Hydrogen Activation with Ru-PN3P Pincer Complexes for the Conversion of C1 Feedstocks.

The hydrogenation of C1 feedstocks (CO and CO2) has been investigated using ruthenium complexes [RuHCl(CO)(PN3P)] as the catalyst. PN3P pincer ligands containing amines in the linker between the central pyridine donor and the phosphorus donors with bulky substituents (tert-butyl (1) or TMPhos (2)) are required to obtain mononuclear single-site catalysts that can be activated by the addition of KOtBu to generate stable five-coordinate complexes [RuH(CO)(PN3P-H)], whereby the pincer ligand has been deprotonated. Activation of hydrogen takes place via heterolytic cleavage to generate [RuH2(CO)(PN3P)], but in the presence of CO, coordination of CO occurs preferentially to give [RuH(CO)2(PN3P-H)]. This complex can be protonated to give the cationic complex [RuH(CO)2(PN3P)]+, but it is unable to activate H2 heterolytically. In the case of the less coordinating CO2, both ruthenium complexes 1 and 2 are highly efficient as CO2 hydrogenation catalysts in the presence of a base (DBU), which in the case of the TMPhos ligand results in a TON of 30,000 for the formation of formate.

Long-term forest monitoring reveals constant mortality rise in European forests.

European forests are an important source for timber production, human welfare, income, protection and biodiversity. During the last two decades, Europe has experienced a number of droughts which have been exceptional within the last 500 years, both in terms of duration and intensity. These droughts seem to leave remarkable imprints on the mortality dynamics of European forests. However, systematic observations on tree decline, with emphasis on a single species, has been scarce so far so that our understanding of mortality dynamics and drought occurrence is still limited at a continental scale. Here, we make use of the ICP Forest crown defoliation dataset, permitting us to retrospectively monitor tree mortality for all major conifers, major broadleaves, as well as a pooled dataset of minor tree species in Europe. In total, we analysed more than three million observations gathered during the last 25 years and employed a high-resolution drought index which can assess soil moisture anomaly based on a hydrological water-balance and runoff model. We found overall and species-specific increasing trends in mortality rates, accompanied by decreasing soil moisture. A generalized linear mixed model identified a previous-year soil moisture anomaly as the most important driver of mortality patterns in conifers, but the response was not uniform across the numerous analysed plots. We conclude that mortality patterns in European forests are currently reaching a concerning upward trend which could be further accelerated by global change-type droughts in the near future.

A DFT-based mechanistic proposal for the light-driven insertion of dioxygen into Pt(ii)-C bonds.

The photocatalyzed insertion of dioxygen into the Pt(ii)-methyl bond in terpyridine platinum complexes has been shown to proceed efficiently, but its mechanism remains a challenge. In particular, there are serious counter-intuitive differences in the reactivity of structurally similar complexes. M06 calculations in solvent with a valence double-ζ basis set supplemented by polarization and diffusion shells (benchmarked against ωB97x-D calculations with a larger basis set) are able to provide a satisfactory mechanistic answer. The proposed mechanism starts with the absorption of a photon by the metal complex, which then evolves into a triplet state that reacts with the triplet dioxygen fragment. A variety of possible reaction paths have been identified, some leading to the methylperoxo product and others reverting to the reactants, and the validity of some of these paths has been confirmed by additional experiments. The balance between the barriers towards productive and unproductive paths reproduces the diverging experimental behavior of similar complexes and provides a general mechanistic picture for these processes.

A DFT Mechanistic Study on Ethylene Tri- and Tetramerization with Cr/PNP Catalysts: Single versus Double Insertion Pathways.

