History Of Coordination Compounds

Perhaps the earliest known coordination compound is the bright

red alizarin dyefirst used in India and known to the ancient Persians and
Egyptians. It is a calcium aluminum chelate complex of
hydroxyanthraquinone. The first scientifically recorded observation of a
completely inorganic coordination compound is German chemist, physician,
and alchemist Andreas Libavius’s description in 1597 of the blue colour (due
to [Cu(NH3)4]2+) formed when lime water containing sal ammoniac (NH4Cl)
comes into contact with brass.
Another example of a coordination compound is the substance Prussian blue,
with formula KFe[Fe(CN)6], which has been used as an artist’s pigment since
the beginning of the 18th century. Another early example of the preparation of
a coordination compound is the use in 1760 of a sparingly soluble
compound, potassium hexachloroplatinate(2−), K2[PtCl6], to refine the
element platinum.
The sustained and systematic development of modern coordination chemistry,
however, usually is considered to have begun with the discovery by the
French chemist B.M. Tassaert in 1798 that ammoniacal solutions of cobalt
chloride, CoCl3, develop a brownish mahogany colour. He failed to follow up
on his discovery, however. It remained for others to isolate orange crystals
with the compositionCoCl3 ∙ 6NH3, the correct formulation of which is
recognized to be [Co(NH3)6]Cl3; this shows that the six ammonia molecules are
associated with the cobalt(3+) ionand the positive charge is balanced by three
chloride anions. The particularly significant feature of this observation was the
recognition that two independently stable compounds (i.e., cobalt chloride
and ammonia) could combine to form a new chemical compound with
properties quite different from those of the constituent compounds.
In the 19th century, as more complexes were discovered, a number of
theories were proposed to account for their formation and properties. The
most successful and widely accepted of these theories was the so-called
chain theory (1869) of the Swedish chemist Christian Wilhelm Blomstrand, as
modified and developed by the Danish chemist Sophus Mads Jørgensen.
Jørgensen’s extensive preparations of numerous complexes provided the
experimental foundation not only for the Blomstrand-Jørgensen chain theory
but for Alsatian-born Swiss chemist Alfred Werner’s coordination theory
(1893) as well.
Blomstrand proposed that ammonia molecules could link together as −NH3−
chains, similar to −CH2− chains in hydrocarbons. The number of
NH3 molecules associated with the metal (i.e., the length of the chain)
depends on the metal and its oxidation state. Werner later explained this
number more adequately with his concept of coordination number. Jørgensen
proposed that atoms or groups that dissociated into ions in solution were
bonded through the NH3chain, whereas those that did not were bonded
directly to the metal ion.
Werner called these two types of bonding ionogenic and nonionogenic,
respectively. He proposed that the first occurred outside the coordination
sphere and the second inside it. In his first experimental work in support of his
coordination theory, Werner, together with the Italian Arturo Miolati,
determined the electrical conductivities of solutions of several series of
coordination compounds and claimed that the number of ions formed agreed
with the constitutions (manners of bonding of the ligands) predicted by his
theory rather than those predicted by Jørgensen.
Werner also established the configuration (the spatial arrangement of ligands
around the metal ion) of complexes by comparing the number and type
of isomers (see below Isomerism) that he actually prepared for various series
of compounds with the number and type theoretically predicted for various
configurations. In this way he was able not only to refute the rival Blomstrand-
Jørgensen chain theory but also to demonstrate unequivocally that
hexacoordinate cobalt(+3) possesses an octahedral configuration. Shortly
after he and his American student Victor L. King resolved (split)
[CoCl(NH3)(en)2]Cl2 into its optical isomers (see below Enantiomers and
Diastereomers) in 1911, Werner received the 1913 Nobel Prize for Chemistry.
The zenith of his quarter-century experimental achievements was attained
with his resolution of the completely inorganic tetranuclear compound,
[tris(tetraammine-μ-dihydroxocobalt(+3))cobalt(+3)](6+) bromide,

first prepared by Jørgensen, which effectively silenced even Werner’s

most vociferous opponents. Today he is universally recognized as the founder
not only of coordination chemistry but of structural inorganic chemistry as well.

Terjemahan :

Sejarah Senyawa Koordinasi

Mungkin kompleks koordinasi yang paling awal dikenal adalah pewarna alizarin merah terang yang
pertama kali digunakan di India dan dikenal oleh orang Persia dan Mesir kuno. Ini adalah kompleks
kalsium aluminium chelate dari hydroxyanthraquinone. Pengamatan ilmiah yang dicatat secara ilmiah
terhadap senyawa koordinasi anorganik yang pertama adalah deskripsi kimiawan Jerman, dokter, dan
alkemis Andreas Libavius pada 1597 warna biru (karena [Cu (NH3) 4] 2+) terbentuk saat air kapur
mengandung sal ammoniac (NH4Cl ) berhubungan dengan kuningan.

