866613-57-2Relevant academic research and scientific papers
O,N,N-Pincer ligand effects on oxidatively induced carbon-chlorine coupling reactions at palladium
Wright, Luka A.,Hope, Eric G.,Solan, Gregory A.,Cross, Warren B.,Singh, Kuldip
, p. 6040 - 6051 (2015/03/30)
The syntheses of two families of sterically tuneable O,N,N pro-ligands are reported, namely the 2-(phenyl-2′-ol)-6-imine-pyridines, 2-(C6H4-2′-OH),6-(CMeNAr)C5H3N [Ar = 4-i-PrC6H4 (HL1a), 2,6-i-Pr2C6H3 (HL1b)] and the 2-(phenyl-2′-ol)-6-(amino-prop-2-yl)pyridines, 2-(C6H4-2′-OH),6-(CMe2NHAr)C5H3N [Ar = 4-i-PrC6H4 (HL2a), 2,6-i-Pr2C6H3 (HL2b)], using straightforward synthetic approaches and in reasonable overall yields. Interaction of HL1a/c and HL2a/b with palladium(ii) acetate affords the O,N,N-pincer complexes, [{2-(C6H4-2′-O)-6-(CMeNAr)C5H3N}Pd(OAc)] (Ar = 4-i-PrC6H4 (1a), 2,6-i-Pr2C6H3 (1b)) and [{2-(C6H4-2′-O)-6-(CMe2NHAr)C5H3N}Pd(OAc)] (Ar = 4-i-PrC6H4 (2a), 2,6-i-Pr2C6H3 (2b)), which can be readily converted to their chloride derivatives, [{2-(C6H4-2′-O)-6-(CMeNAr)C5H3N}PdCl] (Ar = 4-i-PrC6H4 (3a), 2,6-i-Pr2C6H3 (3b)) and [{2-(C6H4-2′-O)-6-(CMe2NHAr)C5H3N}PdCl] (Ar = 4-i-PrC6H4 (4a), 2,6-i-Pr2C6H3 (4b)), respectively, on reaction with an aqueous sodium chloride solution. Treating each of 3a, 3b, 4a and 4b with two equivalents of di-p-tolyliodonium triflate at 100 °C in a toluene/acetonitrile mixture affords varying amounts of 4-chlorotoluene along with the 4-iodotoluene by-product with the conversions highly dependent on the steric and backbone properties of the pincer complex employed (viz.4a > 3a > 4b > 3b); notably, the least sterically bulky and most flexible amine-containing 4a reaches 90% conversion to 4-chlorotoluene in 15 h as opposed to 17% for imine-containing 3b. In the case of 3a, the inorganic palladium species recovered from the reaction has been identified as the Pd(ii) salt [{2-(C6H4-2′-O)-6-(CMeN(4-i-PrC6H4)C5H3N}Pd(NCMe)][O3SCF3] (5a), which was independently prepared by the reaction of 3a with silver triflate in acetonitrile. Single crystal X-ray structures are reported for HL1a, HL2a, 1a, 1b, 2a, 2b, 3a and 5a. This journal is
Phenolate substituent effects on ring-opening polymerization of ε-caprolactone by aluminum complexes bearing 2-(phenyl-2-olate)-6-(1- amidoalkyl)pyridine pincers
Alkarekshi, Wafaa,Armitage, Andrew P.,Boyron, Olivier,Davies, Christopher J.,Govere, Matifadza,Gregory, Andrew,Singh, Kuldip,Solan, Gregory A.
, p. 249 - 259 (2013/02/25)
Interaction of the 2-(phenyl-2-ol)-6-ketiminopyridines 2-(4′-R 1-C6H3-2′-OH)-6-{CMe=N(2″,6″- i-Pr2C6H3)}C5H3N (R 1 = H (L1a-H), But (L
