(-981)] = 6555 KJ mot! For tetrahedral hybridised phosphours. (3 te?2te'3te') the energy will be: Ete = 5x (-1187) = -5935 KJ mol" In this case the hybridisation has cast 620 KJ mol of energy or roughly two bonds worth of energy. This is shown graphically in the figure 1.10. Figure 1.10 The energy difference between the hybridised and unhybridised atom represents the increase in energy of the two electrons in the filled 3s, orbital and the decrease in energy of the electrons in the half-filled 3p orbitals. The energetics of hybridisation, together with the principle of good overlap, are important in determining the electronic structure of molecules. 29 Scanned by CamScanner ‘Seenned with CamScamer15.1 Third and Fourth Groups Halides For promoting an atom to hybridised excited state energy is required. But when the hybrid orbitals give very strong bonds, the energy gained from bonding may be used for excitation, For example, when carbon forms four covalent bonds, although there is, a promotion energy from Is°2s?2p”—> Is°2s'2p’, this is independent of the hybridization to the valence state : | 8 4 4 § e Figure 1.11 Hybridisation energy of carbon This energy of hybridisation is the order of bonding energy. Its important use is to determine structure of molecules. For example, the stability of the halides of the III A (Gr. 13) and IV A Gr. 14) viz BCL, AICh, GaCls, InCly, TiC and CCl, SiCL,, GeCl,, SnClz, PbCla, can be explained on the basis of hybridisation energy. The heaviest elements of these groups (Thallium and, Tin and Lead) the stable oxidation-states are two unit less than the maximum oxidation states (3 and 4 respectively) i.e. One in Thallium, TICI and two in Tin and Lead, SnCl, and PoCl.. Although, in these elements (Compared to the light elements of the group) excitation is easy. It is because, in the heavier elements orbitals are more diffused (Fig 1.12), hence in a volume region, values of YTI or Pb are less, compared to WB or ‘! Si. This results in lesser overlapping of the central atom orbitals with orbitals of chlorine atoms. Hence, in the compounds of heavy elements bonds are weaker, compared to that of the 30 Scanned by CamScanner ‘Seenned with CamScamerlight elements. Because of this less effective overlapping, the heavy elements utilise pure p-orbitals in bonding and letting the lone-pair ‘sink' into a pure s-orbital. Hence, the stable chlorides of thallium and lead are TICI and PbCl, Figure 1.12 Effect of orbital size on overlapping 1.5.2 Fifth and Sixth groups Hydrides & Halides As the energy of hybridization is of the order of magnitude of bond energies and can thus be important in determining the structure of molecules. It is responsible for the tendency of some lone pairs to occupy spherical, nonstereochemically active s-orbitals_ rather — than stereochemically active hybrid orbitals, For example, the hydrides of the Group VA (15) and VIA (16) elements are found to have bond angles considerably reduced as one progresses fro m the first element in each group to those that follow (table 1.2 ). An energy factor Table 1,2: Bond angles in the hydrides of Groups VA (15) and VIA (16) NH, = 107.2" | PH;=938" SbH, = 91.3" OH, =104.5° | SH=92 | SeH)=91° | Tekh =89.5° that favours reduction in bond angle in these compounds is the hybridization discussed above. It costs about 600 KJ mol"! to hybridize Scanned by CamScanner ‘Seenned with CamScamerthe central phosphorus atom. From the standpoint of this energy factor alone the most stable arrangement would be utilizing pure p-orbital in bonding and letting the lone pair "sink" into a pure s-orbital. Opposing this tendency is the repulsion of electrons, both bonding and nonbonding (VSEPR). This favours an approximately tetrahedral arrangement. In the case of the elements N and O the steric effects are most pronounced because of the small size of atoms of these elements. In the larger atoms, such as those of P, As, Sb, S, Se and Te, these effects are somewhat relaxed, allowing the reduced hybridization energy of more p character in the bonding orbitals to come into play. The molecule is thus forced to choose between higher promotion energies and better overlap for an-s- rich hybrid, or lower promotion energies and poorer overlap for an s-poor hybrid, (s-character: sp? (25% )25%; s-poor means<25%) 1.53 Isovalent Hybridisation In many tetravalent molecules the bond angle is seen slightly distorted, than the ideal 109°28' for example in CH;C1, H-C-H bond is 110°20. This deviation may be explained in terms of ‘Tsovalent Hybridisation". Consider an imaginary molecule A-M-B. If in this molecule, B is replaced by a strong electronegative element C, then M is rehybridised in such a way that the orbital used for bonding C has more p character, than the orbital used for bonding B. Hence in A-M-C molecule, M-A bond will have more s-character, compared to that in A-M-B molecule. For example, as compared to CHsNHb, the carbon atom in CHOH uses a hybrid orbital having more s-character to link methyl hydrogen. As a result the C-O bond has more p character as compared to the C-N bond. This is an example of Bent's rule. Scanned by CamScanner ‘Seenned with CamScamerTeq(pm) Tax(pm) PFs 153.4 157.7 PCI; 202 214 SbCl; 231 243 SF, 154 164 CIF; 159.8 169.8 BrF3 172.1 181.0 An sp3d hybrid orbital set may be considered to be a combination d,” hybrids and Sp;Py hybrids. The former make two linear hybrid als bonding axially and the latter form the trigonal, equatorial bonds. sp’ hybrid orbitals are capable of forming stronger bonds, and they shorter than the weaker axial bonds. When the electronegativities of substituents on the phosphorus atom differ, as in the mixed rofluorieds, PC1,Fs.,, and the alkylphosphorus fluorides, R,PFs.x it is rimentally observed that the more electronegative substituent and tha lace elactranecative cnhstitnent is ‘Seenned with CamScamerNotes: 1. Write your answers in the space given below. Compare your answers with those given at the end of this unit. (a). Bent’s rule is exemplified in- (i) Monovalency of.. .and divalency of. (ii) Decreasing bond angles of ... (iii) F-C-F bond angle is ... but H-C-H_ bond angle is ... 