14659-58-6Relevant articles and documents
Competition between π-arene and lone-pair halogen coordination of silylium ions?
Romanato, Paola,Duttwyler, Simon,Linden, Anthony,Baldridge, Kim K.,Siegel, Jay S.
, p. 11844 - 11846 (2011)
In 2,6-diarylphenylSiR2 cations, the 2,6-diarylphenyl (m-terphenyl) scaffold blocks incoming nucleophiles and stabilizes the positive charge at silicon by lateral ring interactions. Direct ortho-halogen and π-electron-rich face coordination to
Fluorination of arylboronic esters enabled by bismuth redox catalysis
Planas, Oriol,Wang, Feng,Leutzsch, Markus,Cornella, Josep
, p. 313 - 317 (2020/01/28)
Bismuth catalysis has traditionally relied on the Lewis acidic properties of the element in a fixed oxidation state. In this paper, we report a series of bismuth complexes that can undergo oxidative addition, reductive elimination, and transmetallation in a manner akin to transition metals. Rational ligand optimization featuring a sulfoximine moiety produced an active catalyst for the fluorination of aryl boronic esters through a bismuth (III)/bismuth (V) redox cycle. Crystallographic characterization of the different bismuth species involved, together with a mechanistic investigation of the carbonfluorine bond-forming event, identified the crucial features that were combined to implement the full catalytic cycle.
Critical factors in determining the heterolytic versus homolytic bond cleavage of terminal oxidants by Iron(III) porphyrin complexes
Yokota, Sawako,Fujii, Hiroshi
, p. 5127 - 5137 (2018/04/24)
Heterolytic versus homolytic cleavage of the metal-bound terminal oxidant is the key for determining the nature of reactive intermediates in metalloenzymes and metal catalyzed oxygenation reactions. Here, we study the bond cleavage process of hypochlorite
Spectroscopic and product studies of the effect of para substituents on the reactivity of triplet bis(2,6-dimethylphenyl)carbenes
Hu, Yingmo,Ishikawa, Yui,Hirai, Katsuyuki,Tomioka, Hideo
, p. 2207 - 2218 (2007/10/03)
A series of diazobis(2,6-dimethylphenyl)methanes (1) bearing eight symmetrical para di-substituents have been prepared and photolyzed to generate the corresponding carbenes (2). Product analysis studies showed that carbenes (2) decay mainly either by dimerization to form tetra(aryl)ethylene (3) or by attack at an o-methyl group to afford 1,2-dihydrobenzocyclobutenes (4) by way of o-quinodimethanes (6) in solution. The zero-field splitting parameters, D and E, were measured in matrices of different viscosities and are analyzed in terms of a sigma-dot (σ.) scale of spin-delocalization substituent constants. Fairly good correlation with σ. was found for the D values of 32 in its minimum energy geometry. Stabilities of 32 were estimated either by measuring the temperature at which the triplet carbene signals disappeared upon thawing the matrix or by analyzing the decay kinetics of 32 in a degassed solution at room temperature. They are examined in terms of the D values in matrix at low temperature and in terms of product distributions in solution at room temperature.
