Highly selective pressure-dependent (transfer) hydrogenative depolymerization of polybutylene succinate.

Ru-MACHO®-BH is an effective catalyst for controlled depolymerization of polybutylene succinate. Under low pressure hydrogen the catalyst produces gamma-butyrolactone via a novel transfer hydrogenation wherein dehydrogenation and hydrogenation deconstruct the polymer chain. Simply increasing the hydrogen pressure selectively generates 1,4-butanediol.

Controlled hydrogenative depolymerization of polyesters and polycarbonates catalyzed by ruthenium(II) PNN pincer complexes.

Ruthenium(II) PNN complexes depolymerize many polyesters into diols and polycarbonates into glycols plus methanol via hydrogenation. Notably, polyesters with two methylene units between ester linkages depolymerize to carboxylic acids rather than diols. This methodology represents a new approach for producing useful chemicals from waste plastics.

Synthesis of high molecular weight polyesters via in vacuo dehydrogenation polymerization of diols.

The Milstein catalyst has proven to be highly effective for the conversion of alcohols to esters, as well as alcohols and amines to amides and polyamides. We have recently found that the catalyst's range can be extended to very efficient in vacuo dehydrogenation polymerization of α,ω-diols to generate polyesters. The gaseous hydrogen byproduct that is produced is easily removed to drive the equilibrium toward product, which leads to the formation of high molecular weight polymer (M(n) up to 145,000 g mol(-1)). This optimized methodology works well to polymerize diols with a spacer of six carbons or more. Diols with fewer carbons are cyclized to lactone; the dividing point is the dehydrogenation of 1,5-pentanediol, which leads to a mixture of polyester and lactone. Reported herein is the synthesis and characterization of five aliphatic polyesters prepared via this novel dehydrogenation polymerization approach.

Tunable high performance cross-linked alkaline anion exchange membranes for fuel cell applications.

Fuel cells are energy conversion devices that show great potential in numerous applications ranging from automobiles to portable electronics. However, further development of fuel cell components is necessary for them to become commercially viable. One component critical to their performance is the polymer electrolyte membrane, which is an ion conductive medium separating the two electrodes. While proton conducting membranes are well established (e.g., Nafion), hydroxide conducting membranes (alkaline anion exchange membranes, AAEMs) have been relatively unexplored by comparison. Operating under alkaline conditions offers significant efficiency benefits, especially for the oxygen reduction reaction; therefore, effective AAEMs could significantly advance fuel cell technologies. Here we demonstrate the use of ring-opening metathesis polymerization to generate new cross-linked membrane materials exhibiting high hydroxide ion conductivity and good mechanical properties. Cross-linking allows for increased ion incorporation, which, in turn supports high conductivities. This facile synthetic approach enables the preparation of cross-linked materials with the potential to meet the demands of hydrogen-powered fuel cells as well as direct methanol fuel cells.

A ring-opening metathesis polymerization route to alkaline anion exchange membranes: development of hydroxide-conducting thin films from an ammonium-functionalized monomer.

We report the development of a facile ring-opening olefin metathesis route to alkaline anion exchange membranes via the copolymerization of a tetraalkylammonium-functionalized norbornene with dicyclopentadiene. The thin films generated are mechanically strong and exhibit high hydroxide conductivities and exceptional methanol tolerance.

Two-dimensional double metal cyanide complexes: highly active catalysts for the homopolymerization of propylene oxide and copolymerization of propylene oxide and carbon dioxide.

The synthesis of two-dimensional double metal cyanide complexes of the formula Co(H2O)2[M(CN)4].4H2O (M=Ni, Pd or Pt) and the X-ray crystal structure of Co(H2O)2[Pd(CN)4].4H2O are presented. The anhydrous forms of these complexes were found to be effective catalyst precursors for the homopolymerization of propylene oxide as well as the random copolymerization of propylene oxide and carbon dioxide to produce poly(propylene oxide-co-propylene carbonate) with no propylene carbonate byproduct. A detailed copolymer microstructure is proposed.

Chromium(II) and chromium(III) complexes supported by tris(2-pyridylmethyl)amine: synthesis, structures, and reactivity.

This report describes the synthesis, structural characterization, and polymerization behavior of a series of chromium(II) and chromium(III) complexes ligated by tris(2-pyridylmethyl)amine (TPA), including chromium(III) organometallic derivatives. For instance, the combination of TPA with CrCl(2) yields monomeric (TPA)CrCl(2) (1). A similar reaction of CrCl(2) with TPA, followed by chloride abstraction with NaBPh(4) or NaBAr(F)(4) (Ar(F) = 3,5-(CF(3))(2)C(6)H(3)), provides the weakly associated cationic dimers [(TPA)CrCl](2)[BPh(4)](2) (2A) and [(TPA)CrCl](2)[BAr(F)(4)](2) (2B), respectively. X-ray crystallographic analysis reveals that each chromium(II) center in 1, 2A, and 2B is a tetragonally elongated octahedron; such Jahn-Teller distortions are consistent with the observed high spin (S = 2) electronic configurations for these chromium(II) complexes. Likewise, reaction of CrCl(3)(THF)(3) with TPA, followed by anion metathesis with NaBPh(4) or NaBAr(F)(4), yields the monomeric, cationic chromium(III) complexes [(TPA)CrCl(2)][BPh(4)] (4A) and [(TPA)CrCl(2)][BAr(F)(4)] (4B), respectively. Treatment of 4A with methyl and phenyl Grignard reagents produces the cationic chromium(III) organometallic derivatives [(TPA)Cr(CH(3))(2)][BPh(4)] (5) and [(TPA)CrPh(2)][BPh(4)] (6), respectively. Similar reactions of 4A with organolithium reagents leads to intractable solids, presumably due to overreduction of the chromium(III) center. X-ray crystallographic analysis of 4A, 5, and 6 confirms that each possesses a largely undistorted octahedral chromium center, consistent with the observed S = (3)/(2) electronic ground states. Compounds 1, 2A, 2B, 4A, 4B, 5, and 6 are all active polymerization catalysts in the presence of methylalumoxane, producing low to moderate molecular weight high-density polyethylene.