That Act as Lewis Acids

Since molecules with incomplete octets have empty orbitals, they can serve as Lewis acids. For example, both AICI3 and BCI3 have incomplete octets  

These both act as Lewis acids, as shown in the following reactions  

Some molecules that may not initially contain empty orbitals can rearrange their electrons to act as Lewis acids. Consider the reaction between carbon dioxide and water  

The electrons in the double bond on carbon move to the terminal oxygen atom, allowing carbon dioxide to act as a Lewis acid by accepting an electron pair from water. The molecnle then undergoes a rearrangement in which the hydrogen atom shown in red bonds with the terminal oxygen atom instead of the internal one. 

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In order to unravel adsorption mechanisms, a detailed knowledge of the composition and reactivity of the adsorption centers on the initial adsorbent is imperative [35-37]. It is well known [37-39] that fractured surfaces can be covered by cations and anions with unoccupied orbitals that act as Lewis acid and Lewis base centers, respectively. After adsorption of water molecules, with the evolution of hydroxyl and hydrogen species, the Lewis centers are transformed into Bronsted centers, which will influence surface properties. In many cases, characterizing the adsorption sites is complicated, and controversy stiU exists in the interpretation of IR spectra of functional groups, even for extensively studied oxides such as silica and alumina [6, 40, 41]. 

Metals that act as Lewis acids can increase the effectiveness of a receptor by directly interacting with an anion, polarizing a hydrogen-bond donor, hence increasing its acidity, providing a structural element, or more usually a combination of both. Direct coordination of anions to metal... 

A proton (H+) is an electron pair acceptor. It is therefore a Lewis acid because it can attach to ( accept") a lone pair of electrons on a Lewis base. In other words, a Bronsted acid is a supplier of one particular Lewis acid, a proton. The Lewis theory is more general than the Bronsted-Lowry theory. For instance, metal atoms and ions can act as Lewis acids, as in the formation of Ni(CO)4 from nickel atoms (the Lewis acid) and carbon monoxide (the Lewis base), but they are not Bronsted acids. Likewise, a Bronsted base is a special kind of Lewis base, one that can use a lone pair of electrons to form a coordinate covalent bond to a proton. For instance, an oxide ion is a Lewis base. It forms a coordinate covalent bond to a proton, a Lewis acid, by supplying both the electrons for the bond ... 

Small, highly charged metal cations that can act as Lewis acids in water, such as Al3+ and Fe3+, produce acidic solutions, even though the cations themselves have no hydrogen ions to donate (Fig. 10.18). 

Carbon is the only member of Group 14/IV that commonly forms multiple bonds with itself singly bonded silicon atoms can act as Lewis acids because a silicon atom can expand its valence shell. 

A good example is B (0113)3 which uses a vacant 2 p orbital to form an adduct with ammonia. The elements in the p block beyond the second row of the periodic table have empty valence d orbitals that allow them to act as Lewis acids. The silicon atom in Sip4 is an example. 

For some strong electron donor molecules the polarization of the X2 molecule may be sufficient that the X atom not complexed to B serves as an electron donor to a second X2 molecule, i.e., the dihalogen is amphoteric , acting as a Lewis acid to Lewis base B, and as a Lewis base to the second X2 molecule, acting as a Lewis acid. For a 1 1 B X2 X2 ratio, an extended adduct (Fig. 1, mode AA) is formed, as illustrated in Fig. 2c for 4,5-bis(bromomethyl)-l,3-dithiole-2-thione-diiodine diiodine (HAMCAA) [58]. This is often referred to as an extended spoke structure. If the second X2 acts as Lewis acid acceptor at either end of the molecule, then a bridged amphoteric adduct (Fig. 1, mode BA) is formed, as illustrated for (acridine I2)2 I2 (QARGIZ) [31] in Fig. 2d. 

Compounds that have atoms with vacant orbitals also can act as Lewis acids. 

Sc(OTf)3 is stable in water, and effectively activates carbonyl and related compounds as a Lewis acid in water. This is remarkable, because most Lewis acids react immediately with water rather than the substrates, and are decomposed or deactivated. It has already been found that lanthanide trifiates Ln(OTf)3 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and yttrium trifiate Y(OTf)3 are stable in water, and can act as Lewis-acid catalysts in aqueous media.46-48 They are used catalytically in many reactions and can often be recovered and reused, because they are stable under the usual water-quenching conditions. 

Significant progress has been achieved in the preceding few years in the study of titanosilicate molecular sieves, especially TS-1, TS-2, Ti-beta, and Ti-MCM-41. In the dehydrated, pristine state most of the Ti4+ ions on the surfaces of these materials are tetrahedrally coordinated, being present in either one of two structures a tetrapodal (Ti(OSi)4) or a tripodal (Ti(OSi)3OH) structure. The former predominates in TS-1, TS-2, and Ti-beta, and the latter is prominent in Ti-MCM-41. The Ti ions are coordinatively unsaturated and act as Lewis acid sites that coordinatively bind molecules such as H20, NH3, CH3CN, and H202. Upon interaction with H202 or H2 + 02, the Ti ions form titanium oxo species. Spectroscopic techniques have been used to identify side-bound hydroperoxo species such as Ti(02H) and superoxo structures such as Ti(02 ) on these catalysts. 

Finally, one should note that metal species in a zeohte may act as Lewis acid sites. These sites are less acidic than Bronsted acid sites, i.e., protons, but contribute to the total acidity of a given zeohte. 

We have recently shown that metal-exchanged zeolites give rise to carbocationic reactions, through the interactions with alkylhalides (metal cation acts as Lewis acid sites, coordinating with the alkylhalide to form a metal-halide species and an alkyl-aluminumsilyl oxonium ion bonded to the zeolite structure, which acts as an adsorbed carbocation (scheme 2). We were able to show that they can catalyze Friedel-Crafts reactions (9) and isobutane/2-butene alkylation (70), with a superior performance than a protic zeolite catalyst. 

