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Chemistry 1976

THE BORANES AND THEIR RELATIVES
Nobel Lecture, December 11, 1976 by WILLIAM N. LIPSCOMB Harvard University, Cambridge, Massachusetts, USA

This year, 1976, the Nobel Prize in Chemistry has been awarded for research in pure inorganic chemistry, in particular the boranes. May I say that I am most pleased and profoundly grateful. My own orientation to this field has been, as it has in all of my studies, the relationships of the chemical behavior of molecules to their three-dimensional geometrical and electronic structures. The early work on the molecular structures of boranes by X-ray diffraction led to a reasonable basis for a theory of chemical bonding different from that which is typical in carbon chemistry, and yielded an understanding of the pleasing polyhedral-like nature of these compounds. Assimilated by the preparative chemists, the principles helped to establish a large body of a hitherto unknown chemistry, which made a reality of the expectation that boron, next to carbon in the periodic table, should indeed have a complex chemistry. In these nearly thirty years both the theoretical and experimental methods have been applied by us and others to areas of inorganic, physical, organic and biochemistry. For examples, these areas include low temperature X-ray diffraction techniques, and the theoretical studies of multicentered chemical bonds including both delocalized and localized molecular orbitals. An early example is extended Hückel theory, originally developed for studies of the boranes, and even now one of the most widely applicable approximate methods for theoretical studies of bonding in complex molecules. More soundly based theories are presently in use by my research students for studying how enzymes catalyze reactions, details of which are based on the three-dimensional structures by X-ray diffraction methods. Besides illuminating particular problems, these developments may contribute toward the redefinition of areas of chemisttry, and thereby broaden the chemist’s view. Our research in the boranes and their related molecular species crosses areas of inorganic, experimental physical, theoretical and organic chemistry, and includes applications in biochemistry. More simply stated, the area is the study of the relationships of molecular structure to function.

BORANES, AND EARLY STRUCTURE STUDIES By now, large numbers of chemical compounds related to polyborane chemistry exist: boron hydrides, carboranes, metalloboranes, metallocarboranes, mixed compounds with organic moieties, and others. These discoveries of preparative chemists are relatively recent. Long ago, Alfred Stock established borane chemistry. He developed the experimental techniques which were required

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for the preparation of the volatile and potentially explosive compounds, B2H6, B4H10, B5H9, B5H11 and B6H10, and the relatively stable white crystalline B10H14. This work, beautifully summarized in his Baker Lectures,1 was celebrated in the Third International Meeting on Boron Chemistry this past July in Munich, 100 years after his birth. Sidgwick2 wrote, “All statements about the hydrides of boron earlier than 1912, when Stock began to work on them, are untrue.” Aside from the classification as either an N+4 or an N+6 series, no simple basis for these unusual formulas was foreseen before their structures were established. A B6 octahedron (Fig. 1) was known in certain crystalline borides, and the B12 icosahedron (Fig. 2) was found in boron carbide, but no one realized that a systematic description of the boron arrangements in these hydrides might be based on fragments of these polyhedra. Most electron diffraction work before 1940 supported more open structures, which Pauling3 described in terms of resonating one-electron bonds. In 1940-1941 Stitt4 produced infrared and thermodynamic evidence for the bridge structure of B2H6 (Fig. 3). More general realization of the correctness of this structure followed the theoretical studies,5-8 and especially the infrared work of Price.9 The three-center bridge BHB bond was clearly formulated by Longuet-Higgins.8

