at acseyoaary Tewal, PENERAL THEORY omewhav greater distance (roca the central bonds relative to the equatariai ones, In the of the lene pair will act more strongly “on the sverding te this treatment bond directions are determined by a xt of rid-orbitals on the central atom: which ere used to form bonds tc the atoms and to hold unshared pairs. Thus AB molecules are linear ‘owing to the use of linear sp-hybrid orbitals. AB, and ABE molecules should be equilateral triangular and angular, respectively, owitig to use of trigonal sp? hybrids. AB,” AB,E, and AB,E, molecules should be tetrahedral, pyramidal, and angular. respectively, because sp? hybrid orbitals are used. ‘These cases ere, of course, very fumiliar and involve no more than an octet of electrons. the ABs, ABE. AB,E,, and ABE, molecules, the hybrids must now chide: d orbitals in their formation, The hybrid orbitals used must obviously fa mor. ie molecules and so a decision has to be made empirically, As already all AB, molecules whose structures are known, with at most three exceptions, are rp. Itis therefore assumed that the sp°1d,2 hybrids and tp ge- etry will generally be appropriate. Once this assumption is made a con= correlation of structures follows, exuctly as in the YSEPR model the basic zhp arrangement was adopted £91 a different reason. Again, however, the preferentiat allocation of tone pairs to equatorial orbitals is essentially arbitrary. It does then follow that ABE molecules ‘or AB, molecules octahedral sp'd? hybrids are used. ABsE molecules must, naturally. be spy. For AB,E, molecules there is nothing in the directed. valesee theory itself to show whether the Jone pitirs should be cis or wans.. The assumption that they mustbe srons tends to consistent results, tt may be seen shat.if we assume formation of hybrid orbitals to determine the basic geometry, it is possible then to berrow a portion of the ¥SEPR dogma, samely, rule (2), that a tone par takes-up more room than a bevdiag | pate inorder te rationalize the finer features of certain structires. ef, the bond angles ia ABLE, ABE, ABE, and AB,E, iolecules, In short, ane siaty sejget the viow tht ek-ctron-pair repulsidteds the peimary Ta tereouhenistry anit aadwene insted that directed hybe:? orimale hase a> baaie inl bit 28 allow thar sbcteriiaic sepulsions enter &to. the prablemy Scanned with CamScannerCOMPOUNDS OP NON-TUNSHTION ELEMENTS, (33 4-4. The Three-center fond Model os proach isn linuted MO treatment. predicated on two main ideas onter d orbitals of the central atoms is 9 slight that they piay de neglected altogether, and (2) that the persistent recurrence of hond clove to 807 and 180° in AB, molecules suggests that orbitals perpen- chewiat to one another, namely, p orbitals, are being used two wpes of chemical bond are considered, First there is the orifinary twe-center. two €lectron (2c-2¢) bond. formed by the overlap of «7 orhital of ntral atom with a ¢ orbital of an outer atom. Secondly, there is the linear three-center. four-electron (3¢-4e) bond (page 109), formed from a orbital Gf the céntral atom and the @ orbitals of two outer atomis For molecules with an octet, or less, of electrons in the vaience shell of the central atom, the hybridization theory, employing sp, sp? and sp? orbitals remains valid. Jt i for molecules in which {ite or more electron pairs on the contra! atom nnust be accounted for that this model was proposed. Since it a, as we shall note below, undoubtedly too great a simplification, it will be apphed only to # few illustrative cases. It is worth mentioning, however since v has a certain heuristic value. In molecules of the AB,E type, the central atom is considered to use p, and p, orbitals to bind the B atoms (ef. Fig. 4-2a) while the B’ atoms are found using the p, orbital 10 form a 3-—de bond. Again some supplemen- tary assumption, such us tule (2) of the VSEPR model must then be invoked ro explain the non-linearity of the B’AB’ Soa eli d Capes FESS MiG a tony Bae < ions and there for these cases. It is also unable to cope with in any simple way. Thus it provides no ~ obvious explanation either for the different lengths of the bonds in mole- ‘or for the deviations of the angles in cules of the AB3F, and ABsE types, such molecules from 90°, but some VSEPR considerations can be grafted a ‘on to it to deal with these matters, as already noted. «ie e ‘The use of correlation diagrams tends to be limited by the number of structure parameters that have fo be varied in order to cover a sufficient range of structural possibilities, The reliability of the conclusions that-can be drawn depends on éhe thoroughneéé of this explorttion of the possibilities ‘and ot the inherent reliability of Hie method used to compute the ener 4y 6, Cornwell and R, 8. Yainasaky; 4, Cher Scanned with CamScannerCOMPOUNDS OF NON-TRANSITION ELEMENTS 143 - § The limitations can be no Jess than those of the computational method employed. weal ee The three-center bond approach is clearly only an aborted MO treatment. In its total neglect of d orbitals it-isin.error, but in many cases less so-than the hybridization-approach with its tora! inclusion of d orbitals. In its neglect of the central-atom valence-shell s orbital. it is rather seriously unrealistic. is As -Hig.