The mechanism of ethylene trimerization and tetramerization with a chromium-diphosphinoamine (Cr-PNP) catalyst system has been studied by theoretical (DFT) methods. Two representative ligands have been explored, namely Ph2 PN(Me)PPh2 and (o-MeC6 H4 )2 PN(Me)P(o-MeC6 H4 )2 . Calculations on the former ligand reveal how a combination of single and double ethylene insertion mechanisms may lead to 1-hexene, 1-octene and the major side products (cyclopentanes and n-alkanes). For the latter ligand, introduction of o-alkyl substitution leads to a more sterically congested active species, which suppresses the available pathways for tetramerization and side product formation. Hence, the high selectivity of o-aryl substituted PNP ligands for trimerization can be rationalized.

Divergent reactivity of platinum(ii) and palladium(ii) methylperoxo complexes and the formation of an unusual hemi-aminal complex.

The 6,6''-diaminoterpyridine palladium(ii) methylperoxo complex eliminates methyl hydroperoxide and reacts with acetone to form a novel hemi-aminal palladium complex, whereas the analogous platinum(ii) complex generates formaldehyde and a platinum(ii) hydroxo complex.

Novel iminopyridine derivatives: ligands for preparation of Fe(ii) and Cu(ii) dinuclear complexes.

A series of imino- and amino-pyridine ligands based on dihydrobenzofurobenzofuran (BFBF) and methanodibenzodioxocine (DBDOC) backbones have been synthesized. These ligands form exclusively dinuclear complexes with metals such as iron(II) and copper(II). The structures for complexes 15, 16, 18, 19, 20, 21, 23, and 24 were determined by X-ray crystallography. The complexes show large distances for the metal nuclei and different geometries depending on the nature of the metal. An octahedral geometry was observed for the iron(II) complexes, while copper(II) complex 24 showed a distorted trigonal bipyramidal geometry. The iron(II) complexes showed activity as catalysts in the cycloaddition of CO2 to epoxides, obtaining moderate yields of cyclic carbonates.

Lanthanide-Assisted Deposition of Strongly Electro-optic PZT Thin Films on Silicon: Toward Integrated Active Nanophotonic Devices.

The electro-optical properties of lead zirconate titanate (PZT) thin films depend strongly on the quality and crystallographic orientation of the thin films. We demonstrate a novel method to grow highly textured PZT thin films on silicon using the chemical solution deposition (CSD) process. We report the use of ultrathin (5-15 nm) lanthanide (La, Pr, Nd, Sm) based intermediate layers for obtaining preferentially (100) oriented PZT thin films. X-ray diffraction measurements indicate preferentially oriented intermediate Ln2O2CO3 layers providing an excellent lattice match with the PZT thin films grown on top. The XRD and scanning electron microscopy measurements reveal that the annealed layers are dense, uniform, crack-free and highly oriented (>99.8%) without apparent defects or secondary phases. The EDX and HRTEM characterization confirm that the template layers act as an efficient diffusion barrier and form a sharp interface between the substrate and the PZT. The electrical measurements indicate a dielectric constant of ∼650, low dielectric loss of ∼0.02, coercive field of 70 kV/cm, remnant polarization of 25 µC/cm(2), and large breakdown electric field of 1000 kV/cm. Finally, the effective electro-optic coefficients of the films are estimated with a spectroscopic ellipsometer measurement, considering the electric field induced variations in the phase reflectance ratio. The electro-optic measurements reveal excellent linear effective pockels coefficients of 110 to 240 pm/V, which makes the CSD deposited PZT thin film an ideal candidate for Si-based active integrated nanophotonic devices.

Unraveling the origins of catalyst degradation in non-heme iron-based alkane oxidation.

A series of potentially tetradentate and pentadentate ligands modelled on BPMEN has been prepared and their iron(II) bis(triflate) complexes have been isolated and characterised by spectroscopic and crystallographic techniques (BPMEN = N,N'-bis(pyridylmethyl)ethylenediamine). Changes to the BPMEN ligand have invariably led to complexes with different coordination modes or geometries and with inferior catalytic efficiencies for the oxidation of cyclohexane with H2O2. The reaction of an iron(II) complex containing a pentadentate BPMEN-type ligand with O2 has resulted in ligand degradation via oxidative N-dealkylation and the isolation of a bis(hydroxo)-bridged dinuclear iron(III) complex with a picolinate-type ligand.

