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Phospholane-phosphites are known to show highly unusual selectivity towards branched aldehydes in the hydroformylation of terminal alkenes. This paper describes the synthesis of hitherto unknown unsaturated phospholene borane precursors and their conversion to the corresponding phospholene-phosphites. The relative stereochemistry of one of these ligands and its Pd complex was assigned with the aid of X-ray crystal structure determinations. These ligands were able to approach the level of selectivity observed for phospholane-phosphites in the rhodium-catalysed hydroformylation of propene. High-pressure infra-red (HPIR) spectroscopic monitoring of the catalyst formation revealed that whilst the catalysts showed good thermal stability with respect to fragmentation, the C=C bond in the phospholene moiety was slowly hydrogenated in the presence of rhodium and syngas. The ability of this spectroscopic tool to detect even subtle changes in structure, remotely from the carbonyl ligands, underlines the usefulness of HPIR spectroscopy in hydroformylation catalyst development. [ABSTRACT FROM AUTHOR]

A manganese catalyst of a facially coordinating P,N,N ligand catalyses the hydrogenation of imines derived from indanone derivatives with high enantioselectivity. There is no requirement for an activating group and imines can be generated in situ. The selectivity can be rationalised by DFT calculations. [ABSTRACT FROM AUTHOR]

DFT calculations on the full catalytic cycle for manganese catalysed enantioselective hydrogenation of a selection of ketones have been carried out at the PBE0‐D3PCM//RI‐BP86PCM level. Mn complexes of an enantiomerically pure chiral P,N,N ligand have been found to be most reactive when adopting a facial coordination mode. The use of a new ligand with an ortho‐substituted dimethylamino‐pyridine motif has been calculated to completely transform the levels of enantioselectivity possible for the hydrogenation of cyclic ketones relative to the first‐generation Mn catalysts. In silico evaluation of substrates has been used to identify those likely to be reduced with high enantiomer ratios (er), and others that would exhibit less selectivity; good agreements were then found in experiments. Various cyclic ketones and some acetophenone derivatives were hydrogenated with er's up to 99 : 1. [ABSTRACT FROM AUTHOR]

The combination of vibrational spectroscopic techniques is used to study the structural information of interfacial proteins and peptides. The development of nonlinear vibrational spectroscopies has helped in understanding the structures and the functions of proteins and peptides at interfaces.

The structural changes of fibrinogen after adsorption to polystyrene (PS) is investigated at the PS/protein solution interface in situ using sum frequency generation (SFG) vibrational spectroscopy and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). The research has indicated that the interactions between adsorbed fibrinogen and the PS surface can induce significant changes of protein secondary structures or global conformations.

A study to investigate the adsorption behavior of fibrinogen to two biomedical polyurethanes and a perfluorinated polymer was conducted. Investigation of fibrinogen adsorption revealed that fibrinogen binds and undergoes conformational changes that are highly dependent on the chemical properties of the surface.

A 'polarization mapping' method has been applied to improve the fitting quality of sum frequency generation (SFG) vibrational spectra of complicated systems and validate the data analysis of simple SFG spectra. Using such a method, two-dimensional SFG spectra can be constructed, from which more reliable spectral information can be obtained from a surface/interface. Model calculations as well as experiments have been employed to illustrate the power of the polarization mapping method for spectral analysis of SFG spectra. By using a deuterated polystyrene surface and interfacial protein molecules as examples, we demonstrate that this method is especially important for complicated molecules, such as polymers and proteins.

This study characterizes the molecular surface structures of polyurethane (PU) and plasticized PU films in air, in water, and in albumin solution in situ using a nonlinear optical technique, sum frequency generation (SFG) vibrational spectroscopy. Two different plasticizers are investigated: dioctyl sebacate (DOS) and o-nitrophenyl octyl ether (NPOE). Plasticization of PU is common for biosensors to achieve better adhesion, malleability, elasticity, and permeability; however, this can adversely affect biocompatibility. Our research indicates that plasticizers can segregate to the PU surface not only in air but also in water. In addition, plasticizer content can affect protein adsorption behaviors of PU surfaces. This is the first time surface-sensitive SFG has been applied to deduce plasticizer surface behavior in situ. More specifically, we found that DOS dominates the surface of the film with DOS surface concentrations higher than DOS bulk concentrations both in air and in contact with an aqueous environment. NPOE has a reduced effect at the surface compared to DOS in both air and aqueous environments. Addition of either DOS or NPOE to PU was also found to cause a change in albumin adsorption.

