Synthesis and Reactivity of the Anionic Iridium(III) Complex [Cp*Ir(OTf)3][Ag{tBu2P(heptanoyl)}]

Synthesis and Reactivity of the Anionic Iridium(III) Complex [Cp*Ir(OTf)3][Ag{tBu2P(heptanoyl)}]:

OrganometallicsDOI: 10.1021/om200639e

Probably not very useful, but interesting since we do so much Cp*Ir work.

On the Diels–Alder Approach to Solely Biomass-Derived Polyethylene Terephthalate (PET): Conversion of 2,5-Dimethylfuran and Acrolein into p-Xylene

On the Diels–Alder Approach to Solely Biomass-Derived Polyethylene Terephthalate (PET): Conversion of 2,5-Dimethylfuran and Acrolein into p-Xylene:

Dean Toste et al. Chem-Eur J: Polyethylene terephthalate (PET) is a polymeric material with high global demand. Conventionally, PET is produced from fossil-fuel-based materials. Herein, we explored the feasibility of a sustainable method for PET production by using solely bio-renewable resources. Specifically, 2,5-dimethylfuran (derived from lignocellulosic biomass through 5-(hydroxymethyl)furfural) and acrolein (produced from glycerol, a side product of biodiesel production) were converted into the key intermediate p-xylene (a precursor of terephthalic acid). This synthesis consists of a sequential Diels–Alder reaction, oxidation, dehydration, and decarboxylation. In particular, the pivotal first step, the Diels–Alder reaction, was studied in detail to provide useful kinetic and thermodynamic data. Although it was found that this reaction requires low temperature to proceed efficiently, which presents a limitation on economic feasibility on an industrial scale, the concept was realized and bio-derived p-xylene was obtained in 34 % overall yield over four steps.

Making PET as green as grass: Polyethylene terephthalate (PET) can be prepared from solely bio-renewable sources by converting 2,5-dimethylfuran and acrolein into the key intermediate p-xylene (see scheme). This atom-economic route consists of a sequential Diels–Alder reaction, oxidation, dehydrative aromatization and decarboxylation. We examined the feasibility of this process with an emphasis on the Diels–Alder reaction step.

Not super-relevant to our approach, but the article highlights possible directions. The main catch is that even the largest scale chemicals do not approach the scale of fuels. And our program is focused on fuels.

Basic ancillary ligands promote O-O bond formation in iridium-catalyzed water oxidation: A DFT study

Basic ancillary ligands promote O-O bond formation in iridium-catalyzed water oxidation: A DFT study:

Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10660K, Paper

Laia Vilella, Pietro Vidossich, David Balcells, Agusti Lledos
A DFT(B3LYP) study on Ir-catalyzed water oxidation shows that the energy barrier associated with the critical O-O bond formation step is lowered by increasing the basicity of the ancillary ligands.
The role of M-C bonds to stabilizing M=O and M-OOH bonds is possibly relevant to our collaboration with Gewirth group.

Structural Study-Guided Development of Versatile Phase-Transfer Catalysts for Asymmetric Conjugate Additions of Cyanide

Structural Study-Guided Development of Versatile Phase-Transfer Catalysts for Asymmetric Conjugate Additions of Cyanide:

Unprecedented phase-transfer catalysts for the first example of an organocatalytic asymmetric conjugate addition of cyanide with acetone cyanohydrin are reported (see scheme). Utilizing an accessible cupreidinium salt and a cyanation reagent suitable for industrial scale, this reaction holds significant promise for practical asymmetric synthesis. The catalysts were developed as a result of key structural insights gained by X-ray analysis.

Novel source of CN-?

Controlled Aqueous Atom Transfer Radical Polymerization with Electrochemical Generation of the Active Catalyst

Controlled Aqueous Atom Transfer Radical Polymerization with Electrochemical Generation of the Active Catalyst:

Enhanced control: Electrochemically mediated atom transfer radical polymerization (ATRP) allows easy modulation of the overall rate and control of polymerization through the variation of an external applied potential, E_app (see picture). This method has been successfully applied to aqueous ATRP of oligo(ethylene glycol) methyl ether methacrylate (OEOMA₄₇₅) catalyzed by Cu/tris(2-pyridylmethyl)amine.
We could probably contribute to this theme with Chris Letko's ligands.  This topic (ATRP) would be a good for a future literature talk).

