Alexei V. Iretskii

One-Pot Catalytic Conversion of Cellulose and of Woody Biomass Solids to Liquid Fuels

Efficient methodologies for converting biomass solids to liquid fuels have the potential to reduce dependence on imported petroleum while easing the atmospheric carbon dioxide burden. Here, we report quantitative catalytic conversions of wood and cellulosic solids to liquid and gaseous products in a single stage reactor operating at 300-320 °C and 160-220 bar. Little or no char is formed during this process. The reaction medium is supercritical methanol (sc-MeOH) and the catalyst, a copper-doped porous metal oxide, is composed of earth-abundant materials. The major liquid product is a mixture of C(2)-C(6) aliphatic alcohols and methylated derivatives thereof that are, in principle, suitable for applications as liquid fuels.

Hydrogen Transfer from Supercritical Methanol over a Solid Base Catalyst: A Model for Lignin Depolymerization

A (super)critical transfer: The consecutive hydrogenolysis and hydrogenation of the lignin model compound dihydrobenzofuran was studied in supercritical methanolic solutions using porous metal oxide catalysts. These catalysts promote H(2) production from methanol followed by hydrogenolysis of the ether linkages and reduction of the aromatic rings, leading principally to a mixture of cyclohexanols.

Nitrite Reduction Mediated by Heme Models. Routes to NO and HNO

The water-soluble ferriheme model Fe(III)(TPPS) mediates oxygen atom transfer from inorganic nitrite to a water-soluble phosphine (tppts), dimethyl sulfide, and the biological thiols cysteine (CysSH) and glutathione (GSH). The products with the latter reductant are the respective sulfenic acids CysS(O)H and GS(O)H, although these reactive intermediates are rapidly trapped by reaction with excess thiol. The nitrosyl complex Fe(II)(TPPS)(NO) is the dominant iron species while excess substrate is present. However, in slightly acidic media (pH ≈ 6), the system does not terminate at this very stable ferrous nitrosyl. Instead, it displays a matrix of redox transformations linking spontaneous regeneration of Fe(III)(TPPS) to the formation of both N2O and NO. Electrochemical sensor and trapping experiments demonstrate that HNO (nitroxyl) is formed, at least when tppts is the reductant. HNO is the likely predecessor of the N2O. A key pathway to NO formation is nitrite reduction by Fe(II)(TPPS), and the kinetics of this iron-mediated transformation are described. Given that inorganic nitrite has protective roles during ischemia/reperfusion (I/R) injury to organs, attributed in part to NO formation, and that HNO may also reduce net damage from I/R, the present studies are relevant to potential mechanisms of such nitrite protection.

Six-coordinate nitro complexes of iron(III) porphyrins with trans S-donor ligands. Oxo-transfer reactivity in the solid state.

Spectroscopic studies demonstrate that the 5-coordinate O-nitrito complexes Fe(Por)(eta(1)-ONO) (Por--meso-tetraphenyl- or meso-tetra-p-tolyl-porphyrinato dianions) react with the thioethers (R(2)S) dimethylsulfide and tetrahydrothiophene to give the 6-coordinate N-nitrito complexes Fe(Por)(R(2)S)(NO(2)). These reactions were conducted in low-temperature porous layered solids formed in a cryostat; however, with excess R(2)S in the atmosphere, the same species are moderately stable at room temperature. Six-coordinate O-nitrito isomers were not observed with the R(2)S proximal ligands, even though DFT calculations for the Fe(P)(DMS)(eta(1)-ONO) and Fe(P)(DMS)(NO(2)) models (P = porphinato dianion, DMS = dimethyl sulfide) show the latter to be only modestly lower energy (approximately 8 kJ/mol) than the former. Leaving this system at room temperature in the presence of excess R(2)S leads eventually to the appearance in the FTIR spectra of the nu(NO) band characteristic of the ferrous nitrosyl Fe(Por)(NO). Concomitantly, the mass spectrum of the gas phase demonstrated the molecular peaks of the sulfoxides R(2)SO, indicating oxygen atom transfer reactivity for the ferric porphryinato complexes of nitrite.

Nitrosyl isomerism in amorphous Mn(TPP)(NO) solids

Reaction of NO with amorphous Mn(TPP) layers gives two Mn(TPP)(NO) isomers with linear and bent Mn-N-O geometries that reversibly interconvert with changes in temperature. DFT computations predict that the linear complex is the singlet ground state while the bent structure is a triplet state.

