- A Bottleable Imidazole-Based Radical as a Single Electron Transfer Reagent
-
Reduction of 1,3-bis(2,6-diisopropylphenyl)-2,4-diphenyl-1H-imidazol-3-ium chloride (1) resulted in the formation of the first structurally characterized imidazole-based radical 2. 2 was established as a single electron transfer reagent by treating it with an acceptor molecule tetracyanoethylene. Moreover, radical 2 was utilized as an organic electron donor in a number of organic transformations such as in activation of an aryl-halide bond, alkene hydrosilylation, and in catalytic reduction of CO2 to methoxyborane, all under ambient temperature and pressure.
- Das, Arpan,Ahmed, Jasimuddin,Rajendran,Adhikari, Debashis,Mandal, Swadhin K.
-
supporting information
p. 1246 - 1252
(2020/12/21)
-
- Interactions of C?F Bonds with Hydridoboranes: Reduction, Borylation and Friedel–Crafts Alkylation
-
The stoichiometric reactions of the alkylfluorides 1-fluoroadamantane (Ad-F), fluorocyclohexane (Cy-F), 1-fluoropentane (Pent-F) and benzyl fluorides with secondary boranes pinacolborane (HBpin), catecholborane (HBcat), 9-borabicyclo(3.3.1)nonane (9-BBN)
- Bamford, Karlee L.,Chitnis, Saurabh S.,Qu, Zheng-wang,Stephan, Douglas W.
-
supporting information
p. 16014 - 16018
(2018/10/15)
-
- Carbodiimides as catalysts for the reduction of CO2 with boranes
-
Carbodiimides catalyse the reduction of CO2 with H-BBN or BH3·SMe2 to give either mixtures of CH2(OBBN)2 and CH3OBBN or (MeOBO)3 and B(OMe)3 under mild conditions (25-60 °C, 1 atm CO2). Stoichiometric reactions and theoretical calculations were performed to unveil the mechanism of these catalytic processes.
- Ramos, Alberto,Anti?olo, Antonio,Carrillo-Hermosilla, Fernando,Fernández-Galán, Rafael,Rodríguez-Diéguez, Antonio,García-Vivó, Daniel
-
supporting information
p. 4700 - 4703
(2018/05/22)
-
- Metal-free disproportionation of formic acid mediated by organoboranes
-
In the presence of dialkylboranes, formic acid can be converted to formaldehyde and methanol derivatives without the need for an external reductant. This reactivity, in which formates serve as the sole carbon and hydride sources, represents the first exam
- Chauvier, Clément,Thuéry, Pierre,Cantat, Thibault
-
p. 5680 - 5685
(2016/09/04)
-
- Phosphine catalyzed reduction of CO2 with boranes
-
Phosphine is shown to catalyse the reaction of CO2 with 9-BBN to give mixtures of HCO2(B(C8H14)) 3, H 2C(OB(C8H14))24 and MeOB(C 8H14) 5; at 0.02 mol% of tBu3P 5 is obtained in 98% yield at 60 °C with TON of almost 5500 and a TOF of 170. Under stoichiometric conditions the species (R3PCH2O)(HC(O)O) B(C8H14) (R = tBu 1,4-MeC6H42) were isolated and characterized. the Partner Organisations 2014.
- Wang, Tongen,Stephan, Douglas W.
-
supporting information
p. 7007 - 7010
(2014/06/23)
-
- Pincer-ligated nickel hydridoborate complexes: The dormant species in catalytic reduction of carbon dioxide with boranes
-
Nickel pincer complexes of the type [2,6-(R2PO) 2C6H3]NiH (R = tBu, 1a; R = iPr, 1b; R = cPe, 1c) react with BH3·THF to produce borohydride complexes [2,6-(R2/su
- Chakraborty, Sumit,Zhang, Jie,Patel, Yogi J.,Krause, Jeanette A.,Guan, Hairong
-
-
- Frustrated lewis pair inspired carbon dioxide reduction by a ruthenium tris(aminophosphine) complex
-
Frustrating ruthenium: The ruthenium complex 1 is shown to bind carbon dioxide or aldehyde in a manner similar to a frustrated Lewis pair. Compound 2 catalyzes the reduction of CO2 in the presence of pinacolborane (HBpin), yielding MeOBpin and O(Bpin)2 (see picture; Ru red, P orange, N green, O light red, C black). Copyright
- Sgro, Michael J.,Stephan, Douglas W.
