Silanones
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Silanones
A silanone in chemistry is the silicon analogue of a ketone. The general description for this class of organic compounds is R1R2Si=O, with silicon connected to a terminal oxygen atom via a double bond and also with two organic residues (R). Silanones are extremely reactive and until 2013 were only detected by argon matrix isolation''On the proposed thermal interconversion of matrix-isolated dimethylsilylene and 1-methylsilene: their reactions with oxygen atom donors'' Charles A. Arrington, Robert West, Josef Michl J. Am. Chem. Soc., 1983, 105 (19), pp 6176–6177 ''Infrared spectroscopic evidence for silicon-oxygen double bonds: silanone and the silanoic and silicic acid molecules'' Robert Withnall, Lester Andrews J. Am. Chem. Soc., 1985, 107 (8), pp 2567–2568 or in the gas phase but not isolated. A synthesis of a stable silanone was reported in 2014. Silanones are of some interest to academic research, with their reactivity being of some relevance to the double bond rule. Sil ...
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Silicone
A silicone or polysiloxane is a polymer made up of siloxane (−R2Si−O−SiR2−, where R = organic group). They are typically colorless oils or rubber-like substances. Silicones are used in sealants, adhesives, lubricants, medicine, cooking utensils, thermal insulation, and electrical insulation. Some common forms include silicone oil, silicone grease, silicone rubber, silicone resin, and silicone caulk. Chemistry More precisely called polymerized siloxanes or polysiloxanes, silicones consist of an inorganic silicon–oxygen backbone chain (⋯−Si−O−Si−O−Si−O−⋯) with two organic groups attached to each silicon center. Commonly, the organic groups are methyl. The materials can be cyclic or polymeric. By varying the −Si−O− chain lengths, side groups, and crosslinking, silicones can be synthesized with a wide variety of properties and compositions. They can vary in consistency from liquid to gel to rubber to hard plastic. The most common siloxan ...
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Double Bond Rule
In chemistry, the double bond rule states that elements with a principal quantum number greater than 2 for their valence electrons (period 3 elements and higher) tend not to form multiple bonds (e.g. double bonds and triple bonds). The double bonds, when they exist, are often weak due to poor orbital overlap. Although such compounds are not intrinsically unstable, they instead tend to polymerize. An example is the rapid polymerization that occurs upon condensation of disulfur, the heavy analogue of . Numerous violations to the rule exist. Other meanings Another unrelated double bond rule exists that relates to the enhanced reactivity of sigma bonds attached to an atom adjacent to a double bond. In bromoalkenes, the C–Br bond is very stable, but in an allyl bromide, this bond is very reactive. Likewise, bromobenzenes are generally inert, whereas benzylic bromides are reactive. The first to observe the phenomenon was Conrad Laar Conrad Peter Laar (22 March 1853 – 11 Fe ...
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Pi Bond
In chemistry, pi bonds (π bonds) are covalent chemical bonds, in each of which two lobes of an orbital on one atom overlap with two lobes of an orbital on another atom, and in which this overlap occurs laterally. Each of these atomic orbitals has an electron density of zero at a shared nodal plane that passes through the two bonded nuclei. This plane also is a nodal plane for the molecular orbital of the pi bond. Pi bonds can form in double and triple bonds but do not form in single bonds in most cases. The Greek letter π in their name refers to p orbitals, since the orbital symmetry of the pi bond is the same as that of the p orbital when seen down the bond axis. One common form of this sort of bonding involves p orbitals themselves, though d orbitals also engage in pi bonding. This latter mode forms part of the basis for metal-metal multiple bonding. Pi bonds are usually weaker than sigma bonds. The C-C double bond, composed of one sigma and one pi bond, has a bon ...
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Lewis Acids And Bases
A Lewis acid (named for the American physical chemist Gilbert N. Lewis) 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, a 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. From p. 142: "We are inclined to think of substances as pos ...
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Cationic
An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convention. The net charge of an ion is not zero because its total number of electrons is unequal to its total number of protons. A cation is a positively charged ion with fewer electrons than protons while an anion is a negatively charged ion with more electrons than protons. Opposite electric charges are pulled towards one another by electrostatic force, so cations and anions attract each other and readily form ionic compounds. Ions consisting of only a single atom are termed atomic or monatomic ions, while two or more atoms form molecular ions or polyatomic ions. In the case of physical ionization in a fluid (gas or liquid), "ion pairs" are created by spontaneous molecule collisions, where each generated pair consists of a free electron and a ...
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Bond Length
In molecular geometry, bond length or bond distance is defined as the average distance between nuclei of two bonded atoms in a molecule. It is a transferable property of a bond between atoms of fixed types, relatively independent of the rest of the molecule. Explanation Bond length is related to bond order: when more electrons participate in bond formation the bond is shorter. Bond length is also inversely related to bond strength and the bond dissociation energy: all other factors being equal, a stronger bond will be shorter. In a bond between two identical atoms, half the bond distance is equal to the covalent radius. Bond lengths are measured in the solid phase by means of X-ray diffraction, or approximated in the gas phase by microwave spectroscopy. A bond between a given pair of atoms may vary between different molecules. For example, the carbon to hydrogen bonds in methane are different from those in methyl chloride. It is however possible to make generalizations when ...