Contoh lain dari senyawa koordinasi adalah zat warna Prusia biru, dengan formula KFe [Fe (CN) 6], yang
telah digunakan sebagai pigmen seorang seniman sejak awal abad ke-18. Contoh awal lain dari
pembuatan senyawa koordinasi adalah penggunaan pada 1760 senyawa yang mudah larut, potassium
hexachloroplatinate (2-), K2 [PtCl6], untuk memperbaiki unsur platinum.

Perkembangan kimia modern koordinasi yang berkelanjutan dan sistematis, bagaimanapun, biasanya
dianggap telah dimulai dengan penemuan oleh ahli kimia B.M. Tassaert pada tahun 1798 bahwa larutan
amonia dari kobalt klorida, CoCl3, mengembangkan warna mahoni yang kecoklatan. Dia gagal
menindaklanjuti penemuannya. Tetap bagi orang lain untuk mengisolasi kristal oranye dengan komposisi
CoCl3 ∙ 6NH3, formulasi yang benar dikenali sebagai [Co (NH3) 6] Cl3; ini menunjukkan bahwa enam
molekul amonia dikaitkan dengan ion kobalt (3+) dan muatan positif diimbangi oleh tiga anion klorida.
Gambaran yang sangat penting dari pengamatan ini adalah pengakuan bahwa dua senyawa stabil secara
independen (yaitu kobalt klorida dan amonia) dapat digabungkan untuk membentuk senyawa kimia
baru dengan sifat yang sangat berbeda dengan senyawa penyusunnya.

Pada abad ke-19, ketika semakin banyak kompleks ditemukan, sejumlah teori diajukan untuk
menjelaskan pembentukan dan sifatnya. Teori yang paling berhasil dan diterima secara luas dari teori-
teori ini adalah apa yang disebut teori rantai (1869) ahli kimia Swedia Christian Wilhelm Blomstrand,
yang dimodifikasi dan dikembangkan oleh ahli kimia Denmark Sophus Mads Jørgensen. Persiapan
ekstensif Jørgensen dari berbagai kompleks memberikan landasan eksperimental tidak hanya untuk
teori rantai Blomstrand-Jørgensen tapi juga untuk teori koordinasi kimiawan kelahiran Bavaria asal Swiss
Alfred Werner (1893).

Blomstrand mengusulkan bahwa molekul amonia dapat dihubungkan bersama sebagai rantai-rantai
NH3, mirip dengan rantai CH2 dalam hidrokarbon. Jumlah molekul NH3 yang terkait dengan logam
(yaitu, panjang rantai) bergantung pada logam dan keadaan oksidasinya. Werner kemudian menjelaskan
jumlah ini lebih memadai dengan konsep nomor koordinasinya. Jørgensen mengusulkan agar atom atau
kelompok yang terdisosiasi menjadi ion dalam larutan diikat melalui rantai NH3, sedangkan yang tidak
terikat langsung ke ion logam.

Werner menyebut kedua jenis ikatan ionogenik dan nonionogenik ini. Dia mengusulkan agar yang
pertama terjadi di luar lingkup koordinasi dan yang kedua di dalamnya. Dalam karya eksperimental
pertamanya untuk mendukung teori koordinasinya, Werner, bersama dengan Arturo Miolati dari Italia,
menentukan konduktivitas listrik dari solusi beberapa rangkaian senyawa koordinasi dan mengklaim
bahwa jumlah ion yang terbentuk sesuai dengan konstitusi (perilaku ikatan ligan) diprediksi oleh
teorinya dan bukan yang diprediksi oleh Jørgensen.
 Werner juga menetapkan konfigurasi (susunan spasial ligan di sekitar ion logam) kompleks dengan
membandingkan jumlah dan jenis isomer (lihat di bawah Isomerisme) yang sebenarnya dipersiapkannya
untuk berbagai rangkaian senyawa dengan jumlah dan jenis yang diperkirakan secara teoritis untuk
berbagai konfigurasi. . Dengan cara ini, dia tidak hanya bisa menolak teori rantai saingan Blomstrand-
Jørgensen tapi juga untuk menunjukkan dengan pasti bahwa kobalt hekskoordinat (+3) memiliki
konfigurasi oktahedral. Tak lama setelah dia dan murid Amerikanya Victor L. King menyelesaikan (split)
[CoCl (NH3) (en) 2] Cl2 ke dalam isomer optiknya (lihat di bawah Enansiomer dan Diastereomer) pada
tahun 1911, Werner menerima Hadiah Nobel untuk Kimia tahun 1913. Pertengahan prestasi eksperimen
seperempat abad dicapai dengan resolusi senyawa tetranuklir yang hampir anorganik, kobalt
(tetraammine-μ-dihydroxocobalt (+3)) kobalt (+3)] (6+) bromida,

pertama disiapkan oleh Jørgensen, yang secara efektif membungkam lawan Werner yang paling gencar
sekalipun. Hari ini ia diakui secara universal sebagai pendiri bukan hanya kimia koordinasi tapi juga kimia
anorganik struktural.

