Base‐Free Iron Catalyzed Transfer Hydrogenation of Esters Using EtOH as Hydrogen Source

Herein, we report on the use of the iron pincer complex Iron‐MACHO‐BH, in the base‐free transfer hydrogenation of esters with EtOH as a hydrogen source. More than 20 substrates including aromatic and aliphatic esters and lactones were reduced affording the desired primary alcohols and diols with moderate to excellent isolated yields. It is also possible to reduce polyesters to the diols with this method, enabling a novel way of plastic recycling. Reduction of the renewable substrate methyl levulinate proceeds to form 1,4‐pentanediol directly. The yields are largely governed by the equilibrium between the alcohol and the ethyl ester.     

Facile Conversion of syn‐[FeIV(O)(TMC)]2+ into the anti Isomer via Meunier's Oxo–Hydroxo Tautomerism Mechanism

The syn and anti isomers of [Fe^IV(O)(TMC)]²⁺ (TMC=tetramethylcyclam) represent the first isolated pair of synthetic non‐heme oxoiron(IV) complexes with identical ligand topology, differing only in the position of the oxo unit bound to the iron center. Both isomers have previously been characterized. Reported here is that the syn isomer [Fe^IV(O_syn)(TMC)(NCMe)]²⁺ ( 2 ) converts into its anti form [Fe^IV(O_anti)(TMC)(NCMe)]²⁺ ( 1 ) in MeCN, an isomerization facilitated by water and monitored most readily by ¹H NMR and Raman spectroscopy. Indeed, when H₂¹⁸O is introduced to 2 , the nascent 1 becomes ¹⁸O‐labeled. These results provide compelling evidence for a mechanism involving direct binding of a water molecule trans to the oxo atom in 2 with subsequent oxo–hydroxo tautomerism for its incorporation as the oxo atom of 1 . The nonplanar nature of the TMC supporting ligand makes this isomerization an irreversible transformation, unlike for their planar heme counterparts.     

First Bis(σ)-borane Complexes of Group 6 Transition Metals: Experimental and Theoretical Studies

A series of bis(σ)-borane complexes of Group 6 transition metals were prepared by direct dihydroborane coordination to the metal center. Reaction of [M(CO)₃(PCy₃)₂] and two dihydroboranes [DurBH₂] and [(Me₃Si)₂NBH₂] (Dur=2,3,5,6-Me₄C₆H) yielded bis(σ)-borane complexes fac-[M(CO)₃(PCy₃){η²-(H₂BR)}] (R=Dur; 1 : M=Cr, 2 : M=W; R=N(SiMe₃)₂; 3 : M=Cr, 4 : M=W). In the case of molybdenum, we have isolated an arene complex ( 5 ) with [DurBH₂] in which the Dur group acts as a η⁶-bound ligand, and with [(Me₃Si)₂NBH₂] a similar bis(σ)-borane complex was isolated, cis,trans-[Mo(CO)₂(PCy₃)₂{η²-(H₂BN(SiMe₃)₂}] ( 6 ), with a different pattern of auxiliary ligands. The complexes were investigated by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and computational methods. Quantum theory of atoms in molecules (QTAIM) calculations demonstrated that the borane complexes may be described as pure bis(σ)-borane complexes rather than elongated or stretched examples given that the calculations do not show the presence of a ring-critical point (RCP) at the ring formed by the interactions of the B−H with metal center.     

Brodie's or Hummers’ Method: Oxidation Conditions Determine the Structure of Graphene Oxide

Synthesis and studies of graphite oxide started more than 150 years ago and turned into a boom by the measurements of the outstanding physical properties of graphene. A series of preparation protocols emanated trying to optimize the synthesis of graphene oxide in order to obtain a less defective material, as source for graphene. However, over-oxidation of the carbon framework hampered establishing structure-property relationships. Here, the fact that two different synthetic methods for graphene oxide preparation lead to very similar types of graphene oxide with a preserved graphene lattice is demonstrated. Either sodium chlorate in nitric acid (similar to Brodie's method) or potassium permanganate in sulfuric acid (similar to Hummers’ method) treatment are possible; however, reaction conditions must be controlled. With a preserved carbon lattice analytical differences between the samples relate to the altered on-plane functionality. Consequently, terming preparation protocols “according to Brodie's/Hummers’ method” is not sufficient.     

Computer-Assisted Solution of Chemical Problems—The Historical Development and the Present State of the Art of a New Discipline of Chemistry

