Boron trifluoride structure

An electrostatic potential map of boron trifluoride is shown. Is BF3 likely to be a nucleophile or an electrophile Draw a Lewis structure for BF3, and explain your answer. 

The pharmaceutical interest in the tricyclic structure of dibenz[6,/]oxepins with various side chains in position 10(11) stimulated a search for a convenient method for the introduction of functional groups into this position. It has been shown that nucleophilic attack at the carbonyl group in the 10-position of the dibenzoxepin structure renders the system susceptible to water elimination. Formally, the hydroxy group in the enol form is replaced by nucleophiles such as amines or thiols. The Lewis acids boron trifluoride-diethyl ether complex and titanium(IV) chloride have been used as catalysts. 

In this case, there are three equivalent hybrid orbitals, each called sp (trigonal hybridization). This method of designating hybrid orbitals is perhaps unfortunate since nonhybrid orbitals are designated by single letters, but it must be kept in mind that each of the three orbitals is called sp. These orbitals are shown in Figure 1.4. The three axes are all in one plane and point to the comers of an equilateral triangle. This accords with the known structure of boron trifluoride (BF3), a planar molecule with angles of 120°. 

Cationic polymerization of dienes using boron trifluoride or aluminum chloride as catalysts seems also to favor the rans-1,4 structure, although 1,2 and 3,4 units also are present. These catalysts also cause cyclization of the structural units, with a consequent decrease in the unsaturation in the polymer. 

Carbocation intermediates are involved and the structure and stereochemistry of the product are determined by the factors that govern substituent migration in the carbocation. Clean, high-yield reactions can be expected only where structural or conformational factors promote a selective rearrangement. Boron trifluoride is frequently used... 

Although all molecules are in constant thermal motion, when all of their atoms are at their equilibrium positions, a specific geometrical structure can usually be assigned to a given molecule. In this sense these molecules are said to be rigid. The first step in the analysis of the structure of a molecule is the determination of the group of operations that characterizes its symmetry. Each symmetry operation (aside from the trivial one, E) is associated with an element of symmetry. Thus for example, certain molecules are said to be planar. Well known examples are water, boron trifluoride and benzene, whose structures can be drawn on paper in the forms shown in Fig. 1. 

Two structures are possible for the interaction of aromatic hydrocarbons with acids.270 In the a-structures a covalent bond is established between the acidic reagent and a particular carbon atom of the benzene ring. The a-structures are essentially classical carbonium ions. In the -structures a non-classical bond is established, not to any particular atom, but to the -electron cloud in general. It is quite likely that both types of structure are represented by actual examples. Thus m-xylene interacts more strongly with hydrogen chloride than does o-xylene, but the difference between the two hydrocarbons is much more pronounced when their interactions with a boron trifluoride-hydrogen fluoride mixture are compared. This is readily understandable... 

Another differential reaction is copolymerization. An equi-molar mixture of styrene and methyl methacrylate gives copolymers of different composition depending on the initiator. The radical chains started by benzoyl peroxide are 51 % polystyrene, the cationic chains from stannic chloride or boron trifluoride etherate are 100% polystyrene, and the anionic chains from sodium or potassium are more than 99 % polymethyl methacrylate.444 The radicals attack either monomer indiscriminately, the carbanions prefer methyl methacrylate and the carbonium ions prefer styrene. As can be seen from the data of Table XIV, the reactivity of a radical varies considerably with its structure, and it is worth considering whether this variability would be enough to make a radical derived from sodium or potassium give 99 % polymethyl methacrylate.446 If so, the alkali metal intitiated polymerization would not need to be a carbanionic chain reaction. However, the polymer initiated by triphenylmethyl sodium is also about 99% polymethyl methacrylate, whereas tert-butyl peroxide and >-chlorobenzoyl peroxide give 49 to 51 % styrene in the initial polymer.445... 

The value of methylation studies in structural determination of carbohydrates is well known. Methylation of sucrose has generally been achieved by the use of dimethyl sulfate-sodium hydroxide,34,35 methyl iodide-silver oxide-acetone,20 sodium hydride-methyl io-dide-N,N-dimethylformamide,35 or diazomethane-boron trifluoride etherate.36,37 The last method (already applied to monosaccharides38,39) has been found particularly useful for sucrose, because it proceeds without concomitant migration of acyl groups. The reaction of 2,3,6,T,3, 4, 6 -hepta-0-acetylsucrose (21) and 2,3,4,6,1, 3, 4 -hepta-O-acetylsucrose (22) with diazomethane in dichloromethane in the presence of a catalytic proportion of boron trifluoride etherate for 0.5 h at —5° gave the corresponding 4-methyl (23) and 6 -methyl (24)... 

Structurally novel /3-lactams were obtained using enantiopure 4-oxoazetidine-2-carbaldehydes and methylene cyclohexane and a-methyl styrene (Equation (4)).7 Boron trifluoride diethyletherate and tin(iv) chloride produced the products in the highest yields, and all ene products possessed yy/z-stereochemistry. 