Oxygen insertion into metal carbon bonds: formation of methylperoxo Pd(II) and Pt(II) complexes via photogenerated dinuclear intermediates.

Platinum(II) and palladium(II) complexes [M(CH3)(L)]SbF6 with substituted terpyridine ligands L undergo light-driven oxygen insertion reactions into metal methyl bonds resulting in methylperoxo complexes [M(OOCH3)(L)]SbF6. The oxygen insertion reactions occur readily for complexes with methyl ligands that are activated due to steric interaction with substituents (NH2, NHMe or CH3) at the 6,6″-positions on the terpyridine ligand. All complexes exhibit attractive intermolecular π···π or M···M interactions in the solid state and in solution, which lead to excited triplet dinuclear M-M complexes upon irradiation. A mechanism is proposed whereby a dinuclear intermediate is generated upon irradiation that has a weakened M-C bond in the excited state, resulting in the observed oxygen insertion reactions.

Ligand tuning of single-site manganese-based catalytic antioxidants with dual superoxide dismutase and catalase activity.

A bio-inspired manganese(ii) complex with a linear pentadentate ligand framework containing soft sulfur donors and an alternating NSNSN binding motif displays excellent dual CAT/SOD-like antioxidant activity with high turnover efficiency and good operation stability in an aqueous environment.

Coordination equilibria between seven- and five-coordinate iron(II) complexes.

Octahedral, tetrahedral, and square planar geometries are the most often encountered coordination geometries for transition metal complexes. In certain cases, coordination equilibria can exist between different geometries, such as between six- and four-coordinate geometries in nickel(II) complexes, which were discovered half a century ago. Here, we present the first examples of a seven-five coordination equilibrium. Extensive spectroscopic studies in solution have provided evidence for a dynamic equilibrium between two iron(II) complexes, one with a seven-coordinate pentagonal bipyramidal geometry and one with a five-coordinate trigonal bipyramidal geometry.

Tri(pyridylmethyl)phosphine: the elusive congener of TPA shows surprisingly different coordination behavior.

Tri(pyridylmethyl)phosphine (TPPh), the remarkably elusive congener of tri(pyridylmethyl)amine (TPA), has been prepared, as well as the relative tri(N-methyl-pyridylamino)phosphine (TPAMP). The coordination properties of these new ligands have been evaluated for chromium(III), iron(II), and ruthenium(II) complexes and compared with the related TPA complexes. In all cases, a different coordination behavior has been observed whereby TPPh and TPAMP always act as tridentate ligands. A chromium(III) complex [Cr(TPPh)Cl3] has been prepared, which has shown low ethylene oligomerization activity. Octahedral low spin iron(II) complexes [Fe(TPPh)2](2+) and [Fe(TPAMP)2](2+) were obtained with two ligands bound to the metal center. Ruthenium(II) chloro complexes of TPA and TPPh undergo ligand exchange reactions in acetonitrile, and the ruthenium(II) complex [Ru(MeCN)2(TPA)](2+) can be oxidized by m-CPBA in acetonitrile to give a transient ruthenium(IV) oxo complex [Ru(O)(MeCN)(TPA)](2+). Attempts to generate high valent ruthenium(IV) oxo TPPh or TPAMP complexes could not be achieved, probably due to insufficient stabilization by these strong field ligands.

Carbodeoxygenation of biomass: the carbonylation of glycerol and higher polyols to monocarboxylic acids.

Glycerol is converted to a mixture of butyric and isobutyric acid by rhodium- or iridium-catalysed carbonylation using HI as the co-catalyst. The initial reaction of glycerol with HI results in several intermediates that lead to isopropyl iodide, which upon carbonylation forms butyric and isobutyric acid. At low HI concentration, the intermediate allyl iodide undergoes carbonylation to give vinyl acetic acid and crotonic acid. Higher polyols C(n)H(n+2)(OH)(n) are carbonylated to the corresponding C(n+1) mono-carboxylic acids.

