Metal ammine complex

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Template:Short description

File:Tetraamminediaquacopper(II)-3D-balls.png
Ball-and-stick model of the tetraamminediaquacopper(II) cation, Template:Chem2

In coordination chemistry, metal ammine complexes are metal complexes containing at least one ammonia (Template:Chem2) ligand. "Ammine" is spelled this way for historical reasons;[1] 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.[2]

History

File:PtAmineOldvsNewView.png
Structural representations used by Alfred Werner (right) and Sophus Mads Jørgensen for one isomer of the dichloride salt of the complex Template:Chem2.[3]

Ammine complexes played a major role in the development of coordination chemistry, specifically determination of the stereochemistry and structure. They are easily prepared, and the metal-nitrogen ratio can be determined by elemental analysis. Through studies mainly on the ammine complexes, Alfred Werner developed his Nobel Prize-winning concept of the structure of coordination compounds (see Figure).[4][2]

Originally salts of [Co(NH3)6]3+ were described as the luteo (Latin: yellow) complex of cobalt. This name has been discarded as modern chemistry considers color less important than molecular structure. Other metal ammine complexes also were labeled according to their color, such as purpureo (Latin: purple) for a cobalt pentammine complex, and praseo (Greek: green) and violeo (Latin: violet) for two isomeric tetrammine complexes.[5]

One of the first ammine complexes to be described was Magnus' green salt, which consists of the platinum tetrammine complex Template:Chem2.[6]

Structure and bonding

Ammonia is a pure σ-donor, in the middle of the spectrochemical series, and shows intermediate hard–soft behaviour (see also ECW model[7][8] ).

Ammonia is classified as an L ligand in the Covalent bond classification method. In the usual electron counting method, it is a two-electron ligand. Ammonia is also compact such that steric effects are negligible. These factors simplify interpretation of structural and spectroscopic results.The Co–N distances in complexes Template:Chem2 have been examined repeatedly by X-ray crystallography.[9]

M–N distances for Template:Chem2
M n+ M–N distance (Å) d-electron configuration comment
Co 3+ 1.936 t2g6 eg0 low-spin trications are small
Co 2+ 2.114 t2g5 eg2 population of eg orbital and lower positive charge
Ru 3+ 2.104 t2g5 eg0 low spin trication, but Ru is intrinsically larger than Co
Ru 2+ 2.144 t2g6 eg0 low spin dication

Examples

Homoleptic poly(ammine) complexes are known for many of the transition metals. Most often, they have the formula Template:Chem2 where n = 2, 3, and even 4 (M = Pt).[10]

Platinum group metals

Platinum group metals form diverse ammine complexes. Pentaamine(dinitrogen)ruthenium(II) and the Creutz–Taube complex are well-studied examples of historic significance. The complex cis-Template:Chem2, under the name Cisplatin, is an important anticancer drug. Pentamminerhodium chloride (Template:Chem2) is an intermediate in the purification of rhodium from its ores.

Cobalt(III) and chromium(III)

The ammines of chromium(III) and cobalt(III) are of historic significance. Both families of ammines are relatively inert kinetically, which allows the separation of isomers.[11] For example, tetraamminedichlorochromium(III) chloride, Template:Chem2, has two forms - the cis isomer is violet, while the trans isomer is green. The trichloride of the hexaammine (hexamminecobalt(III) chloride, Template:Chem2) exists as only a single isomer. "Reinecke's salt" with the formula Template:Chem2 was first reported in 1863.[12]

Nickel(II), zinc(II), copper(II)

File:CoA5ClCl2.jpg
Sample of chloropentamminecobalt chloride Template:Chem2, illustrating the vibrant colors typical of transition metal ammine complexes.

Zinc(II) forms a colorless tetraammine with the formula Template:Chem2.[13] Like most zinc complexes, it has a tetrahedral structure. Hexaamminenickel is violet, and the copper(II) complex is deep blue. The latter is characteristic of the presence of copper(II) in qualitative inorganic analysis.

Copper(I), silver(I), and gold(I)

Copper(I) forms only labile complexes with ammonia, including the trigonal planar [Cu(NH3)3]+.[14] Silver gives the diammine complex [Ag(NH3)2]+ with linear coordination geometry.[15] It is this complex that forms when otherwise rather insoluble silver chloride dissolves in aqueous ammonia. The same complex is the active ingredient in Tollens' reagent. Gold(I) chloride reacts with ammonia to form Template:Chem2.[16]

Reactions

Ligand exchange and redox reactions

Since ammonia is a stronger ligand in the spectrochemical series than water, metal ammine complexes are stabilized relative to the corresponding aquo complexes. For similar reasons, metal ammine complexes are less strongly oxidizing than are the corresponding aquo complexes. The latter property is illustrated by the stability of Template:Chem2 in aqueous solution and the nonexistence of Template:Chem2 (which would oxidize water).

