Optimized syntheses for 1,3-dimesitylnaphthoquinimidazolium chloride [1H][Cl] and the corresponding silver−NHC complex [AgCl(1)] (2) were developed, enabling access to this versatile reagent in near-quantitative yield. Transmetalation from 2 [NiCl2(PPh3)2], trans-[PdCl2(PhCN)2], or trans-[PtCl2(PhCN)2] afforded Group 10 complexes trans-[MCl2(1)2] (3a−c, M = Ni, Pd, Pt, respectively) excellent overall yield (>95%) after three steps commercially available starting materials. Electrochemical...

The ability to control catalytic activity and selectivity via in situ changes catalyst oxidation-state represents an intriguing tool for enhanced polymerization control. Herein, we report foundational evidence that catalysts bearing redox-active moieties may be used synthesize high molecular weight polyethylene with tailored microstructure. modulate branching density identity is facilitated by ligand-based redox chemistry, realized the addition of chemical reductants into reactor. Detailed...

Lignin is the second-most abundant biopolymer in nature and remains a severely underutilized waste product of agriculture paper production.

To investigate effects of redox-active functional groups on the coordination chemistry and electronic properties N-heterocyclic carbenes (NHCs), we prepared a series complexes comprising 1,3-diferrocenylimidazolylidene -benzimidazolylidene (1 2, respectively), 1-ferrocenyl-3-methyl- 1,3-diphenyl-5-ferrocenylbenzimidazolylidene (3 4, N,N′-diisobutyldiaminocarbene[3]ferrocenophane (FcDAC), 1,3-dimesitylnaphthoquinoimidazolylidene (NqMes) ligands coordinated [Ir(COD)Cl] (COD =...

Condensation of N,N′-dimesitylformamidine with phthaloyl chloride afforded 1·HCl, which, upon treatment base, 2,4-dimesitylbenzo[e][1,3]diazepin-1,5-dione-2-ylidene (1), a seven-membered N,N′-diamidocarbene (DAC), in high yield (85%). The free DAC was used to synthesize four new, late transition metal complexes: [Rh(cod)(1)Cl] (2a) (cod = 1,5-cyclooctadiene), [Ir(cod)(1)Cl] (2b), [Rh(CO)2(1)Cl] (3a), and [1−AuCl] (5). Tolman electronic parameter (TEP) 1 calculated be 2047 cm−1 from the IR...

Bimetallic [Ir(COD)Cl] and [Ir(ppy)(2)] (COD = 1,5-cyclooctadiene; ppy 2-phenylpyridyl) complexes bridged by 1,7-dimethyl-3,5-diphenylbenzobis(imidazolylidene) (1), in addition to their monometallic analogues supported 1-methyl-3-phenylbenzimidazolylidene (2), were synthesized studied. Electrochemical analyses indicated that 1 facilitated moderate electronic coupling between units (DeltaE approximately 60 mV), but not [Ir(ppy)(2)]. The metal-based oxidation potentials for the bimetallic...

Reaction of bromanil with N,N'-dimesitylformamidine followed by deprotonation NaN(SiMe(3))(2) afforded 1,1',3,3'-tetramesitylquinobis(imidazolylidene) (1), a bis(N-heterocyclic carbene) (NHC) two NHC moieties connected redox active p-quinone residue, in 72 % yield isolated compound. Bimetallic complexes 1 were prepared coupling to FcN(3) (2) or FcNCS (3; Fc=ferrocenyl) coordination [M(cod)Cl] (4 4 b, where M=Rh Ir, respectively; cod=1,5-cyclooctadiene). Treatment and b excess CO(g) the...

ABSTRACT Sulfur and oleic acid, two components of industrial waste/byproducts, were combined in an effort to prepare more sustainable polymeric materials. Zinc oxide was employed serve the dual role compatibilizing immiscible sulfur acid as well suppress evolution toxic H 2 S gas during reaction at high temperature. The sulfur, zinc led a series composites, ZOS x ( = wt % where is 8–99). materials ranged from sticky tars hard solids room compositions assessed by 1 NMR spectrometry, FTIR...

A turn-on fluorescent sensor for NO (g) in solution was synthesized using a bipyridyl-substituted poly(p-phenylene vinylene) derivative (CP1) as the sensory scaffold. The action of upon CP1−Cu(II) complex reduces it to CP1−Cu(I) with concomitant 2.8-fold increase emission intensity. reagent is selective versus other biological reactive nitrogen species, except nitroxyl, and has detection sensitivity limit 6.3 nM.

