Sn1CB mechanism

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The SN1cB (conjugate base) mechanism describes the pathway by which many metal amine complexes undergo substitution, that is ligand exchange. Typically, the reaction entails reaction of a polyamino metal halide with aqueous base to give the corresponding polyamine metal hydroxide: [1]

In organic chemistry, amines (, UK also ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group (these may respectively be called alkylamines and arylamines; amines in which both types of substituent are attached to one nitrogen atom may be called alkylarylamines). Important amines include amino acids, biogenic amines, trimethylamine, and aniline; see Category:Amines for a list of amines. Inorganic derivatives of ammonia are also called amines, such as chloramine (NClH2); see Category:Inorganic amines.

Base (chemistry) substance that can accept hydrogen ions (protons) or more generally, donate a pair of valence electrons

In chemistry, bases are substances that, in aqueous solution, release hydroxide (OH) ions, are slippery to the touch, can taste bitter if an alkali, change the color of indicators (e.g., turn red litmus paper blue), react with acids to form salts, promote certain chemical reactions (base catalysis), accept protons from any proton donor or contain completely or partially displaceable OH ions. Examples of bases are the hydroxides of the alkali metals and the alkaline earth metals (NaOH, Ca(OH)2, etc.—see alkali hydroxide and alkaline earth hydroxide).

[Co(NH3)5Cl]2+ + OH → [Co(NH3)5OH]2+ + Cl

The rate law for the reaction is:

The rate law is deceptive: hydroxide serves not as a nucleophile but as a base to deprotonate the coordinated ammonia. Simultaneously with deprotonation, the halide dissociates. Water binds to the coordinatively unsaturated complex followed by proton transfer to give the hydroxy complex. The conjugate base resulting from deprotonation of the amine is rarely observed. [2]

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Acid–base reaction

An acid–base reaction is a chemical reaction that occurs between an acid and a base, which can be used to determine pH. Several theoretical frameworks provide alternative conceptions of the reaction mechanisms and their application in solving related problems; these are called the acid–base theories, for example, Brønsted–Lowry acid–base theory.

Hydroxide anion

Hydroxide is a diatomic anion with chemical formula OH. It consists of an oxygen and hydrogen atom held together by a covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It functions as a base, a ligand, a nucleophile, and a catalyst. The hydroxide ion forms salts, some of which dissociate in aqueous solution, liberating solvated hydroxide ions. Sodium hydroxide is a multi-million-ton per annum commodity chemical. A hydroxide attached to a strongly electropositive center may itself ionize, liberating a hydrogen cation (H+), making the parent compound an acid.

An acid dissociation constant, Ka, is a quantitative measure of the strength of an acid in solution. It is the equilibrium constant for a chemical reaction known as dissociation in the context of acid–base reactions.

In chemistry, an amphoteric compound is a molecule or ion that can react both as an acid and as a base. Many metals (such as copper, zinc, tin, lead, aluminium, and beryllium) form amphoteric oxides or hydroxides. Amphoterism depends on the oxidation states of the oxide. Al2O3 is an example of an amphoteric oxide.

Lewis acids and bases

A Lewis acid is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any species that has a filled orbital containing an electron pair which is not involved in bonding but may form a dative bond with a Lewis acid to form a Lewis adduct. For example, NH3 is a Lewis base, because it can donate its lone pair of electrons. Trimethylborane (Me3B) is a Lewis acid as it is capable of accepting a lone pair. In a Lewis adduct, the Lewis acid and base share an electron pair furnished by the Lewis base, forming a dative bond. In the context of a specific chemical reaction between NH3 and Me3B, the lone pair from NH3 will form a dative bond with the empty orbital of Me3B to form an adduct NH3•BMe3. The terminology refers to the contributions of Gilbert N. Lewis.

In organic and inorganic chemistry, nucleophilic substitution is a fundamental class of reactions in which an electron rich nucleophile selectively bonds with or attacks the positive or partially positive charge of an atom or a group of atoms to replace a leaving group; the positive or partially positive atom is referred to as an electrophile. The whole molecular entity of which the electrophile and the leaving group are part is usually called the substrate. The nucleophile essentially attempts to replace the leaving group as the primary substituent in the reaction itself, as a part of another molecule.

Alkylation chemical reaction

Alkylation is the transfer of an alkyl group from one molecule to another. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion or a carbene (or their equivalents). An alkyl group is a piece of a molecule with the general formula CnH2n+1, where n is the integer depicting the number of carbons linked together. For example, a methyl group (n = 1, CH3) is a fragment of a methane molecule (CH4). Alkylating agents use selective alkylation by adding the desired aliphatic carbon chain to the previously chosen starting molecule. This is one of many known chemical syntheses. Alkyl groups can also be removed in a process known as dealkylation. Alkylating agents are often classified according to their nucleophilic or electrophilic character.