It is especially important to investigate the molecular structure of coordination compounds in the vapor phase because the relatively weak coordination interactions may be considerably influenced by intermolecular interactions in solutions and especially in crystals. It has been shown that the geometrical variations can be correlated with other properties of the molecular complexes ). In particular the structural changes in the F3B N(CH3)3 and CI3B N(CH3)3 molecules ) relative to the respective monomeric species unambiguously indicated boron trichloride to be a stronger acceptor than boron trifluoride. Data on the geometry and force field have also been correlated ). 

Compound 388 is an acylating agent for electron-deficient alkenes, in a Michael addition process. It is formed by treating molybdenum hexacarbonyl with an organolithium compound, followed by quenching the intermediate 387 with boron trifluoride (equation 104). The structure of 388 (R = Ph) can be elucidated by NMR spectroscopy. Other examples of enantioselective and diastereoselective Michael-type additions involving lithium-containing intermediates in the presence of chiral additives can be found elsewhere in the literature . 

The stereoselectivity of any particular reaction depends on the details of the structure of the transition state. The structures of several enone-Lewis acid complexes have been determined by X-ray crystallography.11 The site of complexation is the carbonyl oxygen, which maintains a trigonal geometry, but with somewhat expanded angles (130-140°). The Lewis acid is normally anti to the larger carbonyl substituent. Boron trifluoride... 

In contrast to radical polymerizations, ionic polymerizations proceed at high rates even at low temperatures, since the initiation and propagation reactions have only small activation energies. For example, isobutylene is polymerized commercially with boron trifluoride in liquid propane at -100 °C (see Example 3-16). The polymerization temperature often has a considerable influence on the structure of the resulting polymer. 

The transformation of the lanostane keto-epoxide (72) into the cucurbitacin derivative (73) has been achieved with boron trifluoride in acetic anhydride. The presence of the acetic anhydride appears to favour the backbone rearrangement. The structure of (73) was confirmed by correlation with the oxidation product (74) of deoxybryogenin acetate. Two new cucurbitacin glycosides, arvenins 1 (75) and II (76) from Anagallis arvensis, have been reported. ... 

Enolate species 6, derived from 1-oxopropyl complex 5, reacts similarly with monosubstituted epoxides. Under the influence of diethylaluminum chloride, only the diastereomers 7 and 8 were observed in the reaction mixture 7 was the major product. The use of boron trifluoride - diethyl ether complex instead of diethylaluminum chloride caused a complete loss of stereocontrol at C , producing a 50 50 mixture of diastereomers 7 and 8, but stereocontrol at C was retained as no other diastereomers were produced. The major diastereomer produced is consistent with the intermediacy of a transition state like that represented in Newman projection C which has the usual anti-E-snolate geometry and lacks the R methyl gauche interaction of structure D. 

All Br0nsted-Lowry acids are Lewis acids, but in practice, the term Lewis acid is generally reserved for Lewis acids that don t also fit the Bronsted-Lowry definition. The best way to spot a Lewis acid-base pair is to draw a Lewis dot structure of the reacting substances, noting the presence of lone pairs of electrons. (We introduce Lewis structures in Chapter 5.) For example, consider the reaction between ammonia (NH3) and boron trifluoride (BFj) ... 

At first glance, neither the reactants nor the product appears to be an acid or base, but the reactants are revealed as a Lewis acid-base pair when drawn as Lewis dot structures as in Figure 16-1. Ammonia donates its lone pair of electrons to the bond with boron trifluoride, making ammonia the Lewis base and boron trifluoride the Lewis acid. 

The synthesis of AMO involves treatment of 3,3-bis(chloromethyl) oxetane (BCMO) with sodium azide in the DMF medium at 85 °C for 24 h. Similarly, AMMO which is a monofunctional analog of AMO is synthesized by the azidation of chloro/tosylate product of 3-hydroxymethyl-3-methyl oxetane (HyMMO) with sodium azide in DMF medium at elevated temperatures. These energetic monomers are readily polymerized to liquid curable prepolymers with the help of boron trifluoride etherate/l,4-butanediol initiator system and the outlines of synthesis [147-150] of poly(BAMO) [Structure... 

Such a bond, in which the donor molecule (or anion) provides both bonding electrons and the acceptor cation provides the empty orbital, is called a coordinate or dative bond. The resulting aggregation is called a complex. Actually, any molecule with an empty orbital in its valence shell, such as the gas boron trifluoride, can in principle act as an electron pair acceptor, and indeed BF3 reacts with ammonia (which has a lone pair, NH3) to form a complex H3N ->BF3. Our concern here, however, is with metal cations, and these usually form complexes with from 2 to 12 donor molecules at once, depending on the sizes and electronic structures of the cation and donor molecules. The bound donor molecules are called ligands (from the Latin ligare, to bind), and the acceptor and donor species may be regarded as Lewis acids and Lewis bases, respectively. 

---