-4-7-shows,-gnd fs specific calculations such as those on PFs and BrF, show,” the s orbital is heavily involved in the A~B @ bonds snd cannot safely be neglected. . Cicarly, thearmost flexible approach to an understanding, not only of struc- y tures, but also” Of the character of the bonds in them is an MO approuch. As.already. noted, it may-be impossible to get completely reliable «b-initio predictions of structure by MO calculations unless they are of a very rigorous nature, but less rigorous calculations performed with an assumed or kriown structure are very useful. In general, the MO approach, even in a quantita- tively rough form, as-exemplificd-by-Fig-4~7, provides a general, flexible conceptual framework within which the models in which “ruthless approxi- mations” are made can be examined and evaluated. ; : It would be unfair to conclude this discussion without mentioning that there are a few other cases besides the AB,E molecules that none of the models can accommodate. These wre certaith non-linear AB; molecules con- ed valence-shell electrons. In general, when both the’ atom nd CaCl,, these molecules are taining no unsh; and the’B atoms are small, as iil, ¢.g.. BoC linear, as expected. However, with a large central atom pnd small ligand: e.g. with BaF, the molecules are bent? 1t may bé'thiat in these cases an assumption common to all the models, namely, that the inner shells of the central atom may be entirely neglected, is invalid. ‘ 49. dx-pz Bonds While the role of central atom d orbitals in the formation of ¢ bonds to been a controversial subject, there is another role for d (ual participation has been more, generally accepted ff that participation is outer atoms has orbitals where their a for some time, although here, too, the exact extent of subject to some differences of opinion, While the heavier non-t ition elements show little tendency to engage their p orbitals in x-bond formation, they do form at least partial R bonds to hghter elements, expecially t0 oxygen and nitrogen. by using their outer ; ‘Tortutas. The experimental indications of this are chietly the high bond- ie vtaotehng force constants and the shortness of bonds compared to the force constants and bond lengths to be expected for single bonds. More recently, photoelectron spectrascopy has provided clidence for such bonding even : in HSL? on “i; ew ON Ricusperer et ah, J 6 hem Phys, 1963, 39, 2023, 2299; 164, 40, 3491; J Amer, 7. Sac, Heed, hb, at : ” Pee ‘aed BAY. Tbswcrth, Cher: Conan 197i, $7. Scanned with CamScannerGENERAL THEORY | Molecules. “We first consider ea tepals on the basis of compatibility. a Eee Tire pands. For 8 tetrahedral AB, molecule such as SIF, ex Poe ne For che 0 atoms has two filled pr orbitals perpendicular to the ACB bene af me id perpendicular to each other, The centcal atom, A Tamear aa a nd porbitals for c bonding. detailed examination BSuSan bite d orbitals of A for overlapping with the pr orbitals Woon OFAN yar all of them are able to do s0, but two, namely dy an ee vem particularly well suited for this.* Each of these two wuld be exposed fe tve about /3 times as much overlap with the pr orbitals of Ga B atoms as onc of the other three d orbitals. Fig. 4-8 shows in a rough sehematic way the principal dz-pz overlap possibilities. ie Bond length data in the scries of ions SiO-, PO}, SO3-, ClOz indicate that such pr-dx bonding actually does occur. As shown in Table 47, the XO bonds are all short relative to values reasonably expected for TABLE 4-7 and da-pn Overtaps in XOZ~ tons pr-ds Overlap? Oho X-O dist,e Est. X—O singlet ceraran intone # From icf. 24 2 Eom A ty Jatte, J. Phys. Chem. 1954, 58, 185. te} a pa orvitals of the B apg 5 4 ftr ective view of the OveOSF S27), ortals of the A tadapted Pag 48 Quastpetst iy para AB mokecule a (4) TES ay perimssion ‘se, 1968, S86 oe Sika eeabekeaminals oe CP Sanned with CarSeannerCORE MPOUNDS OF