Two-electron three-center

We can consider the hydroboration step as though it involved borane (BH3) It sim phfies our mechanistic analysis and is at variance with reality only m matters of detail Borane is electrophilic it has a vacant 2p orbital and can accept a pair of electrons into that orbital The source of this electron pair is the rr bond of an alkene It is believed as shown m Figure 6 10 for the example of the hydroboration of 1 methylcyclopentene that the first step produces an unstable intermediate called a tt complex In this rr com plex boron and the two carbon atoms of the double bond are joined by a three center two electron bond by which we mean that three atoms share two electrons Three center two electron bonds are frequently encountered m boron chemistry The tt complex is formed by a transfer of electron density from the tt orbital of the alkene to the 2p orbital... 

The range of structural alternatives explored by valency-deficient carbon species and the subtle interplay of substituents is remarkable. Scheme 7.6 (ORTEP adapted from reference 31) illustrates an example of an X-ray structure clearly describing a localized [C-H C+] carbenium ion (A) where a symmetric bridging structure [C-H-C] + (B) could have been assumed. In this case it is proposed that a charge-transfer interaction between the resonance delocalized cation and the adjacent electron-rich carbazol moiety may be responsible for the stabilization of the localized form over the three-center, two-electron (3c-2e) bridging structure. 

In a-B12 the icosahedra are arranged as in a cubic closest-packing of spheres (Fig. 11.16). In one layer of icosahedra every icosahedron is surrounded by six other icosahedra that are linked by three-center two-electron bonds. Every boron atom involved contributes an average of electrons to these bonds, which amounts to -6 = 4 electrons per icosahedron. Every icosahedron is surrounded additionally by six icosahedra of the two adjacent layers, to which it is bonded by normal B-B bonds this requires 6 electrons per icosahedron. In total, this adds up exactly to the above-mentioned 10 electrons for the inter-icosahedron bonds. 

For low values of the valence electron concentration (VEC< 4 for main group elements), covalent 2c2e bonds are not sufficient to overcome the electron deficiency. We have the case of electron-deficient compounds . For these, relief comes from multicenter bonds. In a three-center two-electron bond (3c2e) three atoms share an electron pair. An even larger number of atoms can share one electron pair. With increasing numbers of... 

Figure 8.7 Diborane, BaH. (a) Contour map of pb in the plane of the terminal hydrogens, (b) Contour map of pb in the plane of the bridging hydrogens, (c) Calculated geometry, (d) Experimental geometry. (e) Interatomic H-H distances, (f) Ionic model, (g) Resonance structures, (h) Protonated doublebond model, (i) VSEPR domain model showing the two three-center, two-electron bridging domains, (j) Hybrid orbital model.

It is known that a carborane framework involves three-center two-electron bonding and is thus an elelctron-deficient cluster. Shatenshtein76 reported that the pKa value of the C—H proton of carborane is 23. Therefore, a proton attached to the carbon of o-carborane could be deprotonated easily by a weak base, and the resulting... 

Bonding of this type and other boron hydrides that have three-center two-electron bonds with hydrogen bridges is discussed in Chapter 13. 

This section reviews the developments in the chemistry of monoborane complexes of the transition metals especially borohydride and hydridoborate complexes. Although such complexes are not strictly metallaboranes in the sense that they are not cluster species, they are included here as they share many similarities with polyborane species of the transition metals such as three-center two-electron bonding. Additionally, as will be shown in Section 3.04.3.1 borohydride species can also be intermediates in the formation of larger M By clusters. In this chapter, three-coordinate monoborane species, which are best considered as cr-complexes between a transition metal and HBR2 or metal-boryl (M-B) species, are not considered. 

Three-center two-electron bonds are also created when [Mn N(SiMe3)2 2(THF)] and AlMe3 are reacted (Equation (53)).82 The product is [ Mn(/x-Me)[N(SiMe3)2AlMe3] 2], 51.82... 

Each B-H-B three-center two-electron bridge bond corresponds to a filled three-center localized bonding orbital requiring the hydrogen orbital and one hybrid orbital from each boron atom. 

Consider the closo-BnHn2 (6 < n < 12) boranes (Figure 1-2). Such deltahedral boranes cannot have any terminal BH2 groups or three-center two-electron B-H-B bonds but acquire two extra electrons from the —2 charge on the ion. Therefore s = x = 0 in the equations of balance (la) and (lb) these reduce to (2a) and (2b) in which n is the number of boron atoms in the deltahedron corresponding to p in (la) and (lb) ... 

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