Comparison of the photochemistry of organometallic N-heterocyclic carbene and phosphine complexes of manganese

Comparison of the photochemistry of organometallic N-heterocyclic carbene and phosphine complexes of manganese:

Chem. Commun., 2011, Advance Article
DOI: 10.1039/C1CC14467G, Communication

Madeeha Batool, Thomas A. Martin, M. Abu Naser, Michael W. George, Stuart A. Macgregor, Mary F. Mahon, Michael K. Whittlesey
Agostic interactions in the unsaturated intermediates ([small eta]⁵-C₅H₄Me)Mn(L)(CO) (L = NHC, PPh₃) are revealed by time-resolved IR studies and DFT calculations.
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Preparation and Reactivity of a Nickel Dihydride Complex

Preparation and Reactivity of a Nickel Dihydride Complex:

A generous donor: A dinuclear octahedral bis(μ-hydrido)dinickel(II) complex (see picture; C gray, H black, N blue, Ni green) acts as an electron donor to reduce electron acceptors such as methyl viologen. The complex is proposed as a functional model for the dihydride intermediate of an NiRu hydrogenase mimic and, by extension, of [NiFe]hydrogenase itself.
by Seiji Ogo's Group: Very relevant to us. Note the presence of two picolinyl groups, not just TPA and not tris(picolinyl)amine. The redox and magnetic properties of this species (high spin?) would be interesting.  Note his reference to viologens and his effort to connect to the enzyme.

Balance between Fluorescence Enhancement and Association Affinity in Fluorescent Heteroditopic Indicators for Imaging Zinc Ion in Living Cells

Balance between Fluorescence Enhancement and Association Affinity in Fluorescent Heteroditopic Indicators for Imaging Zinc Ion in Living Cells:

Inorganic Chemistry DOI: 10.1021/ic201728f

Dual Coordination Modes of Ethylene-Linked NP2 Ligands in Cobalt(II) and Nickel(II) Iodides

Dual Coordination Modes of Ethylene-Linked NP2 Ligands in Cobalt(II) and Nickel(II) Iodides:

Inorganic Chemistry

DOI: 10.1021/ic201213c

Noninnocence in Metal Complexes: A Dithiolene Dawn

Noninnocence in Metal Complexes: A Dithiolene Dawn:

Inorganic Chemistry

DOI: 10.1021/ic2011748

Carbon–Hydrogen Bond Cleavage Reaction in Four-Coordinate (2,6-Dimethylbenzenethiolato)platinum(II) Complexes. Dramatic Acceleration by Thiolato Hydrogen Acceptor

Carbon–Hydrogen Bond Cleavage Reaction in Four-Coordinate (2,6-Dimethylbenzenethiolato)platinum(II) Complexes. Dramatic Acceleration by Thiolato Hydrogen Acceptor:

Organometallics

DOI: 10.1021/om200345h

C–S Bond Activation of Thioesters Using Platinum(0)

C–S Bond Activation of Thioesters Using Platinum(0):

Organometallics

DOI: 10.1021/om200452z

Molecular Catalysis in a Fuel Cell

Molecular Catalysis in a Fuel Cell:

Jack of all trades: A fuel cell based on a single molecular catalyst (see picture) uses a [NiFe]hydrogenase mimic to catalyze the oxidation of H₂. Crucially, the catalyst is also active for the reduction of O₂, allowing the construction of a fully functional fuel cell. This molecular catalyst can function both in solid and solution phases, allowing precise observation of the mechanism.

pKas of phosphorus and amine bases

http://www.sciencedirect.com/science/article/pii/S0040402006003164

The effect of peripheral bipyridine ligands on the photocatalytic hydrogen production activity of Ru/Pd catalysts

The effect of peripheral bipyridine ligands on the photocatalytic hydrogen production activity of Ru/Pd catalysts:

Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT11241D, Communication

Gurmeet Singh Bindra, Martin Schulz, Avishek Paul, Suraj Soman, Robert Groarke, Jane Inglis, Mary T. Pryce, Wesley R. Browne, Sven Rau, Brian J. Maclean, Johannes G. Vos
A binuclear Ru(II)/Pd(II) catalyst for photocatalytic H₂ is switched on by tweaking the substitution of non-bridging bipy ligands.
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Fast Carbon Dioxide Fixation by 2,6-Pyridinedicarboxamidato-nickel(II)-hydroxide Complexes: Influence of Changes in Reactive Site Environment on Reaction Rates

