@article {46838,
	title = {Palladium-catalyzed insertion of ethylene and 1,1-disubstituted difunctional olefins: an experimental and computational study},
	journal = {ChemPlusChem},
	volume = {85},
	year = {2020},
	month = {JUN},
	pages = {1200-1209},
	type = {Article},
	abstract = {<p>Insertion or coordination copolymerization of ethylene with di-substituted olefins is challenging and the choice of di-substituted mono-functional olefin versus di-substituted di-functional olefin (DDO) appears to be decisive. Here we show that DDO-inserted species are amenable to ethylene insertion and polymerization. DDOs such as 2-acetamidoacrylic acid (AAA), methyl 2-acetamidoacrylate (MAAA), and ethyl 2-cyanoacrylate (ECA) were treated with palladium complex [{P perpendicular to O}PdMe(L)] (P perpendicular to O=kappa(2)-P,O-Ar2PC6H4SO2O with Ar=2-MeOC6H4; L=C2H6OS) and the existence of respective insertion intermediates in moderate yield (up to 37 \%) was established. These intermediates were exposed to ethylene and corresponding ethylene-inserted products were isolated and characterized. A careful comparison with three model compounds confirmed ethylene insertion and polymerization. Thus, the combined experimental and computational investigations show that DDO-inserted species can undergo ethylene insertion and polymerization.</p>
},
	keywords = {Homogeneous catalysis, insertion copolymerization, Olefins, Palladium, Polyethylene},
	issn = {2192-6506},
	doi = {10.1002/cplu.202000309},
	author = {Gaikwad, Shahaji R. and Patel, Ketan and Deshmukh, Satej S. and Mote, Nilesh R. and Birajdar, Rajkumar S. and Pandole, Satish P. and Chugh, Jeetender and Chikkali, Samir H.}
}
@article {46996,
	title = {Pd-iminocarboxylate complexes and their behavior in ethylene polymerization},
	journal = {Chemistry-An Asian Journal},
	volume = {15},
	year = {2020},
	month = {FEB },
	pages = {398-405},
	type = {Article},
	abstract = {<p>Designing co-catalyst-free late transition metal complexes for ethylene polymerization is a challenging task at the interface of organometallic and polymer chemistry. Herein, a set of new, co-catalyst-free, single-component catalytic systems for ethylene polymerization have been unraveled. Treatment of anthranilic acid with various aldehydes produced four iminocarboxylate ligands (L1-L4) in very good to excellent yield (75-92 \%). The existence of 2-((2-methoxybenzylidene)amino) benzoic acid (L1) has been unambiguously demonstrated using NMR spectroscopy, MS and single-crystal X-ray diffraction. A neutral Pd-iminocarboxylate complex [{N O}PdMe(L1)] (N O=kappa(2)-N,O-ArCHNC6H4CO2 with Ar=2-MeOC6H4) C1 was prepared by treating stoichiometric amount of L1.Na with palladium precursor. The identity of C1 was confirmed by 1-2D NMR spectroscopy and single-crystal X-ray diffraction studies. Along the same lines, palladium complexes C2-C4 were prepared from ligands L2-L4 respectively. In-situ high-pressure NMR investigations revealed that these Pd complexes are amenable to ethylene insertion and undergo facile beta-H elimination to produce propylene. These palladium complexes were then evaluated in ethylene polymerization reaction and various reaction parameters were screened. When C1-C4 were exposed to ethylene pressures of 10-50 bar, formation of low-molecular-weight polyethylene was observed.</p>
},
	keywords = {imine, Imine-carboxylate, Insertion polymerization, Pd complexes, Polyethylene},
	issn = {1861-4728},
	doi = {10.1002/asia.201901501, Early Access Date = JAN 2020},
	author = {Deshmukh, Satej S. and Gaikwad, Shahaji R. and Gonnade, Rajesh G. and Pandole, Satish P. and Chikkali, Samir H.}
}
