1595-09-1Relevant articles and documents
Role of the X Coligands in Cyclometalated [Ni(Phbpy)X] Complexes (HPhbpy = 6-Phenyl-2,2′-bipyridine)
Chin, Mason T.,H?rner, Gerald,Klein, Axel,Kletsch, Lukas,Sandleben, Aaron,Sch?fer, Sascha,Vicic, David A.,Vogt, Nicolas
, p. 1776 - 1785 (2021/06/28)
The coligand X was varied in the organonickel complexes [Ni(Phbpy)X] (X = F, Cl, Br, I, C6F5) carrying the anionic tridentate CNN ligand 6-(phen-2-ide)-2,2′-bipyridine (Phbpy-) to study its effect on electronic structures of these complexes and their activity in Negishi-like C-C cross-coupling catalysis. The complexes were synthesized from the precursor [Ni(COD)2] (COD = 1,5-cyclooctadiene) by chelate-assisted oxidative addition into the phenyl C-X bond of the protoligand 6-(2-halidophenyl)-2,2′-bipyridine) and were obtained as red powders. Protoligands X-Phbpy carrying the halide surrogates X = OMe, OTf (triflate) failed in this reaction. Single-crystal XRD allowed us to add the structures of [Ni(Phbpy)Cl] and [Ni(Phbpy)I] to the previously reported Br derivative. Cyclic voltammetry showed reversible reductions for X = C6F5, F, Cl, while for Br and I the reversibility is reduced through rapid splitting of X- after reduction (EC mechanism). UV-vis spectroelectrochemistry confirmed the decreasing degree of reversibility along the series C6F5 > F > Cl ? Br > I, which parallels the "leaving group character"of the X coligands. This method also revealed mainly bpy centered reduction and essentially Ni(II)/Ni(III) oxidations, as corroborated by DFT calculations. The rather X-invariant long-wavelength UV-vis absorptions and excited states were analyzed in detail using TD-DFT and were consistent with predominant metal to ligand charge transfer (MLCT) character. Initial catalytic tests under Negishi-like conditions showed the complexes to be active as catalysts in C-C cross-coupling reactions but did not display marked differences along the series from Ni-F to Ni-I.
P -Selective (sp2)-C-H functionalization for an acylation/alkylation reaction using organic photoredox catalysis
Pandey, Ganesh,Tiwari, Sandip Kumar,Singh, Bhawana,Vanka, Kumar,Jain, Shailja
, p. 12337 - 12340 (2017/11/20)
p-Selective (sp2)-C-H functionalization of electron rich arenes has been achieved for acylation and alkylation reactions, respectively, with acyl/alkylselenides by organic photoredox catalysis involving an interesting mechanistic pathway.
Terminal-Selective Functionalization of Alkyl Chains by Regioconvergent Cross-Coupling
Dupuy, Stéphanie,Zhang, Ke-Feng,Goutierre, Anne-Sophie,Baudoin, Olivier
, p. 14793 - 14797 (2016/11/23)
Hydrocarbons are still the most important precursors of functionalized organic molecules, which has stirred interest in the discovery of new C?H bond functionalization methods. We describe herein a new step-economical approach that enables C?C bonds to be constructed at the terminal position of linear alkanes. First, we show that secondary alkyl bromides can undergo in situ conversion into alkyl zinc bromides and regioconvergent Negishi coupling with aryl or alkenyl triflates. The use of a suitable phosphine ligand favoring Pd migration enabled the selective formation of the linear cross-coupling product. Subsequently, mixtures of secondary alkyl bromides were prepared from linear alkanes by standard bromination, and regioconvergent cross-coupling then provided access to the corresponding linear arylation product in only two steps.