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Spin States (d Electrons)
Spin states when describing transition metal coordination complexes refers to the potential spin configurations of the central metal's d electrons. For several oxidation states, metals can adopt high-spin and low-spin configurations. The ambiguity only applies to first row metals, because second- and third-row metals are invariably low-spin. These configurations can be understood through the two major models used to describe coordination complexes; crystal field theory and ligand field theory (a more advanced version based on molecular orbital theory). High-spin vs. low-spin Octahedral complexes The Δ splitting of the ''d'' orbitals plays an important role in the electron spin state of a coordination complex. Three factors affect Δ: the period (row in periodic table) of the metal ion, the charge of the metal ion, and the field strength of the complex's ligands as described by the spectrochemical series. Only octahedral complexes of first row transition metals adopt high ...
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Transition Metal
In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can use d orbitals as valence orbitals to form chemical bonds. The lanthanide and actinide elements (the f-block) are called inner transition metals and are sometimes considered to be transition metals as well. Since they are metals, they are lustrous and have good electrical and thermal conductivity. Most (with the exception of group 11 and group 12) are hard and strong, and have high melting and boiling temperatures. They form compounds in any of two or more different oxidation states and bind to a variety of ligands to form coordination complexes that are often coloured. They form many useful alloys and are often employed as catalysts in elemental form or in compounds such as coordination complexes and oxides. Most are strongly param ...
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Bis(trimethylsilyl)amide
Bis(trimethylsilyl)amine (also known as hexamethyldisilazane and HMDS) is an organosilicon compound with the molecular formula CH3)3Sisub>2NH. The molecule is a derivative of ammonia with trimethylsilyl groups in place of two hydrogen atoms. An electron diffraction study shows that silicon-nitrogen bond length (173.5 pm) and Si-N-Si bond angle (125.5°) to be similar to disilazane (in which methyl groups are replaced by hydrogen atoms) suggesting that steric factors are not a factor in regulating angles in this case. This colorless liquid is a reagent and a precursor to bases that are popular in organic synthesis and organometallic chemistry. Additionally, HMDS is also increasingly used as molecular precursor in chemical vapor deposition techniques to deposit silicon carbonitride thin films or coatings. Synthesis and derivatives Bis(trimethylsilyl)amine is synthesized by treatment of trimethylsilyl chloride with ammonia: :2 (CH3)3SiCl + 3 NH3 → CH3)3Sisub>2NH + 2 NH4Cl Ammoniu ...
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Picometre
The picometre (international spelling as used by the International Bureau of Weights and Measures; SI symbol: pm) or picometer (American spelling) is a unit of length in the International System of Units (SI), equal to , or one trillionth of a metre, which is the SI base unit of length. The picometre is one thousand femtometres, one thousandth of a nanometre ( nm), one millionth of a micrometre (also known as a micron), one billionth of a millimetre, and one trillionth of a metre. The symbol μμ was once used for it. It is also one hundredth of an ångström, an internationally known (but non-SI) unit of length. Use The picometre's length is of an order so small that its application is almost entirely confined to particle physics, quantum physics, chemistry and acoustics. Atoms are between 62 and 520 pm in diameter, and the typical length of a carbon–carbon single bond is 154 pm. Smaller units still may be used to describe smaller particles (some of which are ...
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Ionic Radius
Ionic radius, ''r''ion, is the radius of a monatomic ion in an ionic crystal structure. Although neither atoms nor ions have sharp boundaries, they are treated as if they were hard spheres with radii such that the sum of ionic radii of the cation and anion gives the distance between the ions in a crystal lattice. Ionic radii are typically given in units of either picometers (pm) or angstroms (Å), with 1 Å = 100 pm. Typical values range from 31 pm (0.3 Å) to over 200 pm (2 Å). The concept can be extended to solvated ions in liquid solutions taking into consideration the solvation shell. Trends Ions may be larger or smaller than the neutral atom, depending on the ion's electric charge. When an atom loses an electron to form a cation, the other electrons are more attracted to the nucleus, and the radius of the ion gets smaller. Similarly, when an electron is added to an atom, forming an anion, the added electron increases the size of the e ...