The History of Coordination Compounds

1. Last updated
Apr 19, 2016

2. Share
Table of contents

One of the most important properties of metallic elements is their ability to act as Lewis acids
that form complexes with a variety of Lewis bases. A metal complex consists of a central metal
atom or ion that is bonded to one or more ligands (from the Latin ligare, meaning “to bind”),
which are ions or molecules that contain one or more pairs of electrons that can be shared with
the metal. Metal complexes can be neutral, such as Co(NH3)3Cl3; positively charged, such as
[Nd(H2O)9]3+; or negatively charged, such as [UF8]4−. Electrically charged metal complexes are
sometimes called complex ions. A coordination compound contains one or more metal
complexes.

Coordination compounds is a general terms that include compounds composed of a metal atom
or ion and one or more ligands (atoms, ions, or molecules) that formally donate electrons to the
metal. This definition includes compounds with metal-carbon bonds, called organometallic
compounds. Most d-transition metal ions have vacant d orbitals can shares in electron pairs by
actin gas as a Lewis acids and generating one or more coordinate (Dative) covalent
bonds incoordination compounds (coordination complexes, or complex ions). Complexes of
transition metal ions or molecules include cationic complexes
(e.g., [Cr(OH2)6]3+[Cr(OH2)6]3+, [Co(NH3)6]3+[Co(NH3)6]3+, [Ag(NH3)2]+[Ag(NH3)2]+),
anionic complexes (e.g., [Ni(CN4)]2−[Ni(CN4)]2−, [MnCl5]3−[MnCl5]3−), and neutral
complexes (e.g., [Fe(CO)5][Fe(CO)5], [Pt(NH)3))2Cl)2][Pt(NH)3))2Cl)2]). Complexes may
contain all of the same type of ligand, in which case they are termed homoleptic such as
[Co(NH3)6]3+, or they may contain a variety of ligand types, whereby they are described
as heteroleptic such as [Pt(NH3)2Cl2][Pt(NH3)2Cl2].

Coordination compounds have been known and used since antiquity; probably the oldest is the
deep blue pigment called Prussian blue: KFe2(CN)6KFe2(CN)6. The chemical nature of these
substances, however, was unclear for a number of reasons. For example, many compounds called
“double salts” were known, such as AlF3⋅3KFAlF3⋅3KF, Fe(CN))2⋅4KCNFe(CN))2⋅4KCN,
and ZnCl2⋅2CsClZnCl2⋅2CsCl, which were combinations of simple salts in fixed and apparently
arbitrary ratios. Why should \(AlF_3 \cdot 3KF\) exist but
not AlF3⋅4KFAlF3⋅4KF or AlF3⋅2KFAlF3⋅2KF? And why should a
3:1 KF:AlF3KF:AlF3 mixture have different chemical and physical properties than either of its
components? Similarly, adducts of metal salts with neutral molecules such as ammonia were also
known—for example, CoCl3⋅6NH3CoCl3⋅6NH3, which was first prepared sometime before
1798. Like the double salts, the compositions of these adducts exhibited fixed and apparently
arbitrary ratios of the components. For
example, CoCl3⋅6NH3CoCl3⋅6NH3, CoCl)3⋅5NH)3CoCl)3⋅5NH)3, CoCl)3⋅4NH)3CoCl)3⋅4N
H)3, and CoCl)3⋅3NH3CoCl)3⋅3NH3 were all known and had very different properties including
colors (Figure 2.2.1), but despite all attempts, chemists could not
prepare CoCl3⋅2NH3CoCl3⋅2NH3 or CoCl3⋅NH3CoCl3⋅NH3.

Figure 2.2.1: CoCl3⋅6NH3CoCl3⋅6NH3 (amarillo-naranja)

, CoCl3⋅5NH3CoCl3⋅5NH3 (morado) , CoCl3⋅4NH3CoCl3⋅4NH3 (verde)
and CoCl3⋅3NH3CoCl3⋅3NH3 (violeta . Images used with permission from Wikipedia.

While the empirical chemical formula for these coordination compounds were well
characterized, identifying the connectivity and correcting 3D structures were harder. Problem
occurs because in a compound with formula CoCl3⋅6NH3CoCl3⋅6NH3 and looking at advances
in organic bonding theory only three other atoms should be attached to Co-compare to 'normal'
salts such as FeCl3CoFeCl3Co was expected to have a 'valence' of three. If the chlorides are
assigned this role then what happens to six NH3NH3? From observation of the following
reactions

The Blomstrand-Jørgensen Chain Model

Although the chemical composition of such compounds was readily established by existing
analytical methods, their chemical nature was puzzling and highly controversial. The major
problem was that what we now call valence (i.e., the oxidation state) and coordination number
were thought to be identical. As a result, highly implausible (to modern eyes at least) structures
were proposed for such compounds, including the “Chattanooga choo-choo” model for
CoCl3·4NH3 shown here. C. W. Blomstrand (1826-1894) and S. M. Jørgensen (1837-1914)
proposed a "chain model" where ammonia groups in metal ammines are assumed to bonded
together in chains, which was sensible assumption since the description of organic molecules as
chains of \(-CH_2\) groups was very successful. One example would
be Co(NH3)5Cl3Co(NH3)5Cl3, a typical metal ammine with two possible chain theory structures
proposed (Figure 2.2.2).