Manganese catalysed ester reduction using ethanol as a hydrogen transfer agent in place of dihydrogen is reported. High yields can be achieved for a range of substrates using 1 mol% of a Mn(I) catalyst, with an alkoxide promoter. The catalyst is derived from a tridentate P,N,N ligand. [ABSTRACT FROM AUTHOR]

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The protein adsorption on native oxide-covered polycrystalline Ti surfaces is analyzed using the sum frequency generation (SFG) vibrational spectroscopy. The SFG results suggest that structures of adsorbed protein molecules change during the adsorption process.

The scope of carbon monoxide‐free Asymmetric Transfer HydroFormylation (ATHF) procedures using a highly active single catalyst system derived from 1,2‐bis‐((2,5)‐diphenylphospholano)ethane as chiral ligand has been studied. This reveals some highly successful reactions, but also significant limitations. The development of a new protocol in which a catalyst for formaldehyde decomposition to CO and H2 is combined with the catalyst of choice for the subsequent asymmetric hydroformylation is described. This enables ATHF reactions that were problematic to be significantly improved. The new method has been used in the synthesis of several key precursors to biologically active molecules. [ABSTRACT FROM AUTHOR]

High diastereoselectivity was observed in the Rh-catalysed reductive amination of 3-arylcyclohexanones to form tertiary amines. This was incorporated into a one-pot enantioselective conjugate addition and diastereoselective reductive amination, including an example of assisted tandem catalysis. [ABSTRACT FROM AUTHOR]

A porous scandium MOF denoted STA-27 (St Andrews Porous Material-27) has been synthesised solvothermally using the 2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine anion (TCPP4−) as the tetratopic carboxylate linker. STA-27 possesses a unique scandium-based 1D rod secondary building unit (SBU) comprising corner-sharing scandium Sc2O11 dimers connected via carboxylate groups from the linker. After activation under mild conditions STA-27 is an active Lewis acidic catalyst, while heating at elevated temperatures results in rupturing of the Sc–O–Sc linkages and a phase transition to a different topological type. Under similar synthesis conditions the smaller Al3+ and Ga3+ cations give isostructural MOFs with a different, previously reported, topology type based on chains of corner-sharing MO4(OH)2 octahedra: the Al-form possesses attractive properties for CO2 adsorption. [ABSTRACT FROM AUTHOR]

The hydroformylation of propene to give predominantly iso‐butanal has been achieved; class‐leading selectivity is possible even at higher temperatures that deliver fast conversion. Racemic rhodium complexes of bidentate phospholane phosphites derived from tropos‐biphenols and unusual solvent systems are the key to the selectivity observed. [ABSTRACT FROM AUTHOR]

Post‐synthetic modification of the hafnium metal–organic framework MOF‐808(Hf) to include triarylphosphine ligands is reported. Sulfonated phenylphosphines are incorporated without oxidation to give a "MOF ligand" that can complex late transition metals such as Ir and Rh to give a bifunctional catalyst containing both metal–phosphine complexes and the Lewis acidic framework hafnium metal sites. The metallated phosphine‐bearing MOFs act as fully heterogeneous bifunctional catalysts for tandem reductive amination and hydroaminomethylation reactions. Post‐synthetic modification of hafnium MOF‐808 with sulfonated arylphosphines and precious metal catalyst pre‐cursors generates highly active and tunable bifunctional catalysts for reductive amination reactions, including alkene hydroaminomethylation. [ABSTRACT FROM AUTHOR]

A manganese-catalyzed hydrogenation of esters has been accomplished with TONs up to 1000, using cheap, environmentally benign, potassium carbonate and simple alcohols as activator and solvent, respectively. The weakly basic conditions lead to good functional group tolerance and enable the hydrogenation of enantiomerically enriched α-chiral esters with essentially no loss of stereochemical integrity. [ABSTRACT FROM AUTHOR]