NON-TRANSITION ELEMENTS 145 single bonds, and, . and, moreover, th . the trend i m si etd mar op in shortening is closely parallel to 1 in SIF, even after due 1 covstent resonance in acae ese ee fade ed ele they appear to be around O13 A shorter thee the iene Sy Fonds, bonds, and the implication, therefore, i that bere ee er single Oth My refore, is that x bonding is ther Molecules, In less symmetrical molecules the di Eee x bonding is more dificult bocause the d orbitals ofthe ceueal nes wx, interact with diffe ifiorent deesss Homeien interac with diferent types of outer atoms to diferent depres. Hower, Saale (be 123) that bond order and bond length are inversely r , sssible to deduce approximate, relative de i in various compounds containing S10, PO, SO and Co arouse, oy wet at ete acta eres Noes ee Seo GOT Ea are most extensive, The vari P 4 are mos extensive. The various types of PO, bond vay in length rom a and it has been suggested™ that this last value, about the shortest observed distance for any 80, PO, SN or PN bond, correspond: to about a double bond, ie. to a x bond order of about 1. However, itis possible that this is an underestioate, ince in SF4N, where the SN bond Gr scihernaicie Gatiew Seon EROTcle, a the molecules 203, PF,0, CIO,F, ClOz, ClOs and C105, ab initio MO calculations indicate sign a orbital tartivotc Oz, ab ino MO calaations inet spifeat doa partepation In certain instances the existence of da-pa bonding i in-pa bonding is indicat overall molecular geometry. Thus, the SiyN and Ge,N Scion a piset® in (SiH,)sN and (GeH,),N, and in (MeySi)NBeN SiMe) the Si: NBeNSis group has anallenesike configuration (SizNBe groups in two perpendicular planes?7). In cach case the Si--N or Ge-—N bonds are 0.05-0.15 A shorter than expected for single bonds. These structural features can be sccountd fr by atuming hatin he planar configuration about the N atom there is enough N(2p,)-»Si(3d) or Ge(3d) z-bonding to stabilize this eon- figucation relative to the pyramidal one found in most other RN molecules. Tt is worth noting that the mere presence of orbitals suitable for such bonding does not necessarily ead to such pronounced structural effets. Thus, P(SIH)» and AsSi#)y are both pyramidal” (Si—X—Si anges of 96.5"-and 93.8 respectively), as is P(GeHs)a“® and S(SiB,), is bent? (Si—S—Si = 98°). Apparently the 3p orbitals of the P, As and S atoms do nor-overlap with the 3d orbitals of Si and Ge as well as does the 2p orbital of a central N atom. In the, case of (SiH),0 an intermediate situation ‘ccui’s: the molecule is bat but the angle (144°), is quite large.** More+ 49 1, U1, Hillier and V. R. Saunders, Chem, Comm, 1970, 1183. 18 &: Glidewell, D. W. 11. Rankin, and A. G, Rabiette, J. Chem. Soe. Ay 1970, 2935. £7 4H, Clark and A. Haaland, Chem. Commm., 1969, 912. 4 ah teagley, A. G. Robiette, and G. M. Sheldrick, J, Chem. Soe, A, 1968, 3002, 3006. 2 8 Cradock ef al, Chem. Comm, 1965, S15, 26 A. Alinenningen ef al, Acts Chern, Scat, 1963, 17, 2264, 4A, Almoningen, deta Chen Scand. 1963, 17, 2435 Scanned with CamScanner146 GENERAL THEORY ‘ 4 ta) tb) Fig. 4-9. Overlaps of a central px orbital with dn orbitals on outer atoms for (3) Bent ‘and (b) linear configurations. 5 over the Si-O bonds are about 0.14 A’shorter than the value expected for single bonds, and the bond order may be estimated from this shortening to lie in the range 1.3-1.6. : ‘The (SiH,),O case well illustrates the fact that some pr-vdz bonding can occur without there being a completely linear or flat configuration of the molecule, as indicated in Fig. 4-9a. It is probable: that the a bonding js strongest in the linear and flat configurations (Fig. 4.96), but unless the magnitude of the bonding is fairly large # may not be able to overcome other factors favoring the bent configuration, or may, as in (SiH;),0, only be able to reach a compromise with these other factors at some intermediate angle. Further Reading Coulson, C. An J. Chem, Soc., 1964, 1442 (specifically concerned with noble-gas com: vulands, but the bonding theory pertains equally {o many other systems, including att halogen compounds with more than four pairs of valence-shell electrons). Maim, J. G., H. Selig, J. Joriner, andS. Rice, Chem. Rev., 1965, 65, 199 (theoty of bonding as discussed specifically for Xe compounds has wide applicability). . Mitchell, K. A., Chem, Ret., 1989, 69, 137 (use of outer ¢ orbitals in bonding). Pettit, L. D., Quart. Rev., 1971, 25, | (multiple bonding in inorganic compounds) eer H, E. E. Havinga, and K, H, Boswijk, Adv. Inorg. Chem. Radiochem, Scanned with CamScanner