Because of the special difficulties of working with the volatile boranes.11 . and by electron diffraction at the California Institute of Technology. At that time. 13. I chose among other topics. 7) and tetrahedral B 4Cl 4 then set the stage for the beginning of the theory of bonding. a fragment of the B6. It was actually in 1946 that I decided to enter this area of inorganic chemistry. Our methods 19 paralleled those in Fankuchen’s laboratory20 at the then Polytechnic Institute of Brooklyn. The B 6H 10 structure.18 (Fig. which were to include many other boranes and related molecules. a series of X-ray diffraction studies of single crystals grown at low temperatures from low melting liquids for which putative residual entropy problems .14 (Fig. was to be one of our later X-ray diffraction studies. 17. 8) completing the compounds found by Stock. Both of these and then B 4H 10 structures were established by X-ray diffraction in our laboratory. but were quite independent. 12 (Fig. Lucht and Harker10 showed that the boron arrangement was a fragment of a B12 icosahedron in which there are four bridge BHB bonds in the open face. Our X-ray 16 diffraction results on B5H 1115 (Fig. Kasper. 6). no reliable methods were generally available for accumulation of large amounts of X-ray diffraction data at low temperatures. 4). a B4 unit from these polyhedra.226 Chemistry 1976 The first of the higher hydrides to be structurally characterized was B 10H 11 (Fig. 5). octahedron. Next was B5H 9.

Crawford and I examined 22 the open boron hydrides B 2H 6. 2) from the viewpoint of molecular orbitals. H. 7. N 2H 4. for example. B4H 10. when we found a presumed B 8 hydride to be B 9H 15 . the unknown -2 polyhedral molecule B 4H 4. B5H 11 and B 10H 14 from the viewpoint of three-center bonds. 8. The subsequent low temperature studies of single crystals of these volatile and unstable boranes were not without hazards.W. when I had taken Russell Grimes to a hospital in Cambridge after one of these explosions to hear the doctor tell me. formed an early molecular orbital description almost like ours. do have -2 charge. for 6 < n < 12. all of the experimentally known ions. for all values of n from 5 to 24. Eberhardt’s sabbatical. which was calculated in those days from rough visual estimates of intensities of diffraction maxima on films.” I still have in my office the air gun which I. 1) and B 12H 12-2 (Fig. Fig. “Louis Fieser sends me much more interesting cases than you do. and we studied B 5H 9. on one occasion. I mean by this non-sequitur that the three-center two-electron bonds make possible a simple description of these molecules and ions as filled orbital species. the then hypothetical ions B 6H 6 (Fig. Longuet-Higgins 23 also. existed: N 2O 2. B5H 9. One of the simple consequences of these studies was that electron deficient molecules. he. B5 H 11 . Lipscomb 227 Fig. no serious injuries were incurred as a result of several explosions resulting from cracks in these vacuum systems. CH 3OH. all of which have a formal charge of -2. defined as having more valence orbitals than electrons. THREE-CENTER BONDS AMONG BORON ATOMS At the fortunate time in 1953 of W. are not really electron deficient. COCl 2 a n d H2O 2. . Fortunately. I was relieved. used on a number of occasions to destroy a cracked vacuum system from a safe distance. even though hypothetical B 4H 4 is neutral.21 Our only chemical analysis of this compound was the count of the numbers of boron and hydrogen atoms in the electron density map. B6 H 10 . or my young son. We also had chemical surprises. In fact. independently. Vacuum line techniques were learned as we needed them. N. Filled molecular orbitals were later extended to closed polyhedral compounds BnH n. CH 3N H2.

but they are also useful for closed polyhedral molecules and ions. the number of two-center BB bonds as y and the number of extra terminal hydrogens on each BH unit as x. Structures for the boron and carbon arrangements in some of the polyhedral molecules C 2 B n . if each BH unit is recognized as contributing a pair of electrons. orbital and electron balance were formulated in our paper of 1954. allowing prediction of many new chemical species. s and x. These rules. The isoelectronic series C 2B n-2 H n is known for 5 < n < 12. 1) and B 1 2 H 1 2 -2 (Fig. Define the number of BHB bridges as s. The isoelectronic anions are known for G<n< 12. The second comes from the fact that each of the p boron atoms supplies four orbitals and only three electrons.228 Chemistry 1976 in addition to B 6 H 6 -2 (Fig. 9. 2). Fig. Equations for the atom. One simple form of these rules is exemplified for a neutral hydride formula B PH p+q in which each boron atom has at least one terminal hydrogen atom.2 H n . those polyhedra for 5 < n < 10 are shown in Fig. the number of three-center BBB bonds as t. these p pairs are used in BBB or BB bonds. . are especially helpful in describing those polyboron compounds which are open. Then The first equation is the hydrogen balance. 9. and the accompanying valence structures. Finally. which are known for 5<n< 12. or in half of the pairs required for the extra hydrogens. and the extra orbital is utilized in one of the two types of three-center bond.

