Controlled di-lithiation enabled synthesis of phosphine-sulfonamide ligands and implications in ethylene oligomerization.

Catalyst design for ethylene oligomerization has attracted significant interest. Herein, we report the synthesis of phosphine-sulfonamide-derived palladium complexes and examine their performance in ethylene oligomerization. Arresting a dilithiation intermediate of N-(2-bromophenyl)-4-methylbenzenesulfonamide (1) at -84 °C selectively produced N-(2-(bis(2-methoxyphenyl)phosphanyl)phenyl)-4-methylbenzenesulfonamide (L1A).

Palladium-Catalyzed Insertion of Ethylene and 1,1-Disubstituted Difunctional Olefins: An Experimental and Computational Study.

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∧O}PdMe(L)] (P∧O=κ -P,O-Ar PC H SO O with Ar=2-MeOC H ; L=C H OS) and the existence of respective insertion intermediates in moderate yield (up to 37 %) was established.

Pd-Iminocarboxylate Complexes and Their Behavior in Ethylene Polymerization.

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 %).

Neutral Imino-Methyl Benzenesulfonate-Ligated Pd(II) Complexes and Implications in Ethylene Polymerization.

A reaction between sodium 2-formylbenzenesulfonate and aniline revealed the near-quantitative (91%) formation of sodium-2-((phenylimino)methyl)benzenesulfonate . The identity of was unambiguously ascertained using spectroscopic and analytical methods. The scope of this methodology was widened and various electron-donating amines were treated with sodium 2-formylbenzenesulfonate, and a small library of 6 imine ligands was generated.

H-Bonding Assisted Self-Assembly of Anionic and Neutral Ligand on Metal: A Comprehensive Strategy To Mimic Ditopic Ligands in Olefin Polymerization.

Self-assembly of two neutral ligands on a metal to mimic bidentate ligand coordination has been frequently encountered in the recent past, but self-assembly of an anionic ligand on a metal template alongside a neutral ligand remains an elusive target. Such a self-assembly is hampered by additional complexity, wherein a highly negatively charged anion can form intermolecular hydrogen bonding with the supramolecular motif, leaving no scope for self-assembly with neutral ligand. Presented here is the self-association of anionic ligand 3-ureidobenzoic acid (2a) and neutral ligand 1-(3-(diphenylphosphanyl)phenyl)urea (1a) on a metal template to yield metal complex [{COOCHNH(CO)NH}{PhPCHNH(CO)NH}PdMeDMSO] (4a).

Insertion Copolymerization of Difunctional Polar Vinyl Monomers with Ethylene.

A single-step synthesis, structural characterization and application of a neutral, acetonitrile ligated, palladium-phosphinesulfonate complex [{PO}PdMe(L)] (PO = κ-P,O-ArCHSO with Ar = 2-MeOCH; L = CHCN) () in coordination/insertion copolymerization of ethylene with difunctional olefin is investigated. In a significant development, complex was found to catalyze insertion copolymerization of industrially relevant 1,1-disubstituted difunctional vinyl monomers for the first time. Thus, insertion copolymerization of ethyl-2-cyanoacrylate (ECA or super glue) and trifluoromethyl acrylic acid (TFMAA) with ethylene produced the corresponding copolymers with 6.