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Steric Shielding
Steric effects arise from the spatial arrangement of atoms. When atoms come close together there is a rise in the energy of the molecule. Steric effects are nonbonding interactions that influence the shape ( conformation) and reactivity of ions and molecules. Steric effects complement electronic effects, which dictate the shape and reactivity of molecules. Steric repulsive forces between overlapping electron clouds result in structured groupings of molecules stabilized by the way that opposites attract and like charges repel. Steric hindrance Steric hindrance is a consequence of steric effects. Steric hindrance is the slowing of chemical reactions due to steric bulk. It is usually manifested in ''intermolecular reactions'', whereas discussion of steric effects often focus on ''intramolecular interactions''. Steric hindrance is often exploited to control selectivity, such as slowing unwanted side-reactions. Steric hindrance between adjacent groups can also affect torsional ...
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Chromium
Chromium is a chemical element with the symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal. Chromium metal is valued for its high corrosion resistance and hardness. A major development in steel production was the discovery that steel could be made highly resistant to corrosion and discoloration by adding metallic chromium to form stainless steel. Stainless steel and chrome plating (electroplating with chromium) together comprise 85% of the commercial use. Chromium is also greatly valued as a metal that is able to be highly polished while resisting tarnishing. Polished chromium reflects almost 70% of the visible spectrum, and almost 90% of infrared light. The name of the element is derived from the Greek word χρῶμα, ''chrōma'', meaning color, because many chromium compounds are intensely colored. Industrial production of chromium proceeds from chromite ore (mostly FeCr2O4) to produce ferro ...
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Silicon–oxygen Bond
A silicon–oxygen bond ( bond) is a chemical bond between silicon and oxygen atoms that can be found in many inorganic and organic compounds. In a silicon–oxygen bond, electrons are shared unequally between the two atoms, with oxygen taking the larger share due to its greater electronegativity. This polarisation means Si–O bonds show characteristics of both covalent and ionic bonds. Compounds containing silicon–oxygen bonds include materials of major geological and industrial significance such as silica, silicate minerals and silicone polymers like polydimethylsiloxane. Bond polarity, length and strength On the Pauling electronegativity scale, silicon has an electronegativity of 1.90 and oxygen 3.44. The electronegativity difference between the elements is therefore 1.54. Because of this moderately large difference in electronegativities, the bond is polar but not fully ionic. Carbon has an electronegativity of 2.55 so carbon–oxygen bonds have an electronegativity ...
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Polarizability
Polarizability usually refers to the tendency of matter, when subjected to an electric field, to acquire an electric dipole moment in proportion to that applied field. It is a property of all matter, considering that matter is made up of elementary particles which have an electric charge, namely protons and electrons. When subject to an electric field, the negatively charged electrons and positively charged atomic nuclei are subject to opposite forces and undergo charge separation. Polarizability is responsible for a material's dielectric constant and, at high (optical) frequencies, its refractive index. The polarizability of an atom or molecule is defined as the ratio of its induced dipole moment to the local electric field; in a crystalline solid, one considers the dipole moment per unit cell. Note that the local electric field seen by a molecule is generally different from the macroscopic electric field that would be measured externally. This discrepancy is taken into account by ...
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HOMO–LUMO Energy Gap
In chemistry, HOMO and LUMO are types of molecular orbitals. The acronyms stand for ''highest occupied molecular orbital'' and ''lowest unoccupied molecular orbital'', respectively. HOMO and LUMO are sometimes collectively called the ''frontier orbitals'', such as in the frontier molecular orbital theory. Gap The energy difference between the HOMO and LUMO is ''the HOMO–LUMO gap''. Its size can be used to predict the strength and stability of transition metal complexes, as well as the colors they produce in solution.Griffith, J. S. and L. E. Orgel"Ligand Field Theory" ''Q. Rev. Chem. Soc.'' 1957, 11, 381–383. As a rule of thumb, the larger a compound's HOMO-LUMO gap, the more stable the compound. Semiconductors The HOMO level is to organic semiconductors roughly what the maximum valence band is to inorganic semiconductors and quantum dots. The same analogy can be made between the LUMO level and the conduction band minimum.Bredas, J,-L"Mind the gap!" ''Mater. Horiz.'' 201 ...
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Oligomerisation
In chemistry and biochemistry, an oligomer () is a molecule that consists of a few repeating units which could be derived, actually or conceptually, from smaller molecules, monomers.Quote: ''Oligomer molecule: A molecule of intermediate relative molecular mass, the structure of which essentially comprises a small plurality of units derived, actually or conceptually, from molecules of lower relative molecular mass.'' The name is composed of Greek elements '' oligo-'', "a few" and '' -mer'', "parts". An adjective form is ''oligomeric''. The oligomer concept is contrasted to that of a polymer, which is usually understood to have a large number of units, possibly thousands or millions. However, there is no sharp distinction between these two concepts. One proposed criterion is whether the molecule's properties vary significantly with the removal of one or a few of the units. An oligomer with a specific number of units is referred to by the Greek prefix denoting that number, wit ...
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