on the central atom. 14. Bonds in B4 H 10 . 10). a π orbital which overlaps in a bonding manner with an orbital from each of the adjacent boron atoms. 11. 12. 11-14) are well described . Fig. Bonds in B6 H 10 . There are two kinds of three-center bonds among three boron atoms (Fig. B5 H 1 1 and B 6H 10 structures (Figs.W. Bonds in B2 H 6 . according to three-center bond theory. 13. B4 H 1 0 . N. while the open three-center bond involves. Bonds in B5 H 11 . The less compact B 2 H 6 . Lipscomb 229 Fig. The central three-center bond involves positive overlap among hybrid orbitals from each of three boron atoms. Fig. Fig.

17). which has four-fold symmetry. 16) requires a resonance hybrid of 24 valence structures. 15) requires a resonance hybrid of four valence structures.230 Chemistry 1976 with the use of these three-center bonds. and the more compact polyhedral fragments. omitting open three-center BBB bonds for the moment. 24 I realized that the valence rules implied the existence of a large body of boron chemistry. 24. Three-center bond theory was further developed in the following 22 years. to BCB bonds is exemplified in a later part of this manuscript. In B5H 9 there are three pairs of electrons in the boron framework. and then ventured predictions. However. . B5H 9 (Fig. One of four resonance structures for B 5 H 9 .26 More recently. The other three are obtained by reorientation of the framework bonds by 90° about the molecular four-fold axis. geometrical constraints were introduced in order to avoid overcrowding of hydrogen atoms and to preserve known bonding angles about boron atoms among the boranes. so far. to the exclusion of open three-center BBB bonds. Two simple examples will suffice. Epstein27 and I reformulated the topology using central three-center BBB bonds. 28 (Fig. related by the four-fold symmetry. some of which were actually verified experimentally. Also. MOLECULAR ORBITAL STUDIES OF BORANES Molecular orbitals are more appropriate for describing the valence structures of the polyhedral molecules and ions. These orbitals are similar to the bonding orbitals. The bonding is beautifully described without resonance. 15. and B 10H 14 (Fig. Fig. for example. Dickerson 25 and I formalized my intuitive approach into a theory of connectivity of various bonding patterns within the three-center description. The recent work on localized molecular orbitals which has led to the restriction of open three-center bonds. between planar four-fold cyclobutadiene (C 4H 4) and a CH+ placed along the four-fold axis to give the carbonium ion C 5H 5+ . by a simple σ and π set of molecular orbitals 22.

π molecular orbitals which can bond to a similar set of σ. I did not then go 2 quite so far as to suggest bonding of this B 1 1H 1 1 . This set of five orbitals gives σ. for example. Later. π situation occurs 28 if a BH unit is removed from icosahedral B 1 2H 1 2-2 l e a v i n g B1 1H 1 1. These five atomic orbitals form a o(bonding)..fragment to a transition metal. and thereby created the large family of metalloboranes and metallocarboranes 29 (Fig. when large scale computing facilities became available to us. Hawthorne did so. I suggested. . 19. N. a metallocarborane derivative. 18). Although recognizing the similarity of this set of orbitals to those in C5H 5. conceptually.2 having five atomic orbitals containing four electrons (Fig. The structure of (B9 C 2 H 11 )Fe(C 5 H 5 ). which was known to form ferrocene Fe(C5H 5) 2. Roald Hoffmann and Lawrence Lohr independently programmed the Fig.2 . 18. like those in the π electron system of C 5 H 5 . Fig. or C2 B 1 0 H 1 2 . containing four electrons remain when a neutral BH unit is removed from the apex of B 1 2 H 1 2 . using these ideas as a starting point. π orbitals from another atom or group of atoms supplying two more electrons. In the early 1960’s.W. Lipscomb 231 A similar σ. Five atomic orbitals. adding H3+ to predict B11H 14-. 19). π (bonding) and δ (antibonding) set of five molecular orbitals.