Figure 2.2.2: Two possible Blomstrand-Jørgensen Chains for \(Co(NH_3)_5Cl_3\)

These structures agrees with the results of silver precipitation experiments and involves a chain
of four ammonia groups, which Jørgensen regarded as a particularly stable arrangement.

The Warner Coordination Theory

The modern theory of coordination chemistry is based largely on the work of Alfred Werner
(1866–1919; Nobel Prize in Chemistry in 1913). In a series of careful experiments carried out in
the late 1880s and early 1890s, he examined the properties of several series of metal halide
complexes with ammonia. For example, five different “adducts” of ammonia with PtCl4were
known at the time: PtCl4·nNH3 (n = 2–6). Some of Werner’s original data on these compounds
are shown in Table 23.8. The electrical conductivity of aqueous solutions of these compounds
was roughly proportional to the number of ions formed per mole, while the number of chloride
ions that could be precipitated as AgCl after adding Ag+(aq) was a measure of the number of
“free” chloride ions present. For example, Werner’s data on PtCl4·6NH3 in Table 23.8 showed
that all the chloride ions were present as free chloride. In contrast, PtCl4·2NH3 was a neutral
molecule that contained no free chloride ions.
ALFRED WERNER (1866–1919)
Werner, the son of a factory worker, was born in Alsace. He developed an interest in chemistry
at an early age, and he did his first independent research experiments at age 18. While doing his
military service in southern Germany, he attended a series of chemistry lectures, and he
subsequently received his PhD at the University of Zurich in Switzerland, where he was
appointed professor of chemistry at age 29. He won the Nobel Prize in Chemistry in 1913 for his
work on coordination compounds, which he performed as a graduate student and first presented
at age 26. Apparently, Werner was so obsessed with solving the riddle of the structure of
coordination compounds that his brain continued to work on the problem even while he was
asleep. In 1891, when he was only 25, he woke up in the middle of the night and, in only a few
hours, had laid the foundation for modern coordination chemistry.

Table 23.8: Werner’s Data on Complexes of Ammonia with PtCl4PtCl4

Complex Conductivity Number of Ions Number of Cl− Ions

(ohm−1) per Formula Unit Precipitated by Ag+

PtCl4·6NH3 523 5 4

PtCl4·5NH3 404 4 3

PtCl4·4NH3 299 3 2

PtCl4·3NH3 97 2 1

PtCl4·2NH3 0 0 0

These data led Werner to postulate that metal ions have two different kinds of valence: (1) a
primary valence (oxidation state) that corresponds to the positive charge on the metal ion and (2)
a secondary valence (coordination number) that is the total number of ligands bound to the metal
ion. If Pt had a primary valence of 4 and a secondary valence of 6, Werner could explain the
properties of the PtCl4·NH3 adducts by the following reactions, where the metal complex is
enclosed in square brackets:

[Pt(NH3)6]Cl4[Pt(NH3)5Cl]Cl3[Pt(NH3)4Cl2]Cl2[Pt(NH3)3Cl3]Cl[Pt(NH3)2Cl4]→[Pt(NH3)6]4
+(aq)+4Cl−(aq)→[Pt(NH3)5Cl]3+(aq)+3Cl−(aq)→[Pt(NH3)4Cl2]2+(aq)+2Cl−(aq)→[Pt(NH3)3C
l3]+(aq)+Cl−(aq)→[Pt(NH3)2Cl4]0(aq)(23.9)(23.9)[Pt(NH3)6]Cl4→[Pt(NH3)6]4+(aq)+4Cl−(aq)[Pt(NH
3)5Cl]Cl3→[Pt(NH3)5Cl]3+(aq)+3Cl−(aq)[Pt(NH3)4Cl2]Cl2→[Pt(NH3)4Cl2]2+(aq)+2Cl−(aq)[Pt(NH3)3Cl3]Cl
→[Pt(NH3)3Cl3]+(aq)+Cl−(aq)[Pt(NH3)2Cl4]→[Pt(NH3)2Cl4]0(aq)

Further work showed that the two missing members of the series—[Pt(NH3)Cl5]− and [PtCl6]2−—
could be prepared as their mono- and dipotassium salts, respectively. Similar studies established
coordination numbers of 6 for Co3+ and Cr3+ and 4 for Pt2+ and Pd2+.

