A boron-centered radical: a potassium-crown ether stabilized boryl radical anion.
نویسندگان
چکیده
A boron radical contact ion-pair Mes2B{4-(3,5-dimethylpyridinyl)}K(18-crown-6)(THF) (1K) has been isolated and characterized by electron paramagnetic resonance (EPR) spectroscopy, UV-vis absorption spectroscopy and single crystal X-ray diffraction. The geometry, bonding and spin density distribution are shown to be affected by the NK interaction. The unpaired electron resides mainly on the boron atom and falls between those of triarylboron radical anions and neutral boron radicals. The work provides a novel boron-centered radical intermediate, connecting anionic and neutral boryl radicals.
منابع مشابه
Visible‐Light‐Mediated Decarboxylative Radical Additions to Vinyl Boronic Esters: Rapid Access to γ‐Amino Boronic Esters
The synthesis of alkyl boronic esters by direct decarboxylative radical addition of carboxylic acids to vinyl boronic esters is described. The reaction proceeds under mild photoredox catalysis and involves an unprecedented single-electron reduction of an α-boryl radical intermediate to the corresponding anion. The reaction is amenable to a diverse range of substrates, including α-amino, α-oxy, ...
متن کاملFormation of N-heterocyclic, donor-stabilized borenium ions.
Cationic and zwitterionic boryl bromide species and a borenium-boryl bromide cation have been synthesised which represent new N-donor stabilised cationic boron compounds with β-diketiminate ligands. The unexpected borenium-boryl bromide results from a head-to-tail dimerisation of the corresponding zwitterionic boryl bromide accompanied by proton migration. The electronic nature of these new spe...
متن کاملReactions of (-)-sparteine with alkali metal HMDS complexes: conventional meets the unconventional.
'Conventional' (-)-sparteine adducts of lithium and sodium 1,1,1,3,3,3-hexamethyldisilazide (HMDS) were prepared and characterised, along with an unexpected and 'unconventional' hydroxyl-incorporated sodium sodiate, [(-)-sparteine x Na(mu-HMDS)Na x (-)-sparteine](+)[Na(4)(mu-HMDS)(4)(OH)](-)--the complex anion of which is the first inverse crown ether anion.
متن کاملBoron nitride substituted 12-crown-4 ether: Theoretical study of structural, thermochemical, and nonlinear optical properties
The structures and stability of 531 novel boron nitride substituted isomers of 12-crown-4 etherverified theoretically. For a collection of 23 selected BN isomers, structural geometry, vibrationalstability, energy gaps, natural bond population analysis, and nonlinear optical responses investigatedtheoretically. The changes of standard enthalpies for ionization reactions and electron affinityreac...
متن کاملA Different Behaviour of the Phthalimide Ion in Srn1 Reactions
The phthalimide anion reacts by the SRN1 mechanism under photostimulation with different substrates. Whilst with 1-iodonaphthalene only reduction of the naphthyl radical is observed, with 1-iodoadamantane coupling at the carbon instead of at the nitrogen takes place. Introduction The mechanism of Radical Nucleophilic Substitution (SRN1) is a chain process with radicals and radical anions as int...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- Chemical communications
دوره 52 86 شماره
صفحات -
تاریخ انتشار 2016