Its first application was to boron chemistry. One approach was empirical. while electrophilic attack was preferred at a boron furthest removed from carbon. Experimental studies of boranes and carboranes in which one or more hydrogens had been replaced by a halogen or by an amine group confirmed these predictions. rather than X-ray diffraction. t h e application of this method to the complex boranes still lies in the future. One of the rather simple rules which emerged was that nucleophilic attack occurs in a polyhedral carborane at a boron atom closest to carbon. diamagnetic and large temperature-independent paramagnetic effects. it is possible to make linear combinations of molecular orbitals of different symmetries in such a way that the total electron density of the mole- . were tested by their inventors31 with the use of this theory.232 Chemistry 1976 extended Hückel method in my research group. for new polyborane species and for substituted boranes and carboranes. The extended Hückel method became for a time the most widely used program for the study of molecular theory and reactions in complex organic and inorganic molecules. and related orbital concepts.30 where. and which had essentially the accuracy of self-consistent field methods. A striking result was the prediction of the paramagnetic nature of diatomic BH. molecular orbitals are classified according to their symmetry types. One example is the first accurate calculation of the barrier to internal rotation in ethane. yielded molecular constants good to a few to several percent 34 for many diatomic molecules. particularly in the carboranes (compounds of boron. which was applicable to large polyboranes and other molecules. the coupled Hartree-Fock method for a molecule in a magnetic or electric field. LOCALIZED MOLECULAR ORBITALS Ordinarily. For example. 32 while the other was purely theoretical. which were explored in other areas of chemistry. the charge distributions predicted sites of electrophilic and nucleophilic substitution. We achieved by stages 37. This latter approach required the development of a theory for fairly reliable calculation of chemical shifts of 11 B from first principles of quantum mechanics.38 a molecular orbital theory still being extended. Hence we began only a few years ago to explore the connections between these symmetry orbitals and the three-center bonds of the previous section. Molecular orbital methods which do not go beyond symmetry orbitals tend to make each molecule a separate case. even after 13 years of effort. carbon and hydrogen). as well as in the boranes and carboranes. However. could be used. 35 H o w e v e r .36 At this point. I thought then that progress in structure determination. the Woodward-Hoffmann rules. my research students and I set out to explore the gap between extended Hückel theory and self-consistent field 39 theory. While we understand some of the contributions to chemical shift. the use of this method for structure determination of complex polyboranes is still somewhat limited. These programs yielded accurate self-consistent field molecular orbitals. 33 This theory. would be greatly accelerated if the 11B nuclear magnetic resonance spectra.

they test the level at which two-center and three-center bonds require some further delocalization. (b) and (b’). and (b’) the localized slightly unsymmetrical three-center bonds. Three valence structures for B 5 H 1 1 include (a) the disfavored open three-center bond. Including both types there are 111 resonance structures for B 10H 14. Also. (b) the symmetrical central three-center bonds. maximize the repulsions of those electron pairs within each molecular orbital. Lipscomb 233 cule remains invariant. In B 5H 11 (Fig. For clarity. the symmetry orbitals are converted into linear combinations which are a good approximation to the localized electron-pair bond. one terminal B-H bond has been omitted at each boron site in (a). without adjustable parameters. Open three-center and central three-center BBB bonds are almost equivalent descriptions. N. often eliminating or reducing the need for resonance hybrids. and minimize the orbital self-extension of each electron pair. . of which 24 are based only on central three-center bonds. 20.W. The most popular methods are those of Edmiston and Ruedenberg 40 who maximize and of Boys41 who minimizes These procedures. in slightly different manner. Thus. These objective procedures. 20) two slightly unsymmetrical central three-center BBB bonds are Fig. have been compared in some detail. These studies have also provided preferred descriptions of valence structures. 42 They provide support of three-center bond descriptions within a theoretical chemical framework. respectively.

