3213-79-4Relevant articles and documents
Radical cations of 1,2-bis(dialkylamino)benzenes: Restricted rotation about the C-NMe2 bond
Neugebauer, Franz A.,Funk, Britta,Staab, Heinz A.
, p. 4755 - 4758 (1994)
The 1,2-bis(dialkylamino)benzene radical cations 2a-c.+ were generated by oxidation of the parent compounds with iodine or lead tetraacetate. ESR and ENDOR studies of 2a.+ and 2b.+ gave evidence of a restricted rotation about the C-NMe2 bond; based on the results of 2c.+ the different N-methyl proton splittings in 2a++ and 2b.+ were assigned to the exo and endo N-methyl groups.
BORYLIMIDE CATALYSTS
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Paragraph 0081, (2020/06/10)
The present invention provides a borylimide catalyst and further relates to compositions comprising the borylimide catalysts and processes for the polymerisation of olefins (e.g. ethylene) using the borylimide catalysts or the compositions comprising the
Revealing the unusual role of bases in activation/deactivation of catalytic systems: O-NHC coupling in M/NHC catalysis
Chernyshev, Victor M.,Khazipov, Oleg V.,Shevchenko, Maxim A.,Chernenko, Andrey Yu.,Astakhov, Alexander V.,Eremin, Dmitry B.,Pasyukov, Dmitry V.,Kashin, Alexey S.,Ananikov, Valentine P.
, p. 5564 - 5577 (2018/07/06)
Numerous reactions are catalyzed by complexes of metals (M) with N-heterocyclic carbene (NHC) ligands, typically in the presence of oxygen bases, which significantly shape the performance. It is generally accepted that bases are required for either substrate activation (exemplified by transmetallation in the Suzuki cross-coupling), or HX capture (e.g. in a variety of C-C and C-heteroatom couplings, the Heck reaction, C-H functionalization, heterocyclizations, etc.). This study gives insights into the behavior of M(ii)/NHC (M = Pd, Pt, Ni) complexes in solution under the action of bases conventionally engaged in catalysis (KOH, NaOH, t-BuOK, Cs2CO3, K2CO3, etc.). A previously unaddressed transformation of M(ii)/NHC complexes under conditions of typical base-mediated M/NHC catalyzed reactions is disclosed. Pd(ii) and Pt(ii) complexes widely used in catalysis react with the bases to give M(0) species and 2(5)-oxo-substituted azoles via an O-NHC coupling mechanism. Ni(NHC)2X2 complexes hydrolyze in the presence of aqueous potassium hydroxide, and undergo the same O-NHC coupling to give azolones and metallic nickel under the action of t-BuOK under anhydrous conditions. The study reveals a new role of NHC ligands as intramolecular reducing agents for the transformation of M(ii) into ligandless M(0) species. This demonstrates that the disclosed base-mediated O-NHC coupling reaction is integrated into the catalytic M/NHC systems and can define the mechanism of catalysis (molecular M/NHC vs. NHC-free cocktail-type catalysis). A proposed mechanism of the revealed transformation includes NHC-OR reductive elimination, as implied by a series of mechanistic studies including 18O labeling experiments.