Lewis acid-base adducts

The XeF+ cation forms Lewis acid—base adduct cations containing N—Xe—F linkages with nitrogen bases that are resistant to oxidation by the strongly oxidizing XeF+ cation having an estimated electron affinity of the XeF+ cation of 10.9 eV (12). The thermally unstable colorless salt,... 

The chemistry of Lewis acid-base adducts (electron-pair donor-acceptor complexes) has stimulated the development of measures of the Lewis basicity of solvents. Jensen and Persson have reviewed these. Gutmann defined the donor number (DN) as the negative of the enthalpy change (in kcal moL ) for the interaction of an electron-pair donor with SbCls in a dilute solution in dichloroethane. DN has been widely used to correlate complexing data, but side reactions can lead to inaccurate DN values for some solvents. Maria and Gal measured the enthalpy change of this reaction... 

The first example of a neutral aluminum complex of diazaphosphane, the 1,3,2,4-diazaphosphaluminetidine 50, Eq. (4), has been synthesized by the dehydrogenation reaction between Lewis acid-base adduct H3AI <— NMca and fBuP[N(H)fBu 2 49. The product fBuP(NfBu)2(H)Al [Pg.111]

Besides simple Lewis acid-base adducts, numerous compounds of the type [R2MER x and [RMER ]x (x 2), containing real cr-bonds between the group 13 and 15 elements, have been prepared. Epoch-making studies were performed by famous chemists such as Stock and Poland, who synthesized the... 

Later on, this concept was extended to precursors containing both elements of the desired material already connected by a chemical bond in a single molecule. Such precursors are mainly referred to as single source precursors. Their potential application for the deposition of thin films of the corresponding binary materials by MOCVD processes could be demonstrated. In particular Lewis acid-base adducts R3M—ER3 and four- and six-membered heterocycles [R2MER x (Fig- 1) have been in the focus of research groups both in industry and university. Consequently, the development of powerful synthetic pathways for the preparation of such precursors has been forced. 

A major goal was to investigate the solid state structures of such compounds by single crystal X-ray diffraction. It was found that Lewis acid-base adducts R3M—ER3 show general structural trends, which allow estimations on the relative stability of the adducts. The experimental results were confirmed by computational calculations, giving even deeper insights into the structural parameters and the thermodynamic stability of simple Lewis acid-base adducts. In addition, their thermodynamic stability in solution was investigated by temperature-dependent NMR spectroscopy. 

The reaction between a Lewis acid R3M and a Lewis base ER3, usually resulting in the formation of a Lewis acid-base adduct R3M—ER3, is of fundamental interest in main group chemistry. Numerous experiments, in particular reactions of alane and gallane MH3 with amines and phosphines ER3, have been performed [14]. Several general coordination modes, as summarized in Fig. 2, have been identified by X-ray diffraction. 

AHoiss = 19.3 0.2 kcal moP ) are stronger Lewis acid-base adducts than H3B—NMC3 (AHoiss = 34.8 0.5 kcal mol ) and McsB—NMej = 17.6 ... 

Scheme 4. Synthesis of Lewis acid-base adducts R3M—ER3 (E = Sb, Bi) since 1996...

Fig. 5. M—C bond distances of analogously substituted Lewis acid-base adducts...

These particular properties of chloroalanes favor the formation of simple Lewis acid-base adducts, as was observed for the reaction of R2AICI with Sb(Tms)3 (R = Et, f-Bu). In contrast, reactions of the analogous gallanes and indanes yielded the desired heterocycles. The same tendencies were observed in reactions of R2MCI (M = Al, Ga, In R = Et, i-Bu) with P(Tms)3 and As(Tms)3. The gallane and indane react under formation of the expected M—E heterocycles [71], while the corresponding alanes yield the simple adducts... 

Only some Lewis acid-base adducts of group 13 trialkyls R3M or trihalides CI3M and transition metal complexes of the type LnFe—E=CR2, (E = P, As) Weber L, Scheffer MH, Stammler HG, Stammler A (1999) Eur J Inorg Chem 1607 (LnW=P) Scheer M, Muller J, Baum G, Haser M (1998) J Chem Soc Chem Commun 1051, have been synthesized and structurally characterized... 

Removing electrons from a metal atom always generates vacant valence orbitals. As described in Chapter 20, many transition metal cations form complexes with ligands in aqueous solution, hi these complexes, the ligands act as Lewis bases, donating pairs of electrons to form metal-ligand bonds. The metal cation accepts these electrons, so it acts as a Lewis acid. Metal cations from the p block also act as Lewis acids. For example, Pb ((2 g) forms a Lewis acid-base adduct with four CN anions, each of which donates a pair of electrons Pb ((2 ( ) + 4 CN ((2 q) -> [Pb (CN)4] (a g)... 

C21-0025. Write the stmctural formula for an example of each of the following (a) Lewis acid-base adduct (b) polyphosphate (c) fluorine-containing polymer and (d) alkyllithium reagent. 

C21-0030. The reaction between CO2 and H2 O to form carbonic acid (H2 CO3) can be described in two steps formation of a Lewis acid-base adduct followed by Brcjmsted proton transfer. Draw Lewis structures illustrating these two steps, showing electron and proton movement by curved arrows. 

In aprotic solvents that can act as electron pair donors such as ethers, tertiary amines, and sulfides, borane forms Lewis acid-base adducts. 

Group 13/15 compounds have a long-standing history in inorganic chemistry and have been known for almost two centuries. First reports on such compounds go back to 1809, when Gay Lussac synthesized F3B4—NH3,1 the historical prototype of a Lewis acid-base adduct, by reaction of BF3 and NH3. Since this initial study, numerous Lewis acid-base adducts of boranes, alanes, gallanes and indanes MX3, MF13 and MR3 (M = B, Al, Ga, In X = F, Cl, Br, I R = alkyl, aryl) of the type R3M <- ER 3 (E = N, P, As) (Type A) have been synthesized and... 

Dissociation Enthalpies De [kcal/mol] of Group 13/15 Lewis Acid-Base Adducts... 

The potential of group 15 trialkyls ER3 to form Lewis acid-base adducts with group 13 compounds has been demonstrated as shown previously. In contrast, that of low-valent organopenteles such as dipenteles RjE-ERj and cyclopenteles [ER ]X (E = P, As, Sb, Bi) has been studied to a far lesser extent.59 Tetraalkyldipenteles E2R4 belong to the oldest metalorganic main... 

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