Fast Carbon Dioxide Fixation by 2,6-Pyridinedicarboxamidato-nickel(II)-hydroxide Complexes: Influence of Changes in Reactive Site Environment on Reaction Rates:

Inorganic Chemistry

DOI: 10.1021/ic200942u

A Cobalt–Dithiolene Complex for the Photocatalytic and Electrocatalytic Reduction of Protons

A Cobalt–Dithiolene Complex for the Photocatalytic and Electrocatalytic Reduction of Protons:

Journal of the American Chemical Society

DOI: 10.1021/ja207842r

Low-Pressure Hydrogenation of Carbon Dioxide Catalyzed by an Iron Pincer Complex Exhibiting Noble Metal Activity

Low-Pressure Hydrogenation of Carbon Dioxide Catalyzed by an Iron Pincer Complex Exhibiting Noble Metal Activity:

A highly active iron catalyst for the hydrogenation of carbon dioxide and bicarbonates works under remarkably low pressures and achieves activities similar to some of the best noble metal catalysts. A mechanism is proposed involving the direct attack of an iron trans-dihydride on carbon dioxide, followed by ligand exchange and dihydrogen coordination.

Selective CO2 Conversion to Formate Conjugated with H2O Oxidation Utilizing Semiconductor/Complex Hybrid Photocatalysts

Selective CO2 Conversion to Formate Conjugated with H2O Oxidation Utilizing Semiconductor/Complex Hybrid Photocatalysts:

Journal of the American Chemical Society

DOI: 10.1021/ja204881d

Reactivity of Lewis pairs (R2PCH2AlMe2)2 with carbon dioxide

Reactivity of Lewis pairs (R2PCH2AlMe2)2 with carbon dioxide:

Chem. Commun., 2011, Advance Article
DOI: 10.1039/C1CC14641F, Communication

Josee Boudreau, Marc-Andre Courtemanche, Frederic-Georges Fontaine
Species R₂PCH₂AlMe₂ (R = Me, Ph) form stable Lewis adducts at the solid state and in solution but still react with CO₂ to form adducts that were attributed to the chemistry of "frustrated Lewis pairs" (FLPs). Observed adducts exhibit unique reactivity compared to their FLPs' counterparts.
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Mechanistic Considerations for C–C Bond Reductive Coupling at a Cobalt(III) Center

Mechanistic Considerations for C–C Bond Reductive Coupling at a Cobalt(III) Center:

Journal of the American Chemical Society DOI: 10.1021/ja2072548

Methyltransferase Activity of an Iridium Center with Methylpyridinium as Methylene Source

Methyltransferase Activity of an Iridium Center with Methylpyridinium as Methylene Source:

Hop on, hop off: an iridium center transfers a methyl group from pyridinium to an aryl unit, using exclusively the pyridine-bound methyl group as a mild methylene source. The reaction also involves cleavage of an unactivated C(aryl)H bond and nitrile solvent activation. The process is reminiscent of DNA methylation and entails the formation of two new C(sp²)C(sp³) bonds within the metal coordination sphere (see scheme).

Studies of the reactions of tripodal pyridine-containing ligands with Re(CO)5Br leading to rheniumtricarbonyl complexes with potential biomedical applications

Studies of the reactions of tripodal pyridine-containing ligands with Re(CO)5Br leading to rheniumtricarbonyl complexes with potential biomedical applications:

Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT11020A, Paper

D. Vaughan Griffiths, Yuen-Ki Cheong, Philip Duncanson, Majid Motevalli
N-Acylated bis(pyridin-2-yl)methylamines react with [Re(CO)₅Br] to give various complexes including one with an acetyl group in its imidic acid form.

