Oxoborane

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In chemistry, an oxoborane is any chemical compound containing a boron atom with a terminal oxygen atom (a −B=O functional group). The compound class is of some relevance to academic research. The parent compound, HBO, itself called "oxoborane", together with derivatives F B O , ClBO, BrBO, HOBO and MeBO have been detected in matrix isolation or in the gaseous phase at high temperature. [1] [2] In these compounds the boron and oxygen form a triple bond prone to cyclotrimerization to boroxines.

Derivatives

Although monomeric oxoboranes have not been isolated, derivatives have been described.

A Lewis acid-stabilized adduct of an oxoborane is (NacNacB=O.AlCl3. [3] In this compound the oxygen atom is coordinated to aluminium chloride. The BO bond length is 130 pm (compare to 136 pm in regular boronic acids). Related systems are known. [4]

In trans-[(Cy3P)2PtBr(BO)], platinum is coordinated to the BO unit. [5] In this compound the BO bond length is 120 picometers.

Related Research Articles

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In coordination chemistry, a coordinate covalent bond, also known as a dative bond, dipolar bond, or coordinate bond is a kind of two-center, two-electron covalent bond in which the two electrons derive from the same atom. The bonding of metal ions to ligands involves this kind of interaction. This type of interaction is central to Lewis acid–base theory.

Boron trifluoride is the inorganic compound with the formula BF3. This pungent, colourless, and toxic gas forms white fumes in moist air. It is a useful Lewis acid and a versatile building block for other boron compounds.

<span class="mw-page-title-main">Organoboron chemistry</span> Study of compounds containing a boron-carbon bond

Organoboron chemistry or organoborane chemistry is the chemistry of organoboron compounds or organoboranes, which are chemical compounds of boron and carbon that are organic derivatives of borane (BH3), for example trialkyl boranes..

<span class="mw-page-title-main">Borazine</span> Boron compound

Borazine, also known as borazole, is a non-polar inorganic compound with the chemical formula B3H6N3. In this cyclic compound, the three BH units and three NH units alternate. The compound is isoelectronic and isostructural with benzene. For this reason borazine is sometimes referred to as “inorganic benzene”. Like benzene, borazine is a colourless liquid with an aromatic smell.

<span class="mw-page-title-main">Gold compounds</span>

Gold compounds are compounds by the element gold (Au). Although gold is the most noble of the noble metals, it still forms many diverse compounds. The oxidation state of gold in its compounds ranges from −1 to +5, but Au(I) and Au(III) dominate its chemistry. Au(I), referred to as the aurous ion, is the most common oxidation state with soft ligands such as thioethers, thiolates, and organophosphines. Au(I) compounds are typically linear. A good example is Au(CN)−2, which is the soluble form of gold encountered in mining. The binary gold halides, such as AuCl, form zigzag polymeric chains, again featuring linear coordination at Au. Most drugs based on gold are Au(I) derivatives.

<span class="mw-page-title-main">Boronic acid</span> Organic compound of the form R–B(OH)2

A boronic acid is an organic compound related to boric acid in which one of the three hydroxyl groups is replaced by an alkyl or aryl group. As a compound containing a carbon–boron bond, members of this class thus belong to the larger class of organoboranes.

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<span class="mw-page-title-main">Boroxine</span> 6-sided cyclic compound of oxygen and boron

Boroxine is a 6-membered heterocyclic compound composed of alternating oxygen and singly-hydrogenated boron atoms. Boroxine derivatives such as trimethylboroxine and triphenylboroxine also make up a broader class of compounds called boroxines. These compounds are solids that are usually in equilibrium with their respective boronic acids at room temperature. Beside being used in theoretical studies, boroxine is primarily used in the production of optics.

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<span class="mw-page-title-main">Carborane acid</span> Class of chemical compounds

Carborane acidsH(CXB
11
Y
5
Z
6
)
(X, Y, Z = H, Alk, F, Cl, Br, CF3) are a class of superacids, some of which are estimated to be at least one million times stronger than 100% pure sulfuric acid in terms of their Hammett acidity function values (H0 ≤ –18) and possess computed pKa values well below –20, establishing them as some of the strongest known Brønsted acids. The best-studied example is the highly chlorinated derivative H(CHB
11
Cl
11
)
. The acidity of H(CHB
11
Cl
11
)
was found to vastly exceed that of triflic acid, CF
3
SO
3
H
, and bistriflimide, (CF
3
SO
2
)
2
NH
, compounds previously regarded as the strongest isolable acids.

<span class="mw-page-title-main">Borylene</span>

A borylene is the boron analogue of a carbene. The general structure is R-B: with R an organic residue and B a boron atom with two unshared electrons. Borylenes are of academic interest in organoboron chemistry. A singlet ground state is predominant with boron having two vacant sp2 orbitals and one doubly occupied one. With just one additional substituent the boron is more electron deficient than the carbon atom in a carbene. For this reason stable borylenes are more uncommon than stable carbenes. Some borylenes such as boron monofluoride (BF) and boron monohydride (BH) the parent compound also known simply as borylene, have been detected in microwave spectroscopy and may exist in stars. Other borylenes exist as reactive intermediates and can only be inferred by chemical trapping.