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Cyanonickelate
The cyanonickelates are a class of chemical compound containing anions consisting of nickel atoms, and cyanide groups. The most important of these are the tetracyanonickelates containing four cyanide groups per nickel. The tetracyanonickelates contain the i(CN)4sup>2− anion. This can exist in solution or in solid salts. The ion has cyanide groups arranged in a square around the central nickel ion. The symmetry of the ion is D4''h''. The distance from the nickel atom to the carbon is 1.87 Å, and the carbon-nitrogen distance is 1.16 Å. Tetracyanonickelate(II) can be oxidised electrochemically in solution to yield tetracyanonickelate(III) i(CN)4sup>−. i(CN)4sup>− is unstable and Ni(III) oxidises the cyanide to cyanate Cyanate is an anion with the structural formula , usually written . It also refers to any salt containing it, such as ammonium cyanate. It is an isomer of the much less stable fulminate anion .William R. Martin and David W. Ball (2019): "Smal ...
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Tetrachloronickelate
Tetrachloronickelate is the metal complex with the formula iCl4sup>2−. Salts of the complex are available with a variety of cations, but a common one is tetraethylammonium. When concentrated lithium chloride and nickel chloride solution in water is mixed, only a pentaaquachloro complex is formed: i(H2O)5Clsup>+. However in other organic solvents, or molten salts the tetrachloronickelate ion can form. Nickel can be separated from such a solution in water or methanol, by partitioning it into a cyclohexane solution of amines. Organic ammonium salts of the type (R3NH)2 iCl4are often thermochromic (R = Me, Et, Pr). Near room temperature, these salts are yellow , but these solids become blue when heated to near 70 °C. The bright blue color is characteristic of tetrahedral iCl4sup>2−, the intensity being a consequence of the Laporte selection rule. The yellow color results from a polymer consisting of octahedral Ni centers. The corresponding tetrabromonickelates are als ...
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Hexaamminenickel Chloride
Hexaamminenickel chloride is the chemical compound with the formula i(NH3)6l2. It is the chloride salt of the metal ammine complex i(NH3)6sup>2+. The cation features six ammonia (called ammines in coordination chemistry) ligands attached to the nickel(II) ion. Properties and structure i(NH3)6sup>2+, like all octahedral nickel(II) complexes, is paramagnetic with two unpaired electrons localized on each Ni center. i(NH3)6l2 is prepared by treating aqueous nickel(II) chloride with ammonia Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous was .... It is useful as a molecular source of anhydrous nickel(II).G. S. Girolami, T. B. Rauchfuss, and R. J. Angelici (1999) ''Synthesis and Technique in Inorganic Chemistry'', University Science Books: Mill Valley, CA. References {{reflist Nickel ...
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Hexamminecobalt(III) Chloride
Hexaamminecobalt(III) chloride is the chemical compound with the formula o(NH3)6l3. It is the chloride salt of the coordination complex o(NH3)6sup>3+, which is considered an archetypal "Werner complex", named after the pioneer of coordination chemistry, Alfred Werner. The cation itself is a metal ammine complex with six ammonia ligands attached to the cobalt(III) ion. Originally salts of o(NH3)6sup>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 similar complexes also had color names, such as ''purpureo'' (Latin: purple) for a cobalt pentammine complex, and ''praseo'' (Greek: green) and ''violeo'' (Latin: violet) for two isomeric tetrammine complexes. Properties and structure o(NH3)6sup>3+ is diamagnetic, with a low-spin 3d6 octahedral Co(III) center. The cation obeys the 18-electron rule and is considered to be a classic example of an ex ...
