Ammonia borane (H(3)N-BH(3), AB) is a lightweight material containing a high density of hydrogen (H(2)) that can be readily liberated for use in fuel cell-powered applications. However, in the absence of a straightforward, efficient method for regenerating AB from dehydrogenated polymeric spent fuel, its full potential as a viable H(2) storage material will not be realized. We demonstrate that the spent fuel type derived from the removal of greater than two equivalents of H(2) per molecule of AB (i.e., polyborazylene, PB) can be converted back to AB nearly quantitatively by 24-hour treatment with hydrazine (N(2)H(4)) in liquid ammonia (NH(3)) at 40°C in a sealed pressure vessel.

The conversion of biomass into fuels and chemical feedstocks is one part of a drive to reduce the world's dependence on crude oil. For transportation fuels in particular, wholesale replacement of a fuel is logistically problematic, not least because of the infrastructure that is already in place. Here, we describe the catalytic defunctionalization of a series of biomass-derived molecules to provide linear alkanes suitable for use as transportation fuels. These biomass-derived molecules contain a variety of functional groups, including olefins, furan rings and carbonyl groups. We describe the removal of these in either a stepwise process or a one-pot process using common reagents and catalysts under mild reaction conditions to provide n-alkanes in good yields and with high selectivities. Our general synthetic approach is applicable to a range of precursors with different carbon content (chain length). This allows the selective generation of linear alkanes with carbon chain lengths between eight and sixteen carbons.

For years, following the ideas of Shvo and Noyori, the core assumption of metal−ligand bifunctional molecular catalysis has relied on the direct involvement of the chelating ligand in the catalytic reaction via a reversible proton (H + ) transfer through cleavage/formation of one of its X−H bonds (X = O, N, C). A recently revised mechanism of the Noyori asymmetric hydrogenation reaction (Dub, P. A. et al. J. Am. Chem. Soc. 2014, 136, 3505) suggests that the ligand is rather involved in the catalytic reaction via the stabilization of determining transition states through N−H•••O hydrogenbonding interactions (HBIs) and not via a reversible H + transfer, behaving in a chemically intact manner within the productive cycle or predominantly in a chemically intact manner within productive cycles. By reexamining selected examples of computational mechanistic studies involving bifunctional catalysts from the literature in the years between 2012−2017, the purpose of this work is to point out common misconceptions in modeling concerted reactions and show that the actual stepwise nature of key transition states unveils a more complicated catalytic reaction pool (all conceivable catalytic pathways and their crossovers). Such a realization can not only potentially result in a reconsideration of the "accepted" mechanism but also lead us to a new conceptual understanding of the role that the ligand plays in the reaction. The ultimate goal of this paper is, therefore, to encourage the reader to reconsider the function of the ligand in catalytic cycles of hydrogenation/dehydrogenation with bifunctional catalysts, which until recently has relied almost exclusively on a chemically noninnocent ligand.

Dipicolinate vanadium(V) complexes oxidize lignin model complexes pinacol monomethyl ether (A), 2-phenoxyethanol (B), 1-phenyl-2-phenoxyethanol (C), and 1,2-diphenyl-2-methoxyethanol (D). With substrates having C-H bonds adjacent to the alcohol moiety (B-D), the C-H bond is broken in pyridine-d(5) solvent, yielding 2-phenoxyacetaldehyde from B, 2-phenoxyacetophenone from C, and benzoin methyl ether from D. In DMSO-d(6) solvent the reaction is slower, and both C-H and C-C bond cleavage products are observed for D. The vanadium(IV) products of these reactions have been identified and characterized. Catalytic oxidation of C and D has been demonstrated using air and (dipic)V(O)O(i)Pr. For both substrates, the C-C bond between the alcohol and ether groups is broken in the catalytic oxidation. 1-Phenyl-2-phenoxyethanol is oxidized to a mixture of phenol, formic acid, benzoic acid, and 2-methoxyacetophenone. The products of oxidation of 1,2-diphenyl-2-methoxyethanol depend on the solvent; in DMSO benzaldehyde and methanol are the major products, while benzoic acid and methyl benzoate are the major products obtained in pyridine solvent. Phenyl substituents on the model complex facilitate the oxidation, with relative rates of oxidation D > C > B.