A new hydrogenation catalyst based on a manganese complex of a chiral P,N,N ligand has been found to be especially active for the hydrogenation of esters down to 0.1 mol % catalyst loading, and gives up to 97 % ee in the hydrogenation of pro-chiral deactivated ketones at 30-50 °C. [ABSTRACT FROM AUTHOR]

The synthesis of a range of phosphine-diamine, phosphine-amino-alcohol, and phosphine-amino-amide ligands and their ruthenium(II) complexes are reported. Five of these were characterised by X-ray crystallography. The activities of this collection of catalysts were initially compared for the hydrogenation of two model ester hydrogenations. Catalyst turnover frequencies up to 2400 h−1 were observed at 85 °C. However, turnover is slow at near ambient temperatures. By using a phosphine-diamine RuII complex, identified as the most active catalyst, a range of aromatic esters were reduced in high yield. The hydrogenation of alkene-, diene-, and alkyne-functionalised esters was also studied. Substrates with a remote, but reactive terminal alkene substituent could be reduced chemoselectively in the presence of 4-dimethylaminopyridine (DMAP) co-catalyst. The chemoselective reduction of the ester function in conjugated dienoate ethyl sorbate could deliver (2 E,4 E)-hexa-2,4-dien-1-ol, a precursor to leaf alcohol. The monounsaturated alcohol ( E)-hex-4-en-1-ol was produced with reasonable selectivity, but complete chemoselectivity of CO over the diene is elusive. High chemoselectivity for the reduction of an ester over an alkyne group was observed in the hydrogenation of an alkynoate for the first time. The catalysts were also active in the depolymerisation reduction of samples of waste poly(ethylene terephthalate) (PET) to produce benzene dimethanol. These depolymerisations were found to be poisoned by the ethylene glycol side product, although good yields could still be achieved. [ABSTRACT FROM AUTHOR]

As an alternative to conventional asymmetric hydroformylation (AHF), asymmetric transfer hydroformylation (ATHF) by using formaldehyde as a surrogate for syngas is reported. A catalyst derived from commercially available [Rh(acac)(CO)2] (acac=acetylacetonate) and 1,2-bis[(2 S,5 S)-2,5-diphenylphospholano]ethane(1,5-cyclooctadiene) (Ph-BPE) stands out in terms of both activity and enantioselectivity. Remarkably, not only are high selectivities achievable, the reactions are very simple to perform, and higher enantioselectivity (up to 96 % ee) and/or turnover frequencies than those achievable by using the same catalyst (or other leading catalysts) can be obtained by using typical conditions for AHF. [ABSTRACT FROM AUTHOR]

The trivalent metal cations Al3+, Cr3+, and Fe3+ were each introduced, together with Sc3+, into MIL-100(Sc,M) solid solutions (M=Al, Cr, Fe) by direct synthesis. The substitution has been confirmed by powder X-ray diffraction (PXRD) and solid-state NMR, UV/Vis, and X-ray absorption (XAS) spectroscopy. Mixed Sc/Fe MIL-100 samples were prepared in which part of the Fe is present as α-Fe2O3 nanoparticles within the mesoporous cages of the MOF, as shown by XAS, TGA, and PXRD. The catalytic activity of the mixed-metal catalysts in Lewis acid catalysed Friedel-Crafts additions increases with the amount of Sc present, with the attenuating effect of the second metal decreasing in the order Al>Fe>Cr. Mixed-metal Sc,Fe materials give acceptable activity: 40% Fe incorporation only results in a 20% decrease in activity over the same reaction time and pure product can still be obtained and filtered off after extended reaction times. Supported α-Fe2O3 nanoparticles were also active Lewis acid species, although less active than Sc3+ in trimer sites. The incorporation of Fe3+ into MIL-100(Sc) imparts activity for oxidation catalysis and tandem catalytic processes (Lewis acid+oxidation) that make use of both catalytically active framework Sc3+ and Fe3+. A procedure for using these mixed-metal heterogeneous catalysts has been developed for making ketones from (hetero)aromatics and a hemiacetal. [ABSTRACT FROM AUTHOR]