Acid-base reactions

Once complexed to a metal ion, ammonia is no longer basic. This property is illustrated by the stability of some metal ammine complexes in strong acid solutions. When the M–Template:Chem2 bond is weak, the ammine ligand dissociates and protonation ensues. The behavior is illustrated by the respective non-reaction and reaction with Template:Chem2 and Template:Chem2 toward aqueous acids. Related is the reaction of mercury(II) chloride with ammonia (Calomel reaction), where the resulting mercuric amidochloride is highly insoluble.

Template:Chem2

The ammine ligands are more acidic than is ammonia (pKa ~ 33). For highly cationic complexes such as [[Hexaammineplatinum(IV) chloride|Template:Chem2]], the conjugate base can be obtained. The deprotonation of cobalt(III) ammine-halide complexes, e.g. [[chloropentamminecobalt chloride|Template:Chem2]] labilises the Co–Cl bond, according to the Sn1CB mechanism.

Oxidation of ammonia

Deprotonation can be combined with oxidation, allowing the conversion of ammine complexes into nitrosyl complexes:[17]

Template:Chem2

H-atom transfer

In some ammine complexes, the N–H bond is weak. Thus one molybdenum ammine complex evolve hydrogen:[17]

Template:Chem2

This behavior is relevant to the use of metal-ammine complexes as catalysts for the oxidation of ammonia.[18]

Applications

Metal ammine complexes find many uses. Cisplatin (cis-Template:Chem2) is a drug used in treating cancer.[19] Many other amine complexes of the platinum group metals have been evaluated for this application.

In the separation of the individual platinum metals from their ore, several schemes rely on the precipitation of Template:Chem2. In some separation schemes, palladium is purified by manipulating equilibria involving Template:Chem2, Template:Chem2, and Template:Chem2 (Magnus's green salt).

In the processing of cellulose, the copper ammine complex known as Schweizer's reagent (Template:Chem2) is sometimes used to solubilise the polymer. Schweizer's reagent is prepared by treating an aqueous solutions of copper(II) ions with ammonia. Initially, the light blue hydroxide precipitates only to redissolve upon addition of more ammonia:

Template:Chem2
Template:Chem2

Silver diammine fluoride (Template:Chem2) is a topical medicament (drug) used to treat and prevent dental caries (cavities) and relieve dentinal hypersensitivity.[20]

See also

References

  1. ↑ Script error: No such module "citation/CS1".
  2. ↑ a b A. von Zelewsky "Stereochemistry of Coordination Compounds" John Wiley: Chichester, 1995. Template:ISBN.
  3. ↑ Alfred Werner "Beitrag zur Konstitution anorganischer Verbindungen" Zeitschrift für anorganische Chemie 1893, Volume 3, pages 267–330.Script error: No such module "doi".
  4. ↑ "Werner Centennial" George B. Kauffman, Ed. Adv. Chem. Ser., 1967, Volume 62. Template:ISBN
  5. ↑ Script error: No such module "citation/CS1".
  6. ↑ Script error: No such module "Citation/CS1".
  7. ↑ Laurence, C. and Gal, J-F. Lewis Basicity and Affinity Scales, Data and Measurement, (Wiley 2010) pp 50–51 ISBN 978-0-470-74957-9
  8. ↑ Script error: No such module "Citation/CS1". The plots shown in this paper used older parameters. Improved E&C parameters are listed in ECW model.
  9. ↑ Script error: No such module "Citation/CS1".
  10. ↑ Script error: No such module "Citation/CS1".
  11. ↑ Basolo, F.; Pearson, R. G. "Mechanisms of Inorganic Reactions." John Wiley and Son: New York: 1967. Template:ISBN
  12. ↑ Reinecke, A. "Über Rhodanchromammonium-Verbindungen" Annalen der Chemie und Pharmacie, volume 126, pages 113-118 (1863). Script error: No such module "doi"..
  13. ↑ Script error: No such module "Citation/CS1".
  14. ↑ Script error: No such module "Citation/CS1".
  15. ↑ Script error: No such module "Citation/CS1".
  16. ↑ Script error: No such module "Citation/CS1".
  17. ↑ a b Script error: No such module "Citation/CS1".
  18. ↑ Script error: No such module "Citation/CS1".
  19. ↑ S. J. Lippard, J. M. Berg "Principles of Bioinorganic Chemistry" University Science Books: Mill Valley, CA; 1994. Template:ISBN.
  20. ↑ Script error: No such module "Citation/CS1".

Template:Coordination complexes

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