Werner’s studies on the analogous Co3+ complexes also allowed him to propose a structural
model for metal complexes with a coordination number of 6. Thus he found that
[Co(NH3)6]Cl3 (yellow) and [Co(NH3)5Cl]Cl2 (purple) were 1:3 and 1:2 electrolytes.
Unexpectedly, however, two different [Co(NH3)4Cl2]Cl compounds were known: one was red,
and the other was green (part (a) in Figure 23.9). Because both compounds had the same
chemical composition and the same number of groups of the same kind attached to the same
metal, there had to be something different about the arrangement of the ligands around the metal
ion. Werner’s key insight was that the six ligands in [Co(NH3)4Cl2]Cl had to be arranged at the
vertices of an octahedron because that was the only structure consistent with the existence of
two, and only two, arrangements of ligands (part (b) in Figure 23.9. His conclusion was
corroborated by the existence of only two different forms of the next compound in the series:
Co(NH3)3Cl3.

Figure 23.9 Complexes with Different Arrangements of the Same Ligands Have Different
Properties. The [Co(NH3)4Cl2]+ ion can have two different arrangements of the ligands, which
results in different colors: if the two Cl− ligands are next to each other, the complex is red (a), but
if they are opposite each other, the complex is green (b).
EXAMPLE 4
In Werner’s time, many complexes of the general formula MA4B2 were known, but no more than
two different compounds with the same composition had been prepared for any metal. To
confirm Werner’s reasoning, calculate the maximum number of different structures that are
possible for six-coordinate MA4B2 complexes with each of the three most symmetrical possible
structures: a hexagon, a trigonal prism, and an octahedron. What does the fact that no more than
two forms of any MA4B2 complex were known tell you about the three-dimensional structures of
these complexes?

Given: three possible structures and the number of different forms known for MA4B2 complexes

Asked for: number of different arrangements of ligands for MA4B2 complex for each structure

Strategy:

Sketch each structure, place a B ligand at one vertex, and see how many different positions are
available for the second B ligand.

SOLUTION

The three regular six-coordinate structures are shown here, with each coordination position
numbered so that we can keep track of the different arrangements of ligands. For each structure,
all vertices are equivalent. We begin with a symmetrical MA6 complex and simply replace two of
the A ligands in each structure to give an MA4B2 complex:

For the hexagon, we place the first B ligand at position 1. There are now three possible places for
the second B ligand: at position 2 (or 6), position 3 (or 5), or position 4. These are the only
possible arrangements. The (1, 2) and (1, 6) arrangements are chemically identical because the
two B ligands are adjacent to each other. The (1, 3) and (1, 5) arrangements are also identical
because in both cases the two B ligands are separated by an A ligand.

Turning to the trigonal prism, we place the first B ligand at position 1. Again, there are three
possible choices for the second B ligand: at position 2 or 3 on the same triangular face, position 4
(on the other triangular face but adjacent to 1), or position 5 or 6 (on the other triangular face but
not adjacent to 1). The (1, 2) and (1, 3) arrangements are chemically identical, as are the (1, 5)
and (1, 6) arrangements.

In the octahedron, however, if we place the first B ligand at position 1, then we have only two
choices for the second B ligand: at position 2 (or 3 or 4 or 5) or position 6. In the latter, the two
B ligands are at opposite vertices of the octahedron, with the metal lying directly between them.
Although there are four possible arrangements for the former, they are chemically identical
because in all cases the two B ligands are adjacent to each other.

The number of possible MA4B2 arrangements for the three geometries is thus: hexagon, 3;
trigonal prism, 3; and octahedron, 2. The fact that only two different forms were known for all
MA4B2 complexes that had been prepared suggested that the correct structure was the octahedron
but did not prove it. For some reason one of the three arrangements possible for the other two
structures could have been less stable or harder to prepare and had simply not yet been
synthesized. When combined with analogous results for other types of complexes (e.g., MA3B3),
however, the data were best explained by an octahedral structure for six-coordinate metal
complexes.

EXERCISE 4
Determine the maximum number of structures that are possible for a four-coordinate
MA2B2 complex with either a square planar or a tetrahedral symmetrical structure.

Answer: square planar, 2; tetrahedral, 1

Structures of Metal Complexes

The coordination numbers of metal ions in metal complexes can range from 2 to at least 9. In
general, the differences in energy between different arrangements of ligands are greatest for
complexes with low coordination numbers and decrease as the coordination number increases.
Usually only one or two structures are possible for complexes with low coordination numbers,
whereas several different energetically equivalent structures are possible for complexes with
high coordination numbers (n > 6). The following presents the most commonly encountered
structures for coordination numbers 2–9. Many of these structures should be familiar to you from
our discussion of the valence-shell electron-pair repulsion (VSEPR) model because they
correspond to the lowest-energy arrangements of n electron pairs around a central atom.

NOTE
Compounds with low coordination numbers exhibit the greatest differences in energy between
different arrangements of ligands.

Coordination Number 2
Although it is rare for most metals, this coordination number is surprisingly common for
d10 metal ions, especially Cu+, Ag+, Au+, and Hg2+. An example is the [Au(CN)2]− ion, which is
used to extract gold from its ores. As expected based on VSEPR considerations, these complexes
have the linear L–M–L structure shown here.

