Related Experiment Video
Updated: Jun 17, 2025
14:07
Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
13.6K
2-Alkylphosphino-1-boraadamantanes.
Kurt F Hoffmann1, Rayni P Noriega1, Paul D Boyle1
1Department of Chemistry, Western University, 1151 Richmond Street, London, ON, N8K 3G6, Canada. marcus.drover@uwo.ca.
Chemical Communications (Cambridge, England)
|August 7, 2024
Summary
This study introduces bifunctional boraadamantanes with a phosphine group, enabling the creation of novel boraadamantane coordination compounds. These findings expand the Lewis acid-base chemistry of caged group 13 elements.
Area of Science:
- Organometallic Chemistry
- Main Group Chemistry
- Caged Boron Compounds
Background:
- Boraadamantanes are unique caged group 13 compounds with a trigonal pyramidal structure.
- The Lewis acid-base chemistry of boraadamantanes is less explored compared to their acyclic counterparts.
- Existing synthetic routes limit the functionalization of boraadamantane scaffolds.
Purpose of the Study:
- To synthesize novel bifunctional boraadamantanes incorporating a phosphine moiety.
- To establish the first phosphorus-boron bond within a boraadamantane framework.
- To explore the coordination chemistry of these new boraadamantane derivatives.
Main Methods:
- Multi-step organic synthesis to construct the bifunctional boraadamantane scaffold.
- Spectroscopic characterization (NMR, X-ray crystallography) to confirm structure and bonding.
- Reaction of the functionalized boraadamantanes with metal precursors to form coordination complexes.
Main Results:
- Successful synthesis of the first bifunctional boraadamantanes featuring an appended phosphine group.
- Confirmation of a direct phosphorus-boron bond within the boraadamantane cage.
- Demonstration of the utility of the new scaffold in accessing novel boraadamantane coordination compounds.
Conclusions:
- The developed bifunctional boraadamantane scaffold provides a versatile platform for organometallic chemistry.
- This work significantly advances the understanding and application of caged group 13 element chemistry.
- The synthesized coordination compounds open new avenues for catalysis and materials science.
Related Concept Videos
03:08Hydroboration-Oxidation of Alkenes
8.0K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
8.0K
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
17.9K
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
17.9K
01:10Nomenclature of Aryl and Heterocyclic Amines
2.3K
The simplest aromatic amine is phenylamine, which contains an –NH2 functionality directly attached to an aromatic ring. The name aniline is designated for this skeleton. As shown in Figure 1, the common names of the functionalized anilines involve prefixes ortho-, meta-, and para- to indicate the substitution position. Different functionalized aniline derivatives also have notable trivial names.
2.3K
02:45Alkyl Halides
16.4K
Structural Properties
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
16.4K
02:38Electrophilic Addition to Alkynes: Halogenation
8.2K
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
8.2K
02:36Regioselectivity and Stereochemistry of Hydroboration
8.1K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
8.1K