In a series of studies of localized molecular orbitals in all of the boron hydrides. In the simplest molecular orbital description of an open threecenter bond. 20b’). when the Edmiston-Ruedenberg procedure is used. we have never found an open three-center BBB bond. Single bond donation in B 4 H 10 is about 0. 2 . about 0. This donation then causes these Fig. open threecenter BCB bonds do exist. Localized molecular orbitals are shown in the framework of 1.234 Chemistry 1976 found 43 by both localization procedures (Fig.2 e is donated 43 from the single BB bond to each of atoms B 1 and B 4. Another new general result is that almost every single bond within a triangulated borane or carborane framework shows some donation to the nearest adjacent atoms (Fig. when carbon is the middle atom. 21. . For example. to give open three-center bonds rather than nearly equivalent central three-center bonds. However.C2 B 4 H 6 ( F i g . In B4H 10. carboranes. 23. 2 1 ) . the open three-center BCB bond 44 o c c u r s t w i c e i n 1 . It is probable that the extra nuclear charge of carbon stabilizes this distribution. An external hydrogen has been omitted at each B or C atom. which themselves are relatively electron deficient because of the open three-center bonds of the hydrogen bridges (Fig. whereas the open threecenter description is not favored.2-C 2 B 4 H 6 . 22). The open three-center bonds go through carbon. e/2 among these three atoms. and ions of known geometry. A comparison of these results with those of the Boys procedure is given below. the electron pair is distributed as e/2.19e from the B2 B 3 bond to each of the outer doubly bridged BH. Fig. 23). groups of the molecule. e. This tendency for multi-centered bonding usually involves 10 per cent or less of the electron pair.

in Fig. N. 26. Some common patterns of single bond donation cause hydrogen atom displacement and electron withdrawal from the atom to which donation occurs. hydrogen bridges to become unsymmetrical. 24 and 25). 26.W. More generally. These and similar valence diagrams may be useful in understanding intramolecular distortions and reaction mechanisms. respectively (Fig. displaced toward B 2 and B 3. Donation occurs from the B 1 B 2 s i n g l e bond in B 8 H 1 4 . whether or not hydrogen bridges are available for accommodating this electron displacement. I have abstracted from these examples some typical modes of single bond donation. and accompanying electron withdrawal or hydrogen displacement. VB B - B BhR Fig. 25. . Two additional examples are illustrated in B 8H 1345 and in the predicted structure of B 8H 14. this donation causes electron withdrawal along other bonds in the molecule. Lipscomb 235 H Fig. in accord with the results obtained from our X-ray diffraction study.

On the left. The fractional use of orbitals. 27. 29). thr equivalent resonance hybrid is given. does not occur in B6H 10 which Fig. 28. is not limited to boranes and their relatives. and also are preferred over the open three-center bond (Fig. However. 27). the localized molecular orbitals are themselves derived from wavefunctions for which the exclusion principle is rigorously introduced. The four localized molecular orbitals in carboxylate anion have a charge distribution which shows displacement toward oxygen. is described as fractional three-center bonds. in an element in the first row of the periodic table. often to a single preferred structure. Our rather extensive studies of bonding among atoms other than boron have indicated that these simplified localized molecular orbitals may be an informative and useful alternative to the ‘more conventional valence bond and molecular orbital descriptions in other parts of the periodic table. 46 Its simplest interpretation is the replacement of a pair of resonance structures by a single valence structure (Fig. indicated by dotted lines. A very simple example. 28. Also. the bonding of the two carbon atoms in this carborane by both a single bond and a central three-center bond has not been found in boranes. increases the apparent number of bonds to a given boron above the usual four.236 Chemistry 1976 A new type of bonding. Fractional bonds to atom B2 in 4. Fig.5-C2B 4H 8 are preferred 48 over a resonance hybrid of a single and a central three-center bond. in particular. Indeed. which is conceptually transferable among these molecules. . the Pauli exclusion principle is not violated because less than a full atomic orbital is required at a fractional bond.47 is shown in Fig. and. The use of fractional bonds to reduce the number of resonance hybrids. carboxylate anion. Equivalence is shown of the two fractional three-center bonds to a resonance hybrid of a single bond and a three-center bond.