Coordination Number 3

Although it is also rare, this coordination number is encountered with d10 metal ions such as
Cu+ and Hg2+. Among the few known examples is the HgI3− ion. Three-coordinate complexes
almost always have the trigonal planar structure expected from the VSEPR model.

Coordination Number 4
Two common structures are observed for four-coordinate metal complexes: tetrahedral and
square planar. The tetrahedral structure is observed for all four-coordinate complexes of
nontransition metals, such as [BeF4]2−, and d10 ions, such as [ZnCl4]2−. It is also found for four-
coordinate complexes of the first-row transition metals, especially those with halide ligands (e.g.,
[FeCl4]− and [FeCl4]2−). In contrast, square planar structures are routinely observed for four-
coordinate complexes of second- and third-row transition metals with d8 electron configurations,
such as Rh+ and Pd2+, and they are also encountered in some complexes of Ni2+ and Cu2+.
Coordination Number 5
This coordination number is less common than 4 and 6, but it is still found frequently in two
different structures: trigonal bipyramidal and square pyramidal. Because the energies of these
structures are usually rather similar for most ligands, many five-coordinate complexes have
distorted structures that lie somewhere between the two extremes.

Coordination Number 6
This coordination number is by far the most common. The six ligands are almost always at the
vertices of an octahedron or a distorted octahedron. The only other six-coordinate structure is the
trigonal prism, which is very uncommon in simple metal complexes.
Coordination Number 7
This relatively uncommon coordination number is generally encountered for only large metals
(such as the second- and third-row transition metals, lanthanides, and actinides). At least three
different structures are known, two of which are derived from an octahedron or a trigonal prism
by adding a ligand to one face of the polyhedron to give a “capped” octahedron or trigonal prism.
By far the most common, however, is the pentagonal bipyramid.

Coordination Number 8
This coordination number is relatively common for larger metal ions. The simplest structure is
the cube, which is rare because it does not minimize interligand repulsive interactions. Common
structures are the square antiprism and the dodecahedron, both of which can be generated from
the cube.

Coordination Number 9
This coordination number is found in larger metal ions, and the most common structure is the
tricapped trigonal prism, as in [Nd(H2O)9]3+.

Summary
Transition metals form metal complexes, polyatomic species in which a metal ion is bound to
one or more ligands, which are groups bound to a metal ion. Complex ions are electrically
charged metal complexes, and a coordination compound contains one or more metal complexes.
Metal complexes with low coordination numbers generally have only one or two possible
structures, whereas those with coordination numbers greater than six can have several different
structures. Coordination numbers of two and three are common for d10 metal ions. Tetrahedral
and square planar complexes have a coordination number of four; trigonal bipyramidal and
square pyramidal complexes have a coordination number of five; and octahedral complexes have
a coordination number of six. At least three structures are known for a coordination number of
seven, which is generally found for only large metal ions. Coordination numbers of eight and
nine are also found for larger metal ions.

Terjemahan

Salah satu sifat terpenting unsur logam adalah kemampuan mereka untuk bertindak sebagai asam Lewis
yang membentuk kompleks dengan berbagai basa Lewis. Kompleks logam terdiri dari atom logam pusat
atau ion yang terikat pada satu atau lebih ligan (dari bahasa Latin ligare, yang berarti "mengikat"), yaitu
ion atau molekul yang mengandung satu atau lebih pasang elektron yang dapat dibagi dengan logam.
Kompleks logam bisa netral, seperti Co (NH3) 3Cl3; bermuatan positif, seperti [Nd (H2O) 9] 3+; atau
bermuatan negatif, seperti [UF8] 4-. Kompleks logam bermuatan listrik kadang-kadang disebut ion
kompleks. Senyawa koordinasi mengandung satu atau lebih kompleks logam.

Senyawa koordinasi adalah istilah umum yang mencakup senyawa yang tersusun dari atom logam atau
ion dan satu atau lebih ligan (atom, ion, atau molekul) yang secara formal menyumbangkan elektron ke
logam. Definisi ini mencakup senyawa dengan ikatan logam-karbon, yang disebut senyawa
organologam. Sebagian besar ion logam transisi d memiliki orbital d yang kosong dapat berbagi
pasangan elektron dengan gas aktin sebagai asam Lewis dan menghasilkan satu atau lebih koordinat
(Dative) ikatan kovalen senyawa inkoordinasi (kompleks koordinasi, atau ion kompleks). Kompleks ion
logam transisi atau molekul meliputi kompleks kationik (misalnya, [Cr (OH2) 6] 3+, [Co (NH3) 6] 3+, [Ag
(NH3) 2] +), kompleks anionik (misalnya, [Ni (CN4)] 2-, [MnCl5] 3-), dan kompleks netral (misalnya, [Fe
(CO) 5], [Pt (NH) 3)) 2Cl) 2]). Kompleks dapat mengandung semua jenis ligan yang sama, dalam hal ini
disebut homoleptik seperti [Co (NH3) 6] 3+, atau mungkin mengandung berbagai jenis ligan, dimana ia
digambarkan sebagai heteroleptik seperti [Pt (NH3) 2Cl2].