In chemistry, protonation is the addition of a proton (H+) to an atom, molecule, or ion, forming the conjugate acid. Some examples include

Deprotonation is the removal (transfer) of a proton (a hydrogen cation, H+) from a Brønsted–Lowry acid in an acid-base reaction. The species formed is the conjugate base of that acid. The complementary process, when a proton is added (transferred) to a Brønsted–Lowry base, is protonation. The species formed is the conjugate acid of that base.

Methylamine is an organic compound with a formula of CH3NH2. This colorless gas is a derivative of ammonia, but with one hydrogen atom being replaced by a methyl group. It is the simplest primary amine. It is sold as a solution in methanol, ethanol, tetrahydrofuran, or water, or as the anhydrous gas in pressurized metal containers. Industrially, methylamine is transported in its anhydrous form in pressurized railcars and tank trailers. It has a strong odor similar to fish. Methylamine is used as a building block for the synthesis of many other commercially available compounds.

Organotin chemistry branch of organic chemistry

Organotin compounds or stannanes are chemical compounds based on tin with hydrocarbon substituents. Organotin chemistry is part of the wider field of organometallic chemistry. The first organotin compound was diethyltin diiodide ((C2H5)2SnI2), discovered by Edward Frankland in 1849. The area grew rapidly in the 1900s, especially after the discovery of the Grignard reagents, which are useful for producing Sn-C bonds. The area remains rich with many applications in industry and continuing activity in the research laboratory.

<i>n</i>-Butyllithium chemical compound

n-Butyllithium is an organolithium reagent. It is widely used as a polymerization initiator in the production of elastomers such as polybutadiene or styrene-butadiene-styrene (SBS). Also, it is broadly employed as a strong base (superbase) in the synthesis of organic compounds as in the pharmaceutical industry.

Metal ammine complex class of chemical compounds

In coordination chemistry, metal ammine complexes are metal complexes containing at least one ammonia (NH3) ligand. "Ammine" is spelled this way due to historical reasons; in contrast, alkyl or aryl bearing ligands are spelt with a single "m". Almost all metal ions bind ammonia as a ligand, but the most prevalent examples of ammine complexes are for Cr(III), Co(III), Ni(II), Cu(II) as well as several platinum group metals.

Lithium bis(trimethylsilyl)amide chemical compound

Lithium bis(trimethylsilyl)amide is a lithiated organosilicon compound with the formula LiN(SiMe3)2. It is commonly abbreviated as LiHMDS (lithium hexamethyldisilazide - a reference to its conjugate acid HMDS) and is primarily used as a strong non-nucleophilic base and as a ligand. Like many lithium reagents it has a tendency to aggregate and will form a cyclic trimer in the absence of coordinating species.

Associative substitution describes a pathway by which compounds interchange ligands. The terminology is typically applied to coordination and organometallic complexes, but resembles the Sn2 mechanism in organic chemistry. The opposite pathway is dissociative substitution, being analogous to the Sn1 pathway. Intermediate pathways exist between the pure associative and pure dissociative pathways, these are called interchange mechanisms.

Dissociative substitution describes a pathway by which compounds interchange ligands. The term is typically applied to coordination and organometallic complexes, but resembles the Sn1 mechanism in organic chemistry. This pathway can be well described by the cis effect, or the labilization of CO ligands in the cis position. The opposite pathway is associative substitution, being analogous to Sn2 pathway. Intermediate pathways exist between the pure dissociative and pure associative pathways, these are called interchange mechanisms.

The Hinsberg reaction is a lab test for the detection of primary, secondary and tertiary amines. In this test, the amine is shaken well with Hinsberg reagent in the presence of aqueous alkali. A reagent containing an aqueous sodium hydroxide solution and benzenesulfonyl chloride is added to a substrate. A primary amine will form a soluble sulfonamide salt. Acidification of this salt then precipitates the sulfonamide of the primary amine. A secondary amine in the same reaction will directly form an insoluble sulfonamide. A tertiary amine will not react with the sulfonamide but is insoluble. After adding dilute acid this insoluble amine is converted to a soluble Ammonium salt. In this way the reaction can distinguish between the three types of amines.

Metal amides

Metal amides (systematic name metal azanides) are a class of coordination compounds composed of a metal center with amide ligands of the form NR2. Amide ligands have two electron pairs available for bonding. In principle, they can be terminal or bridging. In these two examples, the dimethylamido ligands are both bridging and terminal:

Metal halides

Metal halides are compounds between metals and halogens. Some, such as sodium chloride are ionic, while others are covalently bonded. Covalently bonded metal halides may be discrete molecules, such as uranium hexafluoride, or they may form polymeric structures, such as palladium chloride.

References

  1. G. L. Miessler and D. A. Tarr “Inorganic Chemistry” 3rd Ed, Pearson/Prentice Hall publisher, ISBN   0-13-035471-6.
  2. Clark, C. R. and Buckingham, D. A., "Alkaline hydrolysis of [Co(cyclen)(O2CO)]+ and direct observation of deprotonated SN1CB intermediates", Inorganica Chimica Acta, 1997, 254, 339-343.