Thio-Pybox and Thio-Phebox complexes of chromium, iron, cobalt and nickel and their application in ethylene and butadiene polymerisation catalysis.

A series of bis(thiazolinyl)- and bis(thiazolyl)pyridine Thio-Pybox ligands and their metal complexes of chromium(III), iron(II), cobalt(II) and nickel(II) has been prepared, as well as a nickel(II) complex containing a monoanionic bis(thiazolinyl)phenyl Thio-Phebox ligand. These new metal complexes have been characterised and used as catalysts, in combination with the co-catalyst MAO, for the polymerisation of ethylene and for the polymerisation of butadiene. In the case of ethylene polymerisation, the Thio-Pybox and Thio-Phebox metal complexes have shown relatively low polymerisation activities, much lower compared to the related bis(imino)pyridine complexes of the same metals. In the polymerisation of butadiene, several Thio-Pybox cobalt(II) complexes show very high activities, significantly higher than the other metal complexes with the same ligand. It is the metal, rather than the ligand, that appears to have the most profound effect on the catalytic activity in butadiene polymerisation, unlike in the polymerisation of ethylene, where bis(imino)pyridine ligands provide highly active catalysts for a range of 1st row transition metals.

High activity acetylene polymerisation with a bis(imino)pyridine iron(II) catalyst.

A catalyst system composed of a 2,6-bis(arylimino)pyridineiron(II) dichloride complex and methylaluminoxane is found to be extremely active for acetylene polymerisation. The formation of poly(acetylene) gels and surface films occurs at very low catalyst concentrations, around three orders of magnitude lower than traditional catalyst systems.

First metal complexes of 6,6'-dihydroxy-2,2'-bipyridine: from molecular wires to applications in carbonylation catalysis.

The first square planar rhodium(I) complexes containing the 6,6'-dihydroxy-2,2'-bipyridine ligand have been prepared. The complexes form molecular wires in the solid state and are active catalysts for the carbonylation of methyl acetate.

Iron(II) complexes with tetradentate bis(aminophenolate) ligands: synthesis and characterization, solution behavior, and reactivity with O(2).

Tetradentate bis(aminophenolate) ligands H(2)salan(X) and H(2)bapen(X) (where X refers to the para-phenolate substituent = H, Me, F, Cl) react with [Fe{N(SiMe(3))(2)}(2)] to form iron(II) complexes, which in the presence of suitable donor ligands L (L = pyridine or THF) can be isolated as the complexes [Fe(salan(X))(L)(2)] and [Fe(bapen(X))(L)(2)]. In the absence of donor ligands, either mononuclear complexes, for example, [Fe(salan(tBu,tBu))], or dinuclear complexes of the type [Fe(salan(X))](2) are obtained. The dynamic coordination behavior in solution of the complexes [Fe(salan(F))(L)(2)] and [Fe(bapen(F))(L)(2)] has been investigated by VT (1)H and (19)F NMR spectroscopy, which has revealed equilibria between isomers with different ligand coordination topologies cis-α, cis-ß and trans. Exposure of the iron(II) salan(X) complexes to O(2) results in the formation of oxo-bridged iron(III) complexes of the type [{Fe(salan(X))}(2)(µ-O)] or [{Fe(salan(X))(L)}(2)(µ-O)]. The lack of catalytic activity of the iron(II) salan and bapen complexes in the oxidation of cyclohexane with H(2)O(2) as the oxidant is attributed to the rapid formation of stable and catalytically inactive oxo-bridged iron(III) complexes.

The effect of the central donor in bis(benzimidazole)-based cobalt catalysts for the selective cis-1,4-polymerisation of butadiene.