Observation of Fe(V)=O using variable-temperature mass spectrometry and its enzyme-like C–H and C=C oxidation reactions

Observation of Fe(V)=O using variable-temperature mass spectrometry and its enzyme-like C–H and C=C oxidation reactions:

Observation of Fe(V)=O using variable-temperature mass spectrometry and its enzyme-like C–H and C=C oxidation reactions

Nature Chemistry.
doi:10.1038/nchem.1132

Authors: Irene Prat, Jennifer S. Mathieson, Mireia Güell, Xavi Ribas, Josep M. Luis, Leroy Cronin & Miquel Costas

Variable-temperature mass spectrometry, isotopic labelling and computational analysis have been used to characterize a metastable non-haem oxo-iron(V) intermediate generated at cryogenic temperatures, as well as to study its cis-dihydroxylation reaction with olefins. The study provides experimental evidence for the existence of this powerful and biologically important oxidant, under conditions relevant to catalysis.

RA: Leroy Cronin group is a materials chemistry group pioneered with cryo-mass and VT-mass spectrometric techniques. They have also studied many reaction dynamics with MS and other instrumental methods (e.g. Science 2010 from this group).

Efficient water oxidation catalysts based on readily available iron coordination complexes

Efficient water oxidation catalysts based on readily available iron coordination complexes:

Efficient water oxidation catalysts based on readily available iron coordination complexes

Nature Chemistry.
doi:10.1038/nchem.1140

Authors: Julio Lloret Fillol, Zoel Codolà, Isaac Garcia-Bosch, Laura Gómez, Juan José Pla & Miquel Costas

One of the bottlenecks for the development of sustainable artificial photosynthesis is the water oxidation reaction, which too often relies on expensive and toxic metals. Now, coordination complexes of readily available, environmentally benign iron are found to catalyse homogeneous water oxidation to O2 with high efficiency.

Oxidative properties of a nonheme Ni(II)(O2) complex: Reactivity patterns for C-H activation, aromatic hydroxylation and heteroatom oxidation

Oxidative properties of a nonheme Ni(II)(O2) complex: Reactivity patterns for C-H activation, aromatic hydroxylation and heteroatom oxidation:

Chem. Commun., 2011, Advance ArticleDOI: 10.1039/C1CC13993B, Communication

Reza Latifi, Laleh Tahsini, Devesh Kumar, G. Narahari Sastry, Wonwoo Nam, Sam P. de Visser
Density functional theory calculations on the reactivity of a Ni(II)-superoxo complex in C-H bond activation, aromatic hydroxylation and heteroatom oxidation reactions have been explored.

First-Row Transition-Metal Chloride Complexes of the Wide Bite-Angle Diphosphine iPrDPDBFphos and Reactivity Studies of Monovalent Nickel

First-Row Transition-Metal Chloride Complexes of the Wide Bite-Angle Diphosphine iPrDPDBFphos and Reactivity Studies of Monovalent Nickel:

Inorganic ChemistryDOI: 10.1021/ic200589e

Connie Liu et al. Possible building block

Structure and bonding in three-coordinate N-heterocyclic carbene adducts of iron(II) bis(trimethylsilyl)amide

Structure and bonding in three-coordinate N-heterocyclic carbene adducts of iron(II) bis(trimethylsilyl)amide:

Chem. Commun., 2011, DOI: 10.1039/C1CC14576B

Richard A. Layfield, Joseph J. W. McDouall, Manfred Scheer, Christoph Schwarzmaier, Floriana Tuna
The three-coordinate NHC iron(II) complexes [(NHC)Fe{N(SiMe₃)₂}₂] (NHC = IProrIMes) are stable in the solid-state but dissociate their NHC ligands in solution due to steric overcrowding.

Tuning Chemoselectivity in Iron-Catalyzed Sonogashira-Type Reactions Using a Bisphosphine Ligand with Peripheral Steric Bulk: Selective Alkynylation of Nonactivated Alkyl Halides

Tuning Chemoselectivity in Iron-Catalyzed Sonogashira-Type Reactions Using a Bisphosphine Ligand with Peripheral Steric Bulk: Selective Alkynylation of Nonactivated Alkyl Halides:

The incredible bulk: A highly selective alkynylation of nonactivated alkyl halides with the corresponding Grignard reagents is achieved by using the iron-phosphine complex 1. Primary and secondary alkyl iodides, bromides, and chlorides take part in the reaction to give the substituted alkynes in good to excellent yields. Sequential cyclization/cross-coupling reactions are also demonstrated.

Many: this is an interesting ligand for us