109°28' in CH,F, molecule. (b) Apicophiliaity is .. than 109°28' than It is well illustrated by..... ‘Seenned with CamScameraspects of the subject, to contrast, inorganic chemistry has a wide variety of structural types to consider, and even for a given element there are many factors to consider. Inorganic chemistry has been, and to a large extent still is more concemed with the static structure of reactants or products than with the way in which they interconvert. This has also been largely a result of the paucity of unambiguous data on reaction mechanisms. However, this situation is changing. Interest is increasingly centring on how inorganic molecules change and react. Most of this work has been done on coordinate chemistry, and much of it will be considered later on, but a few simple reactions of covalent molecules will be discussed here. 1.6.1 Atomic Inversion The simplest reaction is seen in a molecule of ammonia, This can undergo the simple inversion of the hydrogen atoms about the nitrogen atom. This is analogous to the inversion of an umbrella in a high wind. One might argue that above equation does not represent a reaction because the product is identical to the reactant and no bonds were formed or broken in the process. Leaving aside, the process illustrated above is of chemical interest and worthy of chemical study. Consider the trisubstituted amines and phophines shown in the figure below. . ce Co CI ee CT oy & (Chiral amines and phophines) 35 Scanned by CamScanner ‘Seenned with CamScamerBecause these molecules are non superimposable upon their mirror images (ic. they are chiral) they are potentially optically active, and separation of the enantiomers is at least theoretically possible. Racemization of the optically active material can take place as shown in mechanism of NH. It is of interest to note that the energy barrier to inversion is strongly dependent on the nature of the central atom and that of subsequent. For example, the barrier to inversion of methyl propyl phenylphosphine is about 120 MJ Mol", This is sufficient to allow the separation of optical isomers, and their racemization may be followed by classical techniques. In contrast, the barrier to inversion in most amines is low (-40 KI mol) with such low barriers to inversion, optical isomers cannot be separated because racemization takes place faster than the resolution can be affected, Since traditional chemical separations cannot effect the resolution of the racemic mixture, the chemist must tum to spectroscopy to study the rate of interconversion of the enantiomers. 1.62 Berry Pseudo Rotation In PF; the fluorine atoms are indistinguishable by means of NMR of F. This means that they are exchanging with each other faster than the NMR instrument can distinguish them. The mechanism for this exchange is related to the inversion reaction we have seen for amines and phosphines. The mechanism for this exchange is believed to take place through conversion of the ground state trigonal bipyramidal into a square pyramidal transition state and back to a new trigonal bipyramidal structure, This process results in complete scrambling of the fluorine atoms at the equatorial and axial positions in phosphorus pentafluoride. If it occurs faster than the time scale of NMR experiment, all the fluorine atoms appear to be identical. Because it was first suggested by Berry, and because, if all of the substituents are the same as in PFs, the two triogonal Scanned by CamScanner ‘Seenned with CamScamerbipyramidal arrangements are related to each other by simple rotation, the entire process is called a Berry pseudorotation. Note that the process can take place very readily because of the similarity in energy between trigonal bypyramidal and square pyramidal structures. (Berry pseudorotation in Pentayalent Phosphorus Compound) In fact the series of 5-coordinated structures collected by Muetterties and Guggenberger, which are intermediate between trigonal bipyramidal and square pyramidal geometrically effectively provides a reaction coordinate between the extreme structures in the Berry pseudorotation. 1.6.3 Nucleophillic Substitution The simplest reaction path for neucleophilic displacement may be illustrated by solvolysis of a chlorodialkylphophine oxide. ° x e Ho S—aslotot_& |+cno— 7 at ey ae We would expect the reaction to proceed with inversion of configuration of the phosphorus atom. This is generally observed especially when the entering and leaving groups are highly electronegative and is thus favorably disposed at the axial positions, and when the leaving group is one that is easily displaced. In contrast in some cases when the leaving group is a poor one, it appears as though front 37 Scanned by CamScanner ‘Seenned with CamScamerside attack takes place because there is retention of configuration. In cither case, the common inversion or the less common retention, there is a contrast with the loss of stereochemistry associated with a carbonium ion mechanism. 1.6.4 Free Radical Mechanism In the atmosphere there are many free radical reactions initiated by sunlight. One of the most important and controversial sets of atmospheric reactions at present is that revolving around stratospheric ozone. The important of ozone and the effect of ultraviolet radiation on life will be discussed later, but we may note briefly that only a small portion of the sun's spectrum reaches the surface of the earth and that parts of UV portion that are largely screened can cause various ill effects to living systems. The earth is screened from extremely high energy UV radiation cleaves the oxygen molecule to form two free radicals of oxygen atoms. 0, + hy (below 242 mm) + O'+ O The oxygen atoms can then attack oxygen molecules to form ozone. 0+0,+m~m+0; The neutral body m carries off some of the kinetic energy of the oxygen atoms. This reduces the energy of the system and allows the bond to form to make ozone. The net reaction is therefore: 30, + hv + 20; The process protects the earth from the very energetic, short wavelength UV radiation and at the same time produces ozone, which absorbs somewhat longer wavelength radiation by similar process: 0, + hv (220-230 mm) + 0, + O Thus the process is repeated. 38 Scanned by CamScanner ‘Seenned with CamScamer