Coupling of pyridine-capped poly(methyl acrylate)s, PyP(M) (where M corresponds to the number average molecular weight in kDa), SCS-cyclometalated dipalladium complex [(1)(CH(3)CN)(2)] afforded organometallic polymers [(1)(PyP(M))(2)] with a concomitant doubling weight. Ultrasonication solutions containing effected mechanical scission palladium-pyridine bond, where liberated was trapped excess HBF(4) as corresponding pyridinium salt, harnessed effect stoichiometric deprotonation colorimetric...

A click by any other name: Coupling bis(N-heterocyclic carbene)s with bis(azide)s afforded a novel class of conjugated polytriazenes. These polymers were rendered electrically conductive upon doping, and fluorene-containing variants exhibited luminescence. This adaptation N-heterocyclic carbene (NHC)/azide coupling chemistry to polymer synthesis reveals the potential NHCs as building blocks for accessing having useful electronic properties.

A major challenge in the pursuit of dynamic materials is dichotomy between reversible structure and electronic conjugation. Guided by precedence for N ‐heterocyclic carbenes (NHCs) to dimerize, couple with electrophiles bind transition metals, we proposed that linearly opposed bis(NHC)s could, a similar manner, afford unsaturated homopolymers, alternating copolymers, metallopolymers. To realize these goals, developed synthetic methods accessing ditopic NHCs investigated their propensities...

Abstract Nature provides a rich panoply of structural motifs comprised composites whose mechanical properties exceed those their individual components. The human endeavor to likewise craft value‐added materials from underappreciated, sustainably sourced feedstocks remains formidable challenge. Herein, efforts are made achieve durable by synergistic combination sulfur and cellulose. Composites achieved in which bulk is reinforced network 1–20% mass cellulose cross‐linked with polysulfide...

Chlorolignin can be copolymerized with sulfur in different ratios to form durable, recyclable materials.

ABSTRACT Efforts to develop sustainable industrial processes have led significant advances toward supplanting petrochemical‐dependent technologies. Some of these otherwise processes, notably animal product rendering and biodiesel production, produce low value waste that is high in free fatty acids. Sulfur turn a primary fossil fuel refining. In the current contribution, copolymers are prepared by reaction elemental sulfur with acids several monomer ratios. Both monounsaturated oleic acid...

RASP (radical-induced aryl halide-sulfur polymerization) is reported as a new route to high sulfur-content materials.

Productive utilization of lignocellulosic biomass is critical to the continued advancement human civilization. Whereas cellulose component can be efficiently upconverted automotive fuel-grade ethanol, lack upconversion methods for lignin constitutes one grand challenges facing science. Lignin an attractive feedstock structural applications, in which its highly-crosslinked architecture endow composite structures with high strengths. Prior work suggests that high-strength composites prepared...

Over 80 MT of elemental sulfur, a byproduct fossil fuel desulfurization, are generated annually. This has spurred the development high sulfur content materials (HSMs) via inverse vulcanization as productive pathway towards utilization. In this study, we evaluate antimicrobial performance SunBG90, an HSM made from brown grease and tiles or infused into fabric squares. The static activity SunBG90 was assessed, revealing excellent efficacy against Gram-positive bacteria, with reductions 96.84%...

Chemical oxidation of poly(enetetramine)s was demonstrated as a new synthetic route to prepare conjugated polyelectrolytes.

Abstract A new, high‐yielding synthesis of 3,3′,4,4′‐tetrachlorobiphenyl was developed, facilitating access to a new family fluorescent 5,5′‐bibenzimidazolium salts bearing phenyl or bulky tertiary alkyl N‐substituents. Deprotonation these afforded the respective 5,5′‐bibenzimidazolylidenes in excellent isolated yields (≥86 %), which were characterized solid state and solution. Treatment ditopic ligands with [Rh(COD)Cl] 2 (COD = 1,5‐cyclooctadiene) bimetallic complexes composed two Rh atoms...

Sulfur and a polystyrene derivative were combined to form thermally-healable recyclable composite materials with dramatically increased structural integrity <italic>versus</italic> sulfur alone.

Copolymers of waste sulfur and bacterially-produced tyrosine are reported.

A composite was prepared from biomass and waste sulfur fossil fuel refining.