Fractional bonds give a particularly simple valence description45 of bonding in B 10H 14 (Fig. where the two pairs offractional bonds are dotted toward atoms B2 and B4. 30). . N.5-C2B 4H 8. rather than toward B 6 and B 9. Lipscomb 237 is isoelectronic with 4.W. where the single valence structure (Fig. 30c) replaces a resonance hybrid of 24 central three-center bond structures. A very similar simplification 45 occurs in B 10H 14-2.

in this molecule. 33). or in those boranes which have a valence pattern similar to that in the aromatics. 7 . the two valence structures represent extremes over a 45° range of orientation angle.C2 B 4 H 6 ( F i g . we tend to prefer42 the almost equivalent open three-center bonds. in accord with the four-fold symmetry which the electron density must have in this molecule. Fractional three-center bonds are not always unique. Moreover. Perhaps this procedure tends to exaggerate the separation of charge centroids of bonds when they lie at or near a single center. For this reason. like those in 1. 2 .2-C 2B 4H 6. An example of this orientational ambiguity occurs in the boron framework bonds in B5H 9 (Fig.238 Chemistry 1976 Similar pairs of fractional bonds are found by Boys’ localization procedure i n t h e p o l y h e d r a l c a r b o r a n e s 1 . if and when the calculations can be made.2-C 2B 4H 6. about the four-fold axis. When it becomes economically feasible to test this alternative in 1. 3 1 ) a n d 1 . 31 may occur in 1. 32. where the Boys localization (right side) shows fractional bonds. particularly in aromatic hydrocarbons. A situation parallel to that of Fig. I would guess that localized open three-center bonds will be found.7-C 2 B 1 0 H 1 2 . Actually. . The open three-center bond description may be found by the Edmiston-Ruedenberg procedure. this ambiguity continues throughout the whole 360”.7-C 2B 10H 12. and each has a total electron density which is consistent with the four-fold molecular symmetry. All of these valence structures are equally preferred. centered at carbon atoms. 32). There is a continuum of valence structures between these extremes. as found by the Edmiston-Ruedenberg procedure in 1. Fig.C2 B 1 0H 1 2 (Fig.

34).W. N. Fig. Fig. In C 2 B 1 0 H 1 3 -. 33. In 1. 35. Lipscomb 239 a b Fig. 4 9 not requiring resonance or appreciable fractional bonding (Fig. There is little fractional bonding in the localized orbitals of the nearly polyhedral C2B10H 13. 7 . 34. another simple idea occurs: the bonding.i c o s a h e d r a l C2 B 10 a r r a n g e m e n t . t h e b o n d i n g i s e s pecially simple. In more complex molecules one can find various degrees of simplicity in the bonding patterns of localized molecular orbitals.ion. There is an orientational ambiguity about the four fold axis of B5H 9 involving a continuum of valence structures between (a) and (b). is to a good approximation just like that in 1 . The localized orbitals obtained for 1. Thus there is some tendency for bonding invariance in closely related geometrical structures.2-C 2 B 1 0 H 1 2 . 35). H12 in spite of the very different positions of the two carbon atoms relative to each other and to their boron neighbors (Fig. In iso-B 1 8 H 2 2 . which has a s o m e w h a t o p e n n e a r .C2 B 10 .2-C2B10H 12 by Boys’ procedure are the same as those found in 1. and extending eventually throughout the complete 360° range.7-C 2 B 10 H 12 in spite of the difference in positions of carbon atoms relative to boron atoms. as found by Boys’ procedure.