Dinitrosyl iron complexes with cysteine. Kinetics studies of the formation and reactions of DNICs in aqueous solution

Kinetics studies provide mechanistic insight regarding the formation of dinitrosyl iron complexes (DNICs) now viewed as playing important roles in the mammalian chemical biology of the ubiquitous bioregulator nitric oxide (NO). Reactions in deaerated aqueous solutions containing FeSO4, cysteine (CysSH), and NO demonstrate that both the rates and the outcomes are markedly pH dependent. The dinuclear DNIC Fe2(μ-CysS)2(NO)4, a Roussins red salt ester (Cys-RSE), is formed at pH 5.0 as well as at lower concentrations of cysteine in neutral pH solutions. The mononuclear DNIC Fe(NO)2(CysS)2(-) (Cys-DNIC) is produced from the same three components at pH 10.0 and at higher cysteine concentrations at neutral pH. The kinetics studies suggest that both Cys-RSE and Cys-DNIC are formed via a common intermediate Fe(NO)(CysS)2(-). Cys-DNIC and Cys-RSE interconvert, and the rates of this process depend on the cysteine concentration and on the pH. Flash photolysis of the Cys-RSE formed from Fe(II)/NO/cysteine mixtures in anaerobic pH 5.0 solution led to reversible NO dissociation and a rapid, second-order back reaction with a rate constant kNO = 6.9 × 10(7) M(-1) s(-1). In contrast, photolysis of the mononuclear-DNIC species Cys-DNIC formed from Fe(II)/NO/cysteine mixtures in anaerobic pH 10.0 solution did not labilize NO but instead apparently led to release of the CysS(•) radical. These studies illustrate the complicated reaction dynamics interconnecting the DNIC species and offer a mechanistic model for the key steps leading to these non-heme iron nitrosyl complexes.

Weak coordination of neutral S- and O-donor proximal ligands to a ferrous porphyrin nitrosyl. Characterization of 6-coordinate complexes at low T

The interaction of the S- and O-donor ligands tetrahydrothiophen (THT) and tetrahydrofuran (THF) with the ferrous nitrosyl complex Fe(TTP)(NO) (TTP(2-) is meso-tetra-p-tolyl-porphyrinatodianion) was studied at various temperatures both in solid state and solution using electronic and infrared absorption spectroscopy. Upon addition of these ligands to a cryostat containing sublimed layers of Fe(TTP)(NO), no complex formation was detected at room temperature. However, upon lowering the temperature, spectral changes were observed that are consistent with ligand binding in axial position trans to the NO (the proximal site) and formation of the six-coordinate adducts. Analogous behavior was observed in solution. In both media, the six-coordinate adducts are stable only at low temperature and dissociate to the 5-coordinate nitrosyl complexes upon warming. The NO stretching frequencies of the six-coordinate thioether and ether complexes were recorded and binding constants for the weak bonding of proximal THF and THT ligands were determined from the spectral changes. These parameters are compared with those obtained for the N-donor ligand pyrrolidine.

Reaction of the Five-Coordinate O-Nitrito Complex Fe(Por)(ONO) (Por = meso-tetra-arylporphyrinato) with THF Gives Two Six-Coordinate Isomers

The effect of the proximal ligand on the coordination of the nitrite ligand to the heme model systems Fe(Por)(η1-ONO) (Por = meso-tetraarylporphyrinato dianion) was investigated by FTIR and UV-vis spectra in solvent free, low temperature, porous layered solids and by density functional computations. The reaction of the five-coordinate complex Fe(Por)(η1-ONO) with the ether tetrahydrofuran gives a mixture of the O-nitrito and N-nitrito isomers Fe(Por)(THF)(η1-ONO) and Fe(Por)(THF)(NO2), respectively. This observation is in contrast to earlier studies with nitrogen donor Lewis bases where the N-nitrito isomers were clearly the more stable of the six-coordinated complexes. The adduct formation is reversible; the five-coordinate O-nitrito complexes Fe(Por)(η1-ONO) were largely restored upon warming under vacuum pumping.

Dinuclear PhotoCORMs: Dioxygen-Assisted Carbon Monoxide Uncaging from Long-Wavelength -Absorbing Metal-Metal-Bonded Carbonyl Complexes

We describe a new strategy for triggering the photochemical release of caged carbon monoxide (CO) in aerobic media using long-wavelength visible and near-infrared (NIR) light. The dinuclear rhenium-manganese carbonyl complexes (CO)5ReMn(CO)3(L), where L = phenanthroline (1), bipyridine (2), biquinoline (3), or phenanthrolinecarboxaldehyde (4), each show a strong metal-metal-bond-to-ligand (σMM → πL*) charge-transfer absorption band at longer wavelengths. Photolysis with deep-red (1 and 2) or NIR (3 and 4) light leads to homolytic cleavage of the Re-Mn bonds to give mononuclear metal radicals. In the absence of trapping agents, these radicals primarily recombine to reform dinuclear complexes. In oxygenated media, however, the radicals react with dioxygen to form species much more labile toward CO release via secondary thermal and/or photochemical reactions. Conjugation of 4, with an amine-terminated poly(ethylene glycol) oligomer, gives a water-soluble derivative with similar photochemistry. In this context, we discuss the potential applications of these dinuclear complexes as visible/NIR-light-photoactivated CO-releasing moieties (photoCORMs).

New hydrogenation and isomerization reactions involving thiaplatinacycles derived from benzothiophene

Hydrogenation of the thiaplatinacycle [Pt{C,S-(CHCHC6H4S)}(dppe)] 2 (dppe = Ph2PCH2CH2PPh2) derived from benzothiophene, leads to [Pt{C,S-(CHMeC6H4S)}(dppe)] 3 in which 2H have added and a H-shift has occurred; the X-ray structures of 2 and 3 are reported.