Phosphasalen yttrium complexes: highly active and stereoselective initiators for lactide polymerization

Preparation and characterization of three yttrium alkoxide complexes with new phosphasalen ligands are reported. The phosphasalens are analogues of the well-known salen ligands but with iminophosphorane donors replacing the imine functionality. The three yttrium alkoxide complexes show mono- and dinuclear structures in the solid state, depending on the substituents on the ligand. The new ligands and complexes are characterized using multinuclear NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction experiments. The complexes are all rapid initiators for lactide polymerization; they show excellent polymerization control on addition of exogeneous alcohol. The mononuclear complex shows extremely rapid rates and a high degree of stereocontrol in rac-lactide polymerization, yielding heterotactic PLA (P(s) of 0.9). The phosphasalens are, therefore, excellent ligands for lactide ring-opening polymerization catalysis showing superior rates and stereocontrol versus salen ligands, which may be related to their excellent donating ability and the high degrees of steric protection they can confer.     

Synthesis of Planar Chiral Iridacycles by Cationic Metal π‐Coordination: Facial Selectivity,and Conformational and Stereochemical Consequences

Facial selectivity during the π‐coordination of pseudo‐tetrahedral iridacycles by neutral (Cr(CO)₃), monocationic (Cp*Ru⁺), and biscationic (Cp*Ir²⁺) metal centers was directly influenced by the coulombic imbalance in the coordination sphere of the chelated Ir center. We also showed by using theoretical calculations that the feasibility of the related metallacycles that displayed metallocenic planar chirality was dependent to the presence of an electron‐donating group, such as NMe₂, which contributed to the overall stability of the complexes. When the π‐bonded moiety was the strongly electron‐withdrawing Cp*Ir²⁺ group, the electron donation from NMe₂ resulted in major conformational changes, with a barrier to rotation of about 17 kcal mol^?1 for this group that became spectroscopically diastereotopic (high‐field ¹H NMR spectroscopy). This peculiar property is proposed as a means to introduce a new type of constitutional chirality at the nitrogen center: planar chirality at tertiary aromatic amines.     

A new quantitative method to measure activity of ice structuring proteins using differential scanning calorimetry

There are very few quantitative assays to measure the activity of antifreeze proteins (AFPs, or Ice Structuring Proteins, ISPs) and these can be prone to various inaccuracies and inconsistencies. Some methods rely only on unassisted visual assessment. When microscopy is used to measure ice crystal size, it is critical that standardized procedures be adopted, especially when image analysis software is used to quantify sizes. Differential Scanning Calorimetry (DSC) has been used to measure the thermal hysteresis activity (TH) of AFPs. In this study, DSC was used isothermally to measure enthalpic changes associated with structural rearrangements as a function of time. Differences in slopes of isothermal heat flow vs. time between winter wheat ISP or AFP type I containing samples, and those without ISP or AFP type I were demonstrated. ISP or AFP type I containing samples had significantly higher slopes compared to those without ISP or AFP type I. Samples with higher concentration of ISP or AFP type I showed higher slope values during the first hour and took up to 3 hr to attain equilibrium. Differences were attributed to activity of the proteins at the ice interface. Proteinaceous activity of ISPs or AFP type I was confirmed by loss of activity after treatment with protease.     

Combined powder neutron and X-ray diffraction study of charge and orbital order in Bi0.75Sr0.25MnO3

The room temperature structure of Bi_0.75Sr_0.25MnO₃ has been fitted to high-resolution synchrotron X-ray and time-of-flight neutron powder diffraction data. Constrained structural models were refined using a Pn11 supercell (, , , and α=89.894(1)°) of the underlying Pnma perovskite structure. The best-fit model evidences a 3:1 Mn³⁺/Mn⁴⁺charge ordering with only 30% of the ideal separation of bond valence sums. An ordered intergrowth of antiferro-orbitally ordered (LaMnO₃ type) and charge and ferro-orbitally ordered (YBaMn₂O₆ type) blocks is observed. Off-centre Bi/Sr displacements are ferroelectrically ordered in this model.     

[5,10,15,20‐Tetrakis­(penta­fluoro­phenyl)­porphyrinato]­iron(II) benzene disolvate

The title compound, [Fe(C₄₄H₈F₂₀N₄)]·2C₆H₆, contains a four‐coordinated Fe^II atom, which lies on a center of symmetry. The porphyrin macrocycle is planar, and the Fe—N bond distances are in the range 1.9891 (13)–1.9982 (13) Å. The spin state of the Fe^II atom is intermediate (S = 1), as confirmed by NMR spectroscopy. The asymmetric unit contains two half benzene mol­ecules, each lying about an independent inversion centre; one of the benzene rings is located just below (and by inversion symmetry, another is just above) the Fe atom, where it interacts weakly with the porphyrin ring.     

Phase relations and crystal structures in the systems (Bi,Ln)2WO6 and (Bi,Ln)2MoO6 (Ln=lanthanide)

Several outstanding aspects of phase behaviour in the systems (Bi,Ln)₂WO₆ and (Bi,Ln)₂MoO₆ (Ln=lanthanide) have been clarified. Detailed crystal structures, from Rietveld refinement of powder neutron diffraction data, are provided for Bi_1.8La_0.2WO₆ (L-Bi₂WO₆ type) and BiLaWO₆, BiNdWO₆, Bi_0.7Yb_1.3WO₆ and Bi_0.7Yb_1.3WO₆ (all H-Bi₂WO₆ type). Phase evolution within the solid solution Bi_2−xLa_xMoO₆ has been re-examined, and a crossover from γ(H)-Bi₂MoO₆ type to γ-R₂MoO₆ type is observed at x∼1.2. A preliminary X-ray Rietveld refinement of the line phase BiNdMoO₆ has confirmed the α-R₂MoO₆ type structure, with a possible partial ordering of Bi/Nd over the three crystallographically distinct R sites.     

Supramolecular Immobilization of Laccase on Carbon Nanotube Electrodes Functionalized with (Methylpyrenylaminomethyl)anthraquinone for Direct Electron Reduction of Oxygen

An efficient way of immobilizing and wiring a large amount of laccase on non‐covalently‐functionalized multi‐walled carbon nanotube (MWCNT) electrodes is reported. 1‐(2‐anthraquinonylaminomethyl)pyrene and 1‐[bis(2‐anthraquinonyl)aminomethyl]pyrene were synthesized and studied for their capability to non‐covalently functionalize MWCNT electrodes and immobilize and orientate laccase on the nanostructured electrodes. This led to high‐performance biocathodes for oxygen reduction by direct electron transfer with maximum current densities of (1±0.2) mA cm^?2. The performance of the resulting bioelectrodes could be doubled simply by using the bis‐anthraquinone compound. The bioelectrodes show excellent stability over weeks and can thus be envisioned in enzymatic biofuel cells.     

Room-temperature palladium-catalyzed Negishi-type coupling: a combined experimental and theoretical study

An air-stable, bulky electron-accepting phosphine ligand (phosphabarrelene) allows the easy reduction of a Pd(II) precursor to a Pd(0) complex, highly active in room-temperature Negishi-type cross-coupling. DFT calculations show that the use of the electron-accepting ligand favors both transmetalation (TM) and reductive-elimination (RE) processes (see scheme; OA = oxidative addition).