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.

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.

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.

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.

Towards robust alkane oxidation catalysts: electronic variations in non-heme iron(ii) complexes and their effect in catalytic alkane oxidation.

A series of non-heme iron(ii) bis(triflate) complexes containing linear and tripodal tetradentate ligands has been prepared. Electron withdrawing and electron donating substituents in the para position of the pyridine ligands as well as the effect of pyrazine versus pyridine and sulfur or oxygen donors instead of nitrogen donors have been investigated. The electronic effects induced by these substituents influence the strength of the ligand field. UV-vis spectroscopy and magnetic susceptibility studies have been used to quantify these effects and VT (1)H and (19)F NMR spectroscopy as well as X-ray diffraction have been used to elucidate structural and geometrical aspects of these complexes. The catalytic properties of the iron(ii) complexes as catalysts for the oxidation of cyclohexane with hydrogen peroxide have been evaluated. In the strongly oxidising environment required to oxidise alkanes, catalyst stability determines the overall catalytic efficiency of a given catalyst, which can be related to the ligand field strength and the basicity of the ligand and its propensity to undergo oxidation.

Electronic effects in oxo transfer reactions catalysed by salan molybdenum(VI) cis-dioxo complexes.

A series of molybdenum(vi) cis-dioxo complexes containing tetradentate salan ligands with different para-substitutions on the phenoxy group have been prepared. These complexes catalyse the oxygen atom transfer reaction between dimethylsulfoxide and triphenylphosphine. During oxo transfer catalysis, the complexes are resistant to formation of catalytically inactive oxo-bridged dimeric Mo(v) complexes. Electronic effects influence the rate of the oxo transfer reaction and the fastest rates are achieved when the para-phenoxy substituent is an electron withdrawing nitro substituent. Hammett correlations have shown that the rate-determining step involves nucleophillic attack of the phosphine on one of the oxo ligands. Electrochemical measurements have shown that all complexes containing tertiary amine ligands exhibit quasi-reversible behaviour and that the para-substituent has a considerable effect on the half potentials (E(1/2)). A linear correlation between the E(1/2) values and the Hammett sigma(p) parameter is observed.