1260019-77-9Relevant academic research and scientific papers
Reactivity of the Bifunctional Ambiphilic Molecule 8-(dimesitylboryl) quinoline: Hydrolysis and Coordination to CuI, AgI and PdII
Son, Jung-Ho,Pudenz, Michael A.,Hoefelmeyer, James D.
, p. 11081 - 11090 (2011/01/10)
The ambiphilic molecule 8-(dimesitylboryl)quinoline (1) was synthesized by treatment of 8-bromoquinoline or 8-iodoquinoline with n-BuLi followed by dimesitylboronfluoride. Hydrolysis of 1 is unusually rapid compared to bulky triorganoboranes with the sequential loss of mesitylene and formation of mesityl(quinolin-8-yl)borinic acid (2) and 8-quinoline boronic acid dimer (3). Cooperativity within the bifunctional ambiphilic site leads to water activation and protodeboronation of the B-C(Mes) bonds. Blocking of the ambiphilic site of 1 by methylation of the quinoline nitrogen atom leads to an air-stable N-methyl-quinolinium salt. Coordination complexes were formed by reaction of 1 with CuCl, Ag(OTf), and PdCl2(PhCN)2 with coordination of the quinolinyl nitrogen to the metal ion. The CuI and AgI centers are stabilized by η3-BCipsoCortho π-interaction. The isolated PdII complex is a product of cyclometalation, resulting from elimination of HCl upon deprotonation of the ortho-methyl group of nearby mesityl. The bonding in 7 could be understood as a 16-electron Pd complex that features an anionic η3-C ipso-Cortho-Cbenzyl allylic ligand fragment plus a Pd→B bond, or an η4-BCipso-C ortho-Cbenzyl boratabutadiene anion fragment. The Royal Society of Chemistry 2010.