<span class="mw-page-title-main">Holger Braunschweig</span>

Holger Braunschweig is Head and Chair of Inorganic Chemistry at the Julius-Maximilians-University of Würzburg in Würzburg, Germany. He is best known for founding the field of transition metal-boron multiple bonding, the synthesis of the first stable compounds containing boron-boron and boron-oxygen triple bonds, the isolation of the first non-carbon/nitrogen main-group dicarbonyl, and the first fixation of dinitrogen at an element of the p-block of the periodic table. By modifying a strategy pioneered by Prof. Gregory Robinson of the University of Georgia, Braunschweig also discovered the first rational and high-yield synthesis of neutral compounds containing boron-boron double bonds (diborenes). In 2016 Braunschweig isolated the first compounds of beryllium in the oxidation state of zero.

The phosphaethynolate anion, also referred to as PCO, is the phosphorus-containing analogue of the cyanate anion with the chemical formula [PCO] or [OCP]. The anion has a linear geometry and is commonly isolated as a salt. When used as a ligand, the phosphaethynolate anion is ambidentate in nature meaning it forms complexes by coordinating via either the phosphorus or oxygen atoms. This versatile character of the anion has allowed it to be incorporated into many transition metal and actinide complexes but now the focus of the research around phosphaethynolate has turned to utilising the anion as a synthetic building block to organophosphanes.

In chemistry, aluminium(I) refers to monovalent aluminium in both ionic and covalent bonds. Along with aluminium(II), it is an extremely unstable form of aluminium.

<span class="mw-page-title-main">(Pentamethylcyclopentadienyl)aluminium(I)</span> Chemical compound

(Pentamethylcyclopentadienyl)aluminium(I) is an organometallic compound with the formula Al(C5Me5) ("Me" is a methyl group; CH3). The compound is often abbreviated to AlCp* or Cp*Al, where Cp* is the pentamethylcyclopentadienide anion (C5Me5). Discovered in 1991 by Dhmeier et al., AlCp* serves as the first ever documented example of a room temperature stable monovalent aluminium compound. In its isolated form, Cp*Al exists as the tetramer [Cp*Al]4, and is a yellow crystal that decomposes at temperatures above 100 °C but also sublimes at temperatures above 140 °C.

<span class="mw-page-title-main">Organoberyllium chemistry</span> Organoberyllium Complex in Main Group Chemistry

Organoberyllium chemistry involves the synthesis and properties of organometallic compounds featuring the group 2 alkaline earth metal beryllium (Be). Beryllium is best known to have a +2 oxidation state and one of the smallest atoms and it is understudied in the periodic table. While metallic beryllium is relatively unreactive, its dust causes berylliosis and compounds are toxic. The Be2+ cation is characterized by the highest known charge density (Z/r = 6.45), making it one of the hardest cations and a very strong Lewis acid. It is most commonly used to coordinate other elements and can portray many types of compound through different ligands attachment. Coordination in beryllium can range from a coordination number of two to four. Most common ligands attached to beryllium are halides, hydride (like beryllium borohydride in a three-center two-electron bond), methyl, aryl, and alkyl. Beryllium can form complexes with known organic compounds such as phosphines, N-hetereocyclic carbenes (NHC), cyclic alkyl amino carbenes (CAAC), and β-diketiminates (NacNac). They can best be prepared by transmetallation or alkylation of beryllium chloride.

Heteroatomic multiple bonding between group 13 and group 15 elements are of great interest in synthetic chemistry due to their isoelectronicity with C-C multiple bonds. Nevertheless, the difference of electronegativity between group 13 and 15 leads to different character of bondings comparing to C-C multiple bonds. Because of the ineffective overlap between p𝝅 orbitals and the inherent lewis acidity/basicity of group 13/15 elements, the synthesis of compounds containing such multiple bonds is challenging and subject to oligomerization. The most common example of compounds with 13/15 group multiple bonds are those with B=N units. The boron-nitrogen-hydride compounds are candidates for hydrogen storage. In contrast, multiple bonding between aluminium and nitrogen Al=N, Gallium and nitrogen (Ga=N), boron and phosphorus (B=P), or boron and arsenic (B=As) are less common.

References

  1. Inorganic chemistry, Egon Wiberg,Nils Wiberg,Arnold Frederick Holleman
  2. Westcott, S. A. (2010), BO Chemistry Comes Full Circle. Angewandte Chemie International Edition, 49: 9045–9046. doi : 10.1002/anie.201003379
  3. Synthesis and Characterization of a Coordinated Oxoborane: Lewis Acid Stabilization of a Boron−Oxygen Double Bond Dragoslav Vidovic, Jennifer A. Moore, Jamie N. Jones, and Alan H. Cowley J. Am. Chem. Soc., 2005, 127 (13), pp 4566–4567 doi : 10.1021/ja0507564
  4. Wang, Y., Hu, H., Zhang, J. and Cui, C. , Comparison of Anionic and Lewis Acid Stabilized N-Heterocyclic Oxoboranes: Their Facile Synthesis from a Borinic Acid. Angewandte Chemie, n/a. doi : 10.1002/ange.201007417
  5. Oxoboryl Complexes: Boron−Oxygen Triple Bonds Stabilized in the Coordination Sphere of Platinum Holger Braunschweig, Krzysztof Radacki and Achim Schneider Science 16 April 2010 Vol. 328 no. 5976 pp. 345-347 doi : 10.1126/science.1186028