A series of bis(benzimidazole)-based cobalt(II) dichloride complexes containing a range of different central donors has been synthesized and characterized. The nature of the central donor affects the binding of the ligand to the cobalt centre and determines the coordination geometry of the metal complexes. All complexes have been shown to catalyse the polymerization of butadiene, in combination with MAO as the co-catalyst, to give cis-1,4-polybutadiene with high selectivity. The nature of the central donor has a marked influence on the polymerization activity of the catalysts, but does not affect the polymer microstructure. The addition of PPh(3) generally increases the polymerization activity of these cobalt catalysts and results in predominantly (60-70%) 1,2-vinyl-polybutadiene.

Reasons for undertreatment with oral anticoagulants in frail geriatric outpatients with atrial fibrillation: a prospective, descriptive study.

OBJECTIVES: The main aims of the study were to explore whether oral anticoagulation (OAC) for atrial fibrillation (AF) in geriatric outpatients is prescribed in accordance with international (American College of Cardiology/American Heart Association/European Society of Cardiology [ACC/AHA/ESC]) and Dutch national guidelines for the general practitioner (GP) and to identify whether age and selected co-morbid conditions are associated with undertreatment. As a secondary objective, we wanted to establish how many patients discontinue OAC because of major bleeding. METHODS: In 2004, at the first visit of all patients to the geriatric day clinic of the Slotervaart Hospital in Amsterdam, the Netherlands, demographic data, Mini-Mental State Examination score, medical history, Charlson Comorbidity Index score, and data on medication use and changes were documented. The presence of AF was established by assessment of medical history information obtained by the GP, the history taken from patients and their caregivers, and the results of clinical evaluation, including ECG findings. Associations between the use of OAC, demographic data and co-morbid conditions registered in the Dutch NHG (Nederlands Huisartsen Genootschap [Dutch College of General Practitioners]) standard for GPs as risk factors for stroke or contraindications to the use of OAC were analysed. The reasons for discontinuing OAC were assessed after 4 years by requesting the information from the anticoagulation services or the GP. RESULTS: At the time of the initial visit, 17.5% of the 807 outpatients had chronic AF (n = 135) or were known to have paroxysmal AF (n = 6). The mean age of the 141 patients in this cohort was 84.3 years (SD 6.2 years). Co-morbid conditions increasing the risk of stroke were present in 129 patients (91.5%). Contraindications to the use of OAC were observed in 118 patients (83.7%). Of the 116 patients with AF in their history before their visit, 57.8% were being treated with OAC at the time of their visit. After comprehensive geriatric assessment, 73 (51.8%) of the 141 patients with chronic or paroxysmal AF were continued on OAC. Of the 141 patients with chronic or paroxysmal AF, 110 (78.0%) had both extra stroke risk factors and contraindications to the use of OAC. Only increasing age was significantly and independently associated with not being prescribed anticoagulants (p < 0.001). At the 4-year follow-up, OAC had been discontinued in 5.5% of patients because of major bleeding; three patients (4.1%) taking OAC had died as a result of major bleeding, and one other patient had discontinued treatment because of a major, non-lethal bleeding episode. CONCLUSION: Applying the NHG standard for appropriate prescription, and disregarding age as a risk factor or contraindication, in this population, 14 of 141 patients (9.9%) were inappropriately prescribed OAC, salicylates or no prophylaxis. Since only patient age was associated with not prescribing OAC in this study, higher age still seems to be considered the most important contraindication to anticoagulation therapy. Implementation of better models for stratifying bleeding risk in the frail elderly is needed. After 4 years, the cumulative rate of bleeding causing discontinuation of anticoagulation therapy in this usual-care study of frail older patients was not alarmingly higher than in other usual-care studies.

EPR spectroscopic trapping of the active species of nonheme iron-catalyzed oxidation.

The key intermediate of a bioinspired iron catalyst for selective hydrocarbon oxidation based on hydrogen peroxide and an iron complex with a tetradentate aminopyridine ligand was trapped by EPR. On the basis of EPR and reactivity data this intermediate is tentatively proposed to be an oxoiron(V) complex.