ABC and ABAB Block Copolymers by Electrochemically Controlled Ring-Opening Polymerization.

An electrochemically controlled synthesis of multiblock copolymers by alternating the redox states of (salfan)Zr(OtBu)2 (salfan = 1,1'-di(2-tert-butyl-6-N-methylmethylenephenoxy)ferrocene) is reported. Aided by electrochemistry with a glassy carbon working electrode, an in situ potential switch alters the catalyst's oxidation state and its subsequent monomer (l-lactide, ß-butyrolactone, or cyclohexene oxide) selectivity in one pot. Various multiblock copolymers were prepared, including an ABAB tetrablock copolymer, poly(cyclohexene oxide-b-lactide-b-cyclohexene oxide-b-lactide), and an ABC triblock copolymer, poly(hydroxybutyrate-b-cyclohexene oxide-b-lactide). The polymers produced using this technique are similar to those produced via a chemical redox reagent method, displaying moderately narrow dispersities (1.1-1.5) and molecular weights ranging from 7 to 26 kDa.

Exploring Oxidation State-Dependent Selectivity in Polymerization of Cyclic Esters and Carbonates with Zinc(II) Complexes.

Neutral zinc alkoxide complexes show high activity toward the ring-opening polymerization of cyclic esters and carbonates, to generate biodegradable plastics applicable in several areas. Herein, we use a ferrocene-chelating heteroscorpionate complex in redox-switchable polymerization reactions, and we show that it is a moderately active catalyst for the ring-opening polymerization of L-lactide, ɛ-caprolactone, trimethylene carbonate, and δ-valerolactone. Uniquely for this type of catalyst, the oxidized complex has a similar polymerization activity as the corresponding reduced compound, but displays significantly different rates of reaction in the case of trimethylene carbonate and δ-valerolactone. Investigations of the oxidized compound suggest the presence of an organic radical rather than an Fe(III) complex. Electronic structure and density functional theory (DFT) calculations were performed to support the proposed electronic states of the catalytic complex and to help explain the observed reactivity differences. The catalyst was also compared with a monomeric phenoxide complex to show the influence of the phosphine-zinc interaction on catalytic properties.

Palladium complexes with Pd-->B dative bonds: analysis of the bonding in the palladaboratrane compound [kappa4-B(mimBut)3]Pd(PMe3).

The dinuclear complex {[mu-kappa(1),kappa(3)-B(mim(Bu(t)))(3)]Pd}(2), which features a Pd-->B dative bond, may be obtained by the reaction of [Tm(Bu(t))]K with Pd(OAc)(2); treatment of {[mu-kappa(1),kappa(3)-B(mim(Bu(t)))(3)]Pd}(2) with PMe(3) affords the mononuclear boratrane derivative [kappa(4)-B(mim(Bu(t)))(3)]Pd(PMe(3)), for which a molecular orbital analysis indicates that the palladium center possesses a d(8) configuration.

High activity of an indium alkoxide complex toward ring opening polymerization of cyclic esters.

An indium complex supported by a ferrocene-derived Schiff base ligand has an unprecedented high activity toward ε-caprolactone, δ-valerolactone, and ß-butyrolactone. l-Lactide, d,l-lactide, and trimethylene carbonate polymerizations also showed moderate to high activity.

Tetrahedral nickel nitrosyl complexes with tripodal [N3] and [Se3] donor ancillary ligands: structural and computational evidence that a linear nitrosyl is a trivalent ligand.

Linear nickel nitrosyl compounds supported by tridentate nitrogen and selenium ligands, namely the tris(3,5-dimethylpyrazolyl)hydroborato and tris(2-seleno-1-mesitylimidazolyl)hydroborato complexes, [TpMe2]NiNO and [TseMes]NiNO, have been synthesized and structurally characterized by X-ray diffraction. Computational studies demonstrate that the linear nitrosyl ligand behaves as a trivalent X3 ligand such that the Ni-N interaction has multiple bond character.