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Diamagnetic
Diamagnetic materials are repelled by a magnetic field; an applied magnetic field creates an induced magnetic field in them in the opposite direction, causing a repulsive force. In contrast, paramagnetic and ferromagnetic materials are attracted by a magnetic field. Diamagnetism is a quantum mechanical effect that occurs in all materials; when it is the only contribution to the magnetism, the material is called diamagnetic. In paramagnetic and ferromagnetic substances, the weak diamagnetic force is overcome by the attractive force of magnetic dipoles in the material. The magnetic permeability of diamagnetic materials is less than the permeability of vacuum, ''μ''0. In most materials, diamagnetism is a weak effect which can be detected only by sensitive laboratory instruments, but a superconductor acts as a strong diamagnet because it repels a magnetic field entirely from its interior. Diamagnetism was first discovered when Anton Brugmans observed in 1778 that bismuth was repel ...
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Ferricyanide
Ferricyanide is the anion e(CN)6sup>3−. It is also called hexacyanoferrate(III) and in rare, but systematic nomenclature, hexacyanidoferrate(III). The most common salt of this anion is potassium ferricyanide, a red crystalline material that is used as an oxidant in organic chemistry. Properties e(CN)6sup>3− consists of a Fe3+ center bound in octahedral geometry to six cyanide ligands. The complex has Oh symmetry. The iron is low spin and easily reduced to the related ferrocyanide ion e(CN)6sup>4−, which is a ferrous (Fe2+) derivative. This redox couple is reversible and entails no making or breaking of Fe–C bonds: : e(CN)6sup>3− + e− ⇌ e(CN)6sup>4− This redox couple is a standard in electrochemistry. Compared to main group cyanides like potassium cyanide, ferricyanides are much less toxic because of the strong bond between the cyanide ion (CN− ) and the Fe3+. They do react with mineral acids, however, to release highly toxic hydrogen cyanide gas. Us ...
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Tris(acetylacetonato)iron(III)
Tris(acetylacetonato) iron(III), often abbreviated Fe(acac)3, is a ferric coordination complex featuring acetylacetonate (acac) ligands, making it one of a family of metal acetylacetonates. It is a red air-stable solid that dissolves in nonpolar organic solvents. Preparation Fe(acac)3 is prepared by treating freshly precipitated Fe(OH)3 with acetylacetone. :Fe(OH)3 + 3 HC5H7O2 → Fe(C5H7O2)3 + 3 H2O Structure and properties Fe(acac)3 is an octahedral complex with six equivalent Fe-O bonds with bond distances of about 2.00 Å. The regular geometry is consistent with a high-spin Fe3+ core. As the metal orbitals are all evenly occupied the complex is not subject to Jahn-Teller distortions and thus adopts a D3 molecular symmetry. In contrast, the related metal acetylacetonate Mn(acac)3 adopts a more distorted octahedral structure. The 5 unpaired ''d''-electrons also result in the complex being paramagnetic, with a magnetic moment of 5.90 μB. Fe(acac)3 possesses helical chirali ...
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Noninnocent Ligand
In chemistry, a (redox) non-innocent ligand is a ligand in a metal complex where the oxidation state is not clear. Typically, complexes containing non-innocent ligands are redox active at mild potentials. The concept assumes that redox reactions in metal complexes are either metal or ligand localized, which is a simplification, albeit a useful one. C.K. Jørgensen first described ligands as "innocent" and "suspect": "Ligands are innocent when they allow oxidation states of the central atoms to be defined. The simplest case of a suspect ligand is NO..." Redox reactions of complexes of innocent vs. non-innocent ligands Conventionally, redox reactions of coordination complexes are assumed to be metal-centered. The reduction of MnO4− to MnO42− is described by the change in oxidation state of manganese from 7+ to 6+. The oxide ligands do not change in oxidation state, remaining 2-. Oxide is an innocent ligand. Another example of conventional metal-centered redox couple is ...
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