Senyawa koordinasi telah dikenal dan digunakan sejak jaman dahulu; Mungkin yang tertua adalah
pigmen biru tua yang disebut Prusia biru: KFe2 (CN) 6. Sifat kimiawi zat ini, bagaimanapun, tidak jelas
karena sejumlah alasan. Sebagai contoh, banyak senyawa yang disebut "garam ganda" diketahui, seperti
AlF3⋅3KF, Fe (CN)) 2⋅4KCN, dan ZnCl2⋅2CsCl, yang merupakan kombinasi dari garam sederhana dalam
rasio tetap dan nampaknya sewenang-wenang. Mengapa harus \ (AlF_3 \ cdot 3KF \) ada tapi tidak
AlF3⋅4KF atau AlF3⋅2KF? Dan mengapa campuran 3: 1 KF: AlF3 memiliki sifat kimia dan fisik yang
berbeda dari komponennya? Demikian pula, adisi garam logam dengan molekul netral seperti amonia
juga diketahui - misalnya CoCl3⋅6NH3, yang pertama kali disiapkan sekitar tahun 1798. Seperti garam
ganda, komposisi aduct ini menunjukkan rasio tetap dan nampaknya sewenang-wenang komponennya. .
Misalnya CoCl3⋅6NH3, CoCl) 3⋅5NH) 3, CoCl) 3⋅4NH) 3, dan CoCl) 3⋅3NH3 semuanya diketahui dan
memiliki sifat yang sangat berbeda termasuk warna (Gambar 2.2.1), namun terlepas dari semua upaya ,
ahli kimia tidak dapat menyiapkan CoCl3⋅2NH3 atau CoCl3⋅NH3.
6FADF573A.png

Gambar 2.2.1: CoCl3⋅6NH3 (amarillo-naranja), CoCl3⋅5NH3 (morado), CoCl3⋅4NH3 (verde) dan

CoCl3⋅3NH3 (violeta. Gambar yang digunakan dengan izin dari Wikipedia.

Sementara rumus kimia empiris untuk senyawa koordinasi ini ditandai dengan baik, mengidentifikasi
konektivitas dan memperbaiki struktur 3D lebih sulit. Masalah terjadi karena dalam senyawa dengan
formula CoCl3⋅6NH3 dan melihat kemajuan teori ikatan organik hanya tiga atom lainnya yang harus
dilekatkan pada Co-bandingkan dengan garam 'normal' seperti FeCl3Co diharapkan memiliki 'valensi'
tiga. Jika klorida diberi peran ini maka apa yang terjadi pada enam NH3? Dari pengamatan reaksi berikut

Model Rantai Blomstrand-Jørgensen

Meskipun komposisi kimia dari senyawa semacam itu mudah terbentuk dengan metode analisis yang
ada, sifat kimiawi mereka membingungkan dan sangat kontroversial. Masalah utamanya adalah bahwa
apa yang sekarang kita sebut valensi (yaitu, keadaan oksidasi) dan nomor koordinasi dianggap identik.
Akibatnya, struktur yang sangat tidak masuk akal (setidaknya untuk modern setidaknya) diusulkan untuk
senyawa semacam itu, termasuk model "Chattanooga choo-choo" untuk CoCl3 · 4NH3 yang ditunjukkan
di sini. CW Blomstrand (1826-1894) dan SM Jørgensen (1837-1914) mengusulkan "model rantai" di
mana kelompok amonia di amin logam diasumsikan terikat bersama dalam rantai, yang merupakan
asumsi yang masuk akal karena deskripsi molekul organik sebagai rantai \ -CH_2 \) kelompok sangat
sukses. Salah satu contohnya adalah Co (NH3) 5Cl3, logam ammine khas dengan dua struktur teori rantai
yang mungkin diusulkan (Gambar 2.2.2).

Gambar 2.2.2: Dua kemungkinan Rantai Blomstrand-Jørgensen untuk \ (Co (NH_3) _5Cl_3 \)
Struktur ini sesuai dengan hasil eksperimen presipitasi perak dan melibatkan rantai empat kelompok
amonia, yang menurut Jørgensen sebagai pengaturan yang sangat stabil.

Teori Koordinasi Warner

Teori modern tentang koordinasi kimia sebagian besar didasarkan pada karya Alfred Werner (1866-
1919; Hadiah Nobel untuk Kimia pada tahun 1913). Dalam serangkaian percobaan hati-hati yang
dilakukan pada akhir 1880-an dan awal 1890-an, dia memeriksa sifat beberapa rangkaian kompleks
halida logam dengan amonia. Sebagai contoh, lima "adducts" amonia yang berbeda dengan PtCl4
diketahui saat itu: PtCl4 · nNH3 (n = 2-6). Beberapa data asli Werner pada senyawa ini ditunjukkan pada
Tabel 23.8. Konduktivitas listrik larutan berair dari senyawa ini kira-kira sebanding dengan jumlah ion
yang terbentuk per mol, sedangkan jumlah ion klorida yang dapat diendapkan karena AgCl setelah
menambahkan Ag + (aq) adalah ukuran dari jumlah klorida "bebas" ion hadir Sebagai contoh, data
Werner pada PtCl4 · 6NH3 pada Tabel 23.8 menunjukkan bahwa semua ion klorida hadir sebagai klorida
bebas. Sebaliknya, PtCl4 · 2NH3 adalah molekul netral yang tidak mengandung ion klorida bebas.