The topic of this article is the development and the present state of the art of computer chemistry, the computer-assisted solution of chemical problems. Initially the problems in computer chemistry were confined to structure elucidation on the basis of spectroscopic data, then programs for synthesis design based on libraries of reaction data for relatively narrow classes of target compounds were developed, and now computer programs for the solution of a great variety of chemical problems are available or are under development. Previously it was an achievement when any solution of a chemical problem could be generated by computer assistance. Today, the main task is the efficient, transparent, and non-arbitrary selection of meaningful results from the immense set of potential solutions—that also may contain innovative proposals. Chemistry has two aspects, constitutional chemistry and stereochemistry, which are interrelated, but still require different approaches. As a result, about twenty years ago, an algebraic model of the logical structure of chemistry was presented that consisted of two parts: the constitution-oriented algebra of be- and r-matrices, and the theory of the stereochemistry of the chemical identity group. New chemical definitions, concepts, and perspectives are characteristic of this logic-oriented model, as well as the direct mathematical representation of chemical processes. This model enables the implementation of formal reaction generators that can produce conceivable solutions to chemical problems—including unprecedented solutions—without detailed empirical chemical information. New formal selection procedures for computer-generated chemical information are also possible through the above model. It is expedient to combine these with interactive methods of selection. In this review, the Munich project is presented and discussed in detail. It encompasses the further development and implementation of the mathematical model of the logical structure of chemistry as well as the experimental verification of the computer-generated results. The article concludes with a review of new reactions, reagents, and reaction mechanisms that have been found with the PC-programs IGOR and RAIN.     

Amino substituted 1-oxa-3-azabutatrienium salts: preparation, structure and reaction with carbonyl compounds

N,N-Dimethylformamide ($\text{4a}$) and N,N-dimethylpivalamide ($\text{4b}$) react with carbonyl chloride isocyanate ($\text{5}$) in the presence of antimony pentachloride to afford the amino substituted 1-oxa-3-azabutatrienium hexachloroantimonates $\text{6a}$,$\text{b}$. An X-ray diffraction analysis of $\text{6a}$ confirms the proposed structure. The heterocumulenes $\text{6a}$,$\text{b}$ react with aldehydes, ketones and tertiary carboxamides to give the amino substituted 2-azaallenium salts $\text{13a}$-$\text{O}$ in high yields.     

Anion dependence of crown ether selectivities for alkali picrates and sulfonates in dioxane and toluene. A synergistic effect

The binding constants,K _N, of sodium and potassium 8-anilinonaphthalene-1-sulfonate (ANS) and of sodium 5-dimethylamino-1-naphthalenesulfonate (DNS) to benzo-18-crown-6 bound to a 2% cross-linked polystyrene network (RN18C6) were measured spectrophotometrically in dioxane and the results compared with those obtained for picrate salts. The network RN18C6 was then used to measure in dioxane and toluene by a competition method the equilibrium constant,K, of the reaction A^–M⁺N+CrA^–M⁺Cr+N.A^–M⁺N denotes the ionic solute (ANS, DNS, methyl orange or picrate salt) bound to the network RN18C6 (N) and A^–M⁺Cr is the solute bound to a soluble ligand Cr, where Cr represents a series of 18-crown-6 and 15-crown-5 compounds. Combining theK _N andK values the formation constants,K _L, of the crown ether complexes of the respective salts were obtained in dioxane. The data show a reversal in the complexation strength of the 18-crown-6 compounds in dioxane when sodium picrate is replaced by sodium ANS. The results were rationalized in terms of a synergistic effect exerted by dioxane, with dioxane forming a 1:1 dioxanate with the crown ion pair complex. This effect is especially strong with ANS and with a rigid planar crown ether like dibenzo-18-crown-6. The binding constants,K _N, of NaANS and NaDNS to RN18C6 in dioxane are nearly three times larger than for sodium picrate, and the same holds for the potassium salts. Differences in anion interactions with the network appear to be a plausible cause for the anion dependence ofK _N.     

Aryl Triflates in On-Surface Chemistry

The reactivity of aryl triflates in on-surface C−C coupling is reported. It is shown that the triflate group in aryl triflates enables regioselective homo coupling with preceding or concomitant hydrodetriflation on Cu(111). Three different symmetrical π-systems with two and three triflate functionalities were used as monomers leading to oligomeric conjugated π-systems. The cascade, comprising different intermediates at different reaction temperatures as observed for one of the molecules, proceeds via initial removal of the trifluoromethyl sulfonyl group to give an aryloxy radical which in turn is deoxygenated to the corresponding aryl radical. Thermodynamically driven regioselective 1,2-hydrogen atom transfer leads to a translocated aryl radical which in turn undergoes coupling. For a sterically more hindered bistriflate, where one ortho position was blocked, dehydrogenative coupling occurred at remote position with good regioselectivity. Starting materials, intermediates as well as products were analyzed by scanning tunneling microscopy. Structures and suggested mechanism were further supported by DFT calculations.     

Substrate electric dipole moment exerts a pH-dependent effect on electron transfer in Escherichia coli photolyase

Transient absorption spectroscopy is used to demonstrate that the electric dipole moment of the substrate cyclobutane thymine dimer affects the charge recombination reaction between fully reduced flavin adenine dinucleotide (FADH-) and the neutral radical tryptophan 306 (Trp306*) in Escherichia coli DNA photolyase. At pH 7.4, the charge recombination is slowed by a factor of 1.75 in the presence of substrate, but not at pH 5.4. Photolyase does bind substrate at pH 5.4, and it seems that this pH effect originates from the conversion of FADH- to FADH2 at lower pH. The free-energy changes calculated from the electric field parameters and from the change in electron transfer rate are in good agreement and support the idea that the substrate electric dipole is responsible for the observed change in electron transfer rate. It is expected that the substrate electric field will also modify the physiologically important from excited 1FADH- to the substrate in the DNA repair reaction.