38) rather than like that in B 10 H 14 (Fig. Single bond donation and fractional bonds occur in iso-B 18 H 22 . Fig. . the single bond donations are greater toward B 9. Boron atoms B 4 B 1 6 . 37. Each of these eight boron atoms has only two framework bonds in the figure at the right. particularly toward the electron deficient B9-B 16 atoms.240 Chemistry 1976 we find50 both single bond donation. inclusive (Fig. 36). a molecule having a two-fold axis only. in which the four borons nearest the equatorial belt have no terminal hydrogens. and fractional bonds. Fig. 36. In B 20H 16 there is a remarkable amount of single-bond donation. than toward B 3 and B13. inclusive. to B6 and B 16 (Fig. are particulaly electron deficient. 37) and the valence structure of each half is clearly like that in B 10H 14-2 (Fig. 30). and receive substantial donation from single bonds. Donation and non-donation localized orbitals are shown for B2 0 H 1 6 . and no terminal hydrogen atoms on atoms B 9 and B 10 . Here. from B 4B 8 a n d Bl4 H 18 . which is relatively electron deficient.

This single valence structure replaces a resonance hybrid of 216 valence structures based upon central three-center bonds and single bonds. The preferred localized orbital structure is shown on the left side. In BH5 (Fig. 40) there is only a very weak donor bond from H2 to the vacant orbital of BH3. Finally. Fig. I offer the reader a challenge to find the close relative valence structures which do not have fractional bonding or single bond donation in this molecule.241 Fig. the bonding in reaction intermediates is a new area of study. Atoms B 9 a n d B 10 do not have terminal hydrogens. The rather complex localized molecular orbitals in B 16 H 20 (Fig. 50 With recognition that atoms B 9 a n d B10 have no terminal hydrogens attached to them. 39) are dominated by the three-center bond approximation. On the other . 39. Bond donations can be withdrawn by the reader in order to discover the preferred valence bond structures of the simpler theory. in addition they are modified by single bond donation accompanied by electron withdrawal from atoms to which donation occurs . A rather complex pattern of localized orbitals is shown for B 16 H 20 . A relationship similar to that in B 2 0 H 16 occurs in B 1 0 H 1 4 -2 . 38.51-55 This weakness is probably due to the absence of a pathway for back donation. primarily by purely theoretical methods. while the open three-center bond structure without donation is an oversimplified valence structure.

Our other recent progress in theoretical studies of bonding in reaction intermediates. because of the strain involved when that vacant orbital is filled by converting a terminal BH bond to a BH. the field of boron chemistry has grown enormously. undergraduates. molecules. Also. and particularly the use of bonding theory in bringing some degree of order to chemical transformations of the boranes have been omitted. 41. Approximate geometry of the transition state when two BH. For the figures of this . hydrogen atom tautomerism. 41). in the dimerization of two BH 3 molecules to form B2H 6. polyhedral rearrangements. to my research associates: graduate students.242 Chemistry 1976 hand. and then to discover a systematic valence description of the vast numbers of “electron deficient” intermetallic compounds. omitting descriptions of bonding in large polyhedral borane anions and other related compounds. bridge BHB bond. donation of electron density from one terminal H to B of the other BH3 group is balanced by a symmetrically related donation toward the first BH 3 group 56 (Fig. molecule is Fig. Attention has thus been concentrated on those aspects of chemical bonding which have been especially illuminated by the molecular and crystal structures that we and others have studied over these many years. My original intention in the late 1940’s was to spend a few years understanding the boranes. postdoctoral fellows and my other colleagues who have coauthored nearly all of these studies. molecules form B 2 H 6 . I shall stop here. Actually less is known of the detailed reaction mechanisms for reactions of boranes and their related compounds than is known for organic reactions of comparable complexity. this is a fruitful area for future research. Instead. I have made little progress toward this latter objective. This geometry is favored over that in an unsymmetrical approach of two BH. Surely. and a systematic understanding of some of its complexities has now begun. shows that the more stable transient species may have a vacant orbital57 on one boron atom. It remains to give credits where they really belong. such as B3H 7 and B4H 8.

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