ALFRED WERNER (1866-1919)

Werner, anak seorang pekerja pabrik, lahir di Alsace. Dia mengembangkan minat pada bidang kimia
sejak usia dini, dan dia melakukan eksperimen penelitian independen pertamanya pada usia 18 tahun.
Saat melakukan tugas militernya di Jerman selatan, dia menghadiri serangkaian kuliah kimia, dan
kemudian dia menerima gelar PhD di Universitas Zurich di Swiss, di mana dia diangkat menjadi profesor
kimia pada usia 29. Dia memenangkan Hadiah Nobel bidang Kimia pada tahun 1913 untuk karyanya
mengenai senyawa koordinasi, yang dia lakukan sebagai mahasiswa pascasarjana dan pertama kali
dipresentasikan pada usia 26. Rupanya, Werner begitu terobsesi dengan pemecahan teka-teki struktur
senyawa koordinasi yang otaknya terus bekerja pada masalah bahkan saat ia sedang tidur. Pada tahun
1891, ketika ia berusia 25 tahun, ia terbangun di tengah malam dan, hanya dalam beberapa jam, telah
meletakkan dasar untuk koordinasi kimia modern.

Data ini menyebabkan Werner mendalilkan bahwa ion logam memiliki dua jenis valensi yang berbeda:
(1) valensi primer (keadaan oksidasi) yang sesuai dengan muatan positif pada ion logam dan (2) valensi
sekunder (bilangan koordinasi) yaitu jumlah ligan terikat pada ion logam. Jika Pt memiliki valensi utama
4 dan valensi sekunder 6, Werner dapat menjelaskan sifat-sifat dari PtCl4 · NH3 yang diakumulasikan
oleh reaksi berikut, di mana kompleks logam dilekatkan dalam tanda kurung siku:
Pekerjaan lebih lanjut menunjukkan bahwa dua anggota seri yang hilang- [Pt (NH3) Cl5] - dan [PtCl6] 2 -
dapat dibuat sebagai garam mono dan dipotasumnya. Studi serupa menetapkan jumlah koordinasi 6
untuk Co3 + dan Cr3 + dan 4 untuk Pt2 + dan Pd2 +.

Studi Werner pada kompleks Co3 + yang analog juga memungkinkannya untuk mengusulkan model
struktural untuk kompleks logam dengan jumlah koordinasi 6. Jadi, ia menemukan bahwa [Co (NH3) 6]
Cl3 (kuning) dan [Co (NH3) 5Cl] Cl2 ( ungu) adalah 1: 3 dan 1: 2 elektrolit. Namun, tak terduga, dua
senyawa ClCl yang berbeda [Co (NH3) 4Cl2] diketahui: satu berwarna merah, dan yang lainnya berwarna
hijau (bagian (a) pada Gambar 23.9). Karena kedua senyawa memiliki komposisi kimia yang sama dan
jumlah kelompok yang sama dengan jenis logam yang sama, harus ada sesuatu yang berbeda tentang
pengaturan ligan di sekitar ion logam. Werner's key insight adalah bahwa enam ligan di [Co (NH3) 4Cl2]
Cl harus diatur pada simpul dari oktahedron karena itulah satu-satunya struktur yang sesuai dengan
keberadaan dua, dan hanya dua, susunan ligan (bagian b) pada Gambar 23.9 Kesimpulannya dikuatkan
dengan adanya hanya dua bentuk senyawa berikutnya yang berbeda dalam seri: Co (NH3) 3Cl3.

Struktur Kompleks Logam

Jumlah koordinasi ion logam di kompleks logam dapat berkisar dari 2 sampai setidaknya 9. Secara
umum, perbedaan energi antara pengaturan ligan yang berbeda sangat besar untuk kompleks dengan
jumlah koordinasi yang rendah dan menurun saat jumlah koordinasi meningkat. Biasanya hanya satu
atau dua struktur yang mungkin terjadi pada kompleks dengan jumlah koordinasi rendah, sedangkan
beberapa struktur ekuivalen yang berbeda bergantung pada kompleks dengan nomor koordinasi tinggi
(n> 6). Berikut ini adalah struktur yang paling sering ditemui untuk nomor koordinasi 2-9. Banyak
struktur ini harus Anda ketahui dari diskusi kita mengenai model toleransi mutasi elektron valensi
(VSEPR) karena sesuai dengan pengaturan energi terendah dari pasangan elektron di sekitar atom pusat.