Lewis acid sites may be formed following dehydroxylation of zeolite surface in H-form. At sufficiently high temperatures two Bronsted acid sites can drive off a water molecule and leave behind a coordinatively unsaturated Al site, as illustrated in Figure 13.16 [32]. Here not only the resulting tri-coordinated Al but also the tri-coordinated positively charged Si can act as a Lewis acid. Furthermore dehydroxylation may be followed by framework dealumination, leading to cationic extra-framework species like AlO AlfOHij that can act as Lewis acids [33-37]. 

Jacobsen and coworkers discovered that chiral salicylimidato transition metal complexes activate epoxides in a stereoselective manner. The published mechanism indicates that one Cr° (salen)-N3 with (/ ,/ )-cyclohexyl backbone acts as Lewis acid and coordinates to the oxygen of PO, while a second catalyst molecule transfers the azide to the activated epoxide and thus opens the ring. The coplanar arrangement of the two chromium complexes prefers one enantiomer of PO and so induces stereochemical information [99,100, 121-129]. (cf. also Sect. 8.3) (Fig. 42). 

Another approach to the "greening of catalysts has been the use of rare-earth compounds known as inflates. The term inflate is an abbreviation for the trifluoromethanesulfonate (SO3CF3) cation. Some typical triflates that have been used in research include the lanthanides, scandium, and hafnium. These triflates act as Lewis acids (electron acceptors) and can, therefore, be substituted for stronger mineral acids (such as sulfuric acid) with undesirable environmental... 

The authors also investigated the mode of activation of these BINOL-derived catalysts. They proposed an oligomeric structure, in which one Ln-BINOL moiety acts as a Brpnsted base, that deprotonates the hydroperoxide and the other moiety acts as Lewis acid, which activates the enone and controls its orientation towards the oxidant . This model explains the observed chiral amplification effect, that is the ee of the epoxide product exceeds the ee of the catalyst. The stereoselective synthesis of cw-epoxyketones from acyclic cw-enones is difficult due to the tendency of the cw-enones to isomerize to the more stable fraw5-derivatives during the oxidation. In 1998, Shibasaki and coworkers reported that the ytterbium-(f )-3-hydroxymethyl-BINOL system also showed catalytic activity for the oxidation of aliphatic (Z)-enones 129 to cw-epoxides 130 with good yields... 

Williams group observed low enantioselectivities for the Michael addition of a prochiral nucleophile, ethyl 2-cyanopropionate 623, to methyl vinyl ketone 624 catalyzed by chiral platinum complexes (Scheme 8.196)." The NMR analysis indicated that these cationic Pt complexes act as Lewis acids toward nitriles. The X-ray crystal structure as well NMR analysis showed that the solvent ligand that is readily displaced by an organic substrate is situated cis to the nitrogen donor in the Pt complex and, therefore, is in a chiral pocket created by the oxazoline ring. 

Interestingly, Cao and Hamers found in the same set of studies that trimethylamine also forms a dative-bonded adduct on the Si(l 11)—7 x 7 surface, reacting similarly to the Si(100)-2 x 1 surface [47]. They note that the positively charged adatoms on Si(l 11)—7 x 7 act as Lewis acids, and are the most likely site for the nucleophilic amine to bond. The main difference observed between the two surfaces is that the coverage of trimethylamine molecules on Si(lll)-7 x 7 is only about half the coverage on Si(100)-2 x 1. 

The simultaneous investigation of the methanol conversion on weakly dealuminated zeolite HZSM-5 by C CF MAS NMR and UV/Vis spectroscopy has shown that the first cyclic compounds and carbenium ions are formed even at 413 K. This result is in agreement with UV/Vis investigations of the methanol conversion on dealuminated zeolite HZSM-5 performed by Karge et al (303). It is probably that extra-framework aluminum species acting as Lewis acid sites are responsible for the formation of hydrocarbons and carbenium ions at low reaction temperatures. NMR spectroscopy allows the identification of alkyl signals in more detail, and UV/Vis spectroscopy gives hints to the formation of low amounts of cyclic compounds and carbenium ions. 

Transition metal complexes act as templates that regulate organic reactions that occur in the coordination sphere (4). Ligands are often activated or stabilized by participation of metal d orbitals, where the central metals are electronically amphoteric in contrast to the main group elements, which normally act as Lewis acids. The bonding scheme of an olefin-transition metal complex is illustrated in Scheme 2. The olefin 7T electrons are donated to a vacant metal orbital to make a a-type bond the metal d elections are back-donated to olefin anti-bonding orbitals with the same symmetry to form a ir-type bond. In this way, the olefin is activated by formal electron promotion from the tt to tt orbital, as... 

Like electrophilic addition to diazo compounds [7] from which diazonium ions and, subsequently, carbocations are generated, transition-metal compounds that can act as Lewis acids are potentially effective catalysts for metal carbene transformations. These compounds possess an open coordination site that allows the formation of a diazo carbon-metal bond with a diazo compound and, after loss of dinitrogen, affords a metal carbene (Scheme 5.2). 

Since they have both a vacant low-energy orbital and a lone pair, silylenes might behave either as electron pair donors or acceptors. There is scant evidence for silylenes reacting as Lewis bases, but complexes of silylenes acting as Lewis acids are now well-established these complexes can also be described as silaylides, R2>Si —B+262. Trinquier has calculated that even SiLL should form a weak complex with 112S i , in which a silane hydrogen binds to the p-orbital of the silylene263. 

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