Lewis base behavior

That being the case, it is appealing to refer to anion receptors as ligands. However, traditionally the commonly understood definition of ligand has been a Lewis base capable of forming a coordinate-covalent bond with a metal ion. Since for anions, the ligand actually behaves as a Lewis acid, the definition needs to be expanded to include both Lewis acid and Lewis base behavior. 

Deprotonated surface hydroxyls exhibit Lewis base behavior. Adsorption of metal ions is therefore understood as competitive complex formation involving one or two surface hydroxyl groups ... 

Protonation and Lewis Base Behavior. In electron-rich complexes the metal atom may have substantial non-bonding electron density located on it and consequently may be attacked by the proton or by other electrophilic reagents. An example is (/z5-C5H5)2ReH which is a base comparable in strength to ammonia, cf. h3n + H+H4N+... 

The Lewis base behavior of coordinated dinitrogen has been studied and related to In many cases, stable Lewis base-Lewis acid... 

Coordination Complexes. The abiUty of the various oxidation states of Pu to form complex ions with simple hard ligands, such as oxygen, is, in order of decreasing stabiUty, Pu + > PuO " > Pu + > PuO Thus, Pu(Ill) forms relatively weak complexes with fluoride, chloride, nitrate, and sulfate (105), and stronger complexes with oxygen ligands (Lewis-base donors) such as carbonate, oxalate, and polycarboxylates, eg, citrate, and ethylenediaminetetraacetic acid (106). The complexation behavior of Pu(Ill) is quite similar to that of the light lanthanide(Ill) ions, particularly to Nd(Ill)... 

Most other studies have indicated considerably more complex behavior. The rate data for reaction of 3-methyl-l-phenylbutanone with 5-butyllithium or n-butyllithium in cyclohexane can be fit to a mechanism involving product formation both through a complex of the ketone with alkyllithium aggregate and by reaction with dissociated alkyllithium. Evidence for the initial formation of a complex can be observed in the form of a shift in the carbonyl absorption band in the IR spectrum. Complex formation presumably involves a Lewis acid-Lewis base interaction between the carbonyl oxygen and lithium ions in the alkyllithium cluster. 

A further important concept related to electronegativity and polarity is that of acidity and basicity. We ll see, in fact, that much of the chemistry of organic molecules can be explained by their acid-base behavior. You may recall from a course in general chemistry that there are two frequently used definitions of acidity the Brtfnsted-Lowry definition and the Lewis definition. We ll look at the... 

Nucleophilicity roughly parallels basicity when comparing nucleophiles that have the same reacting atom. For example, OH- is both more basic and more nucleophilic than acetate ion, CH3CO2-, which in turn is more basic and more nucleophilic than H20. Since "nucleophilicity" is usually taken as the affinity of a Lewis base for a carbon atom in the Sfj2 reaction and "basicity" is the affinity of a base for a proton, it s easy to see why there might be a correlation between the two kinds of behavior. 

Silicon compounds can also act as Lewis acids, whereas carbon compounds typically cannot. Because a silicon atom is bigger than a carbon atom and can expand its valence shell by using its d-orbitals, it can accommodate the lone pair of an attacking Lewis base. A carbon atom is smaller and has no available d-orbitals so in general it cannot act as a Lewis acid. An exception to this behavior is when the carbon atom has multiple bonds, because then a Tt-bond can give... 

Lewis Acid-Base Behavior in Aqueous Solution Some Implications for Metal Ions in Biology Robert D. Hancock and Arthur E. Martell... 

LEWIS ACID-BASE BEHAVIOR IN AQUEOUS SOLUTION SOME IMPLICATIONS FOR METAL IONS... 

Thermodynamics of complex formation of silver with several ligands such amines,368 hindered pyridine bases,369 nitrogen donor solvents,370 and azoles371 have been carried out. Other studies include the secondary-ion mass spectra of nonvolatile silver complexes,372 the relationship between Lewis acid-base behavior in the gas phase and the aqueous solution,373 or the rates of hydride abstraction from amines via reactions with ground-state Ag+.374... 

In a manner similar to OsH(OH)(CO)(P Pr3)2, the hydride-metallothiol complex OsH(SH)(CO)(P Pr3)2 adds Lewis bases that are not bulky such as CO and P(OMe)3 to give the corresponding six-coordinate hydride-metallothiol derivatives OsH(SH)(CO)L(P Pr3)2 (L = CO, P(OMe)3). OsH(OH)(CO)(PiPr3)2 and OsH(SH)(CO)(P Pr3 also show a similar behavior toward dimethyl acetylenedi-carboxylate. Treatment of OsH(SH)(CO)(P Pr3)2 with this alkyne affords 6sH SC(C02Me)CHC(OMe)6 (CO)P Pr3)2, which is the result of the tram addition of the S—H bond to the carbon-carbon triple bond of the alkyne. Phenyl-acetylene, in contrast to dimethyl acetylenedicarboxylate, reacts with OsH(SH) (CO)(P Pr3)2 by insertion of the carbon-carbon triple bond into the Os—H bond to give the unsaturated alkenyl-metallothiol derivative Os ( )-CH=CHPh (SH) (CO)(P Pr3 )2, the inorganic counterpart of the organic a, (3-unsaturated mercaptans (Scheme 46).92... 

Lewis Bases. A variety of other ligands have been studied, but with only a few of the transition metals. There is still a lot of room for scoping work in this direction. Other reactant systems reported are ammoni a(2e), methanol (3h), and hydrogen sulfide(3b) with iron, and benzene with tungsten (Tf) and plati num(3a). In a qualitative sense all of these reactions appear to occur at, or near gas kinetic rates without distinct size selectivity. The ammonia chemisorbs on each collision with no size selective behavior. These complexes have lower ionization potential indicative of the donor type ligands. Saturation studies have indicated a variety of absorption sites on a single size cluster(51). 

Acid-base behavior according to the Lewis theory has many of the same aspects as does acid-base theory according to the Bronsted-Lowry theory. 

In many ways, TiCl4 behaves as a covalent compound of a nonmetal. It is a strong Lewis acid that forms complexes with many types of Lewis bases, and it hydrolyzes in water. It also reacts with alcohols to yield compounds having the formula Ti(OR)4. However, it is the behavior of TiCl4 (reacting with [A1(C2H5)3]2) as a catalyst in the Ziegler-Natta polymerization of ethylene that is the most important use of the compound (see Chapter 22). 

---