-
supporting information
p. 11343 - 11345
(2013/01/15)
-
- Catalytic properties of nickel bis(phosphinite) pincer complexes in the reduction of CO2 to methanol derivatives
-
A new nickel bis(phosphinite) pincer complex [2,6-(R2PO) 2C6H3]NiCl (LRNiCl, R = cyclopentyl) has been prepared in one pot from resorcinol, ClP(C5H 9)2, NiCl2, and 4-dimethylaminopyridine. The reaction of this pincer compound with LiAlH4 produces a nickel hydride complex, which is capable of reducing CO2 rapidly at room temperature to give a nickel formate complex. X-ray structures of two related nickel formate complexes LRNiOCHO (R = cyclopentyl and isopropyl) have shown an "in plane" conformation of the formato group with respect to the coordination plane. The stoichiometric reaction of nickel formate complexes LRNiOCHO (R = cyclopentyl, isopropyl, and tert-butyl) with catecholborane has suggested that the reaction is favored by a bulky R group. LRNiOCHO (R = tert-butyl) does not react with PhSiH3 at room temperature; however, it reacts with 9-borabicyclo[3.3.1]nonane and pinacolborane to generate a methanol derivative and a boryl formate species, respectively. The catalytic reduction of CO2 with catecholborane is more effectively catalyzed by a more sterically hindered nickel pincer hydride complex with bulky R groups on the phosphorus donor atoms. The nickel pincer hydride complexes are inactive catalysts for the hydrosilylation of CO 2 with PhSiH3.
- Chakraborty, Sumit,Patel, Yogi J.,Krause, Jeanette A.,Guan, Hairong
-
experimental part
p. 30 - 34
(2012/03/12)
-
- The First Organoboron-Tellurium Compounds
-
Na2Te and Na2Te2, prepared from Te and Na, react with 9-Cl-9-BBN to form bis(1,5-cyclooctanediylboryl) telluride (1) and bis(1,5-cyclooctandiylboryl) ditelluride (2), resp. 1 reacts with water to give elemental Te, (9-BBN)2O, and (9H-9-BBN)2. - Key
- Koester, Roland,Seidel, Guenter,Schuessler, Wilhelm,Wrackmeyer, Bernd
-
-
- Dithiocarboxylic Acids and Derivatives from Carboxylic Esters and Lactones with the Organoboron Sulfide Reagent (9-BBN)2S
-
Bis(1,5-cyclooctanediylboryl) sulfide (1) reacts with carboxylic esters to give the dithiocarboxylic 1,5-cyclooctanediylboryl esters 2a-f in high yields (2a: X-ray crystal structure analysis).Methanolysis of 2a-f leads to the dithiocarboxylic acids 5a-f, which form the corresponding piperidinium salts in the presence of piperidine.When cyclic esters (γ-, δ-lactones) are allowed to react with 1, the boryloxy-substituted dithiocarboxylic 1,5-cyclooctanediylboryl esters 3a-c are obtained.Key Words: (9-BBN)2S, reagent / OC-Sulfoborations / 1,2-Eliminations, of R2BOR', (R2B)2O / Dithiocarboxylic 1,5-cyclooctanediylboryl esters / Dithiocarboxylic acids
- Koester, Roland,Kucznierz, Ralf,Seidel, Guenter,Betz, Peter
-
p. 1023 - 1032
(2007/10/02)
-
- Reactions of (Organo)phosphorus-Oxygen Compounds with Diorgano-hydro-boranes
-
Trialkyl phosphites P(OR)3 react with tetraalkyldiboranes(6) (R'2-BH)2 in a temperature-dependent manner between 20 and 130 deg C to form the trialkyl phosphite-boranes (RO)3P-BHR'2, (RO)3P-BH2R', and (RO)3P-BH3, which have various stabilities toward alcohols.With bis(9-borabicyclononane) (1c)2 the easily protolyzed addition compounds are obtained . - Diorgano phosphites (RO)2P(O)H , triorgano phosphates (RO)3PO , and the monosaccharide-diphenyl phosphates 4f, 4g, and 4h are reduced by (1a)2 or (1c)2 to give H2, PH3, and insoluble yellow phosphorus compounds, respectively.Phosphoric acid (4e), their derivatives OP(OBR2)3 , and phenylphosphonic acid C6H5P(O)(OH)2 (6) are not deoxygenated at 130 deg C by (1a)2 to (1c)2. - Diorganophosphoiic acids R2P(O)OH and phenylphosphinic acid C6H5(H)P(O)OH (5c) are reduced by (1a)2-(1c)2.Reaction of 5a with (1a)2 leads to the compounds B(C2H5)2 (8a-BH3), 2BC2H5 , and 3B . 5a reacts with (1c)2 under simultaneous formation of (C6H5)2PH (7) or (C6H5)PH-HBC8H14 (7-1c) and (C6H5)2POBC8H14 (8c) or (C6H5)2P(OBC8H14)-HBC8H14 (8c-1c). - 6 reacts with tetraethyldiboroxane (11a) to form a mixture of the oligomeric compounds - n - (6'a)n.
- Koester, Roland,Schuessler, Wilhelm,Synoradzki, Ludwik
-
p. 1105 - 1116
(2007/10/02)
-