The mechanism of catalytic hydrogenation of acetophenone by the chiral complex trans-[RuCl2{(S)-binap}{(S,S)-dpen}] and KO-t-C4H9 in propan-2-ol is revised on the basis of DFT computations carried out in dielectric continuum and the most recent experimental observations. The results of these collective studies suggest that neither a six-membered pericyclic transition state nor any multibond concerted transition states are involved. Instead, a hydride moiety is transferred in an outer-sphere manner to afford an ion-pair, and the corresponding transition state is both enantio- and rate-determining. Heterolytic dihydrogen cleavage proceeds neither by a (two-bond) concerted, four-membered transition state, nor by a (three-bond) concerted, six-membered transition state mediated by a solvent molecule. Instead, cleavage of the H-H bond is achieved via deprotonation of the η(2)-H2 ligand within a cationic Ru complex by the chiral conjugate base of (R)-1-phenylethanol. Thus, protonation of the generated (R)-1-phenylethoxide anion originates from the η(2)-H2 ligand of the cationic Ru complex and not from NH protons of a neutral Ru trans-dihydride complex, as initially suggested within the framework of a metal-ligand bifunctional mechanism. Detailed computational analysis reveals that the 16e(-) Ru amido complex [RuH{(S)-binap}{(S,S)-HN(CHPh)2NH2}] and the 18e(-) Ru alkoxo complex trans-[RuH{OCH(CH3)(R)}{(S)-binap}{(S,S)-dpen}] (R = CH3 or C6H5) are not intermediates within the catalytic cycle, but rather are off-loop species. The accelerative effect of KO-t-C4H9 is explained by the reversible formation of the potassium amidato complexes trans-[RuH2{(S)-binap}{(S,S)-N(K)H(CHPh)2NH2}] or trans-[RuH2{(S)-binap}{(S,S)-N(K)H(CHPh)2NH(K)}]. The three-dimensional (3D) cavity observed within these molecules results in a chiral pocket stabilized via several different noncovalent interactions, including neutral and ionic hydrogen bonding, cation-π interactions, and π-π stacking interactions. Cooperatively, these interactions modify the catalyst structure, in turn lowering the relative activation barrier of hydride transfer by ~1-2 kcal mol(-1) and the following H-H bond cleavage by ~10 kcal mol(-1), respectively. A combined computational study and analysis of recent experimental data of the reaction pool results in new mechanistic insight into the catalytic cycle for hydrogenation of acetophenone by Noyori's catalyst, in the presence or absence of KO-t-C4H9.

Ammonia-borane (NH(3)BH(3), AB) has garnered interest as a hydrogen storage material due to its high weight percent hydrogen content and ease of H(2) release relative to metal hydrides. As a consequence of dehydrogenation, B-N-containing oligomeric/polymeric materials are formed. The ability to control this process and dictate the identity of the generated polymer opens up the possibility of the targeted synthesis of new materials. While precious metals have been used in this regard, the ability to construct such materials using earth-abundant metals such as Fe presents a more economical approach. Four Fe complexes containing amido and phosphine supporting ligands were synthesized, and their reactivity with AB was examined. Three-coordinate Fe(PCy(3))[N(SiMe(3))(2)](2) (1) and four-coordinate Fe(DEPE)[N(SiMe(3))(2)](2) (2) yield a mixture of (NH(2)BH(2))(n) and (NHBH)(n) products with up to 1.7 equiv of H(2) released per AB but cannot be recycled (DEPE = 1,2-bis(diethylphosphino)ethane). In contrast, Fe supported by a bidentate P-N ligand (4) can be used in a second cycle to afford a similar product mixture. Intriguingly, the symmetric analogue of 4 (Fe(N-N)(P-P), 3), only generates (NH(2)BH(2))(n) and does so in minutes at room temperature. This marked difference in reactivity may be the result of the chemistry of Fe(II) vs Fe(0).

Interest in sustainable non‐hydrocarbon‐based fuels for transportation has grown as the realization that the supply of fossil fuels is limited and the deleterious environmental effects of burning them has come into public focus. The use of hydrogen (H2) has been proposed as an alternative, but its use in pure form is undesirable due to the high pressures or low temperatures required to store useful quantities. Approaches to ameliorate this issue, which stem from the low volumetric energy density of H2, include the pursuit of sorbents capable of containing H2 in greater density than liquid H2 at reasonable temperatures and pressures, metal hydrides such as NaBH4, and chemical hydrides such as ammonia borane (AB, NH3BH3). AB contains 19.6 wt.‐% H2, which is well suited to practical applications, but issues with extracting the optimal quantities of H2 at reasonable temperatures and at useful rates as well as recycling of the spent fuel back into AB with good efficiency and reasonable cost remain to be solved. These problems are inextricably intertwined, as the needs of the regeneration process dictate which catalysts are used (i.e. what kind of spent fuel is generated). This Microreview focuses on recent developments in transition metal complexes for the catalytic dehydrogenation of AB. Neither solvolysis of AB nor thermolysis of AB in the absence of a catalyst are covered in this review.

Understanding the bonding trends within, and the differences between, the 4f and 5f element series with soft donor atom ligands will aid elucidation of the fundamental origins of actinide (An) versus lanthanide (Ln) selectivity that is integral to many advanced nuclear fuel cycle separation concepts. One of the principal obstacles to acquiring such knowledge is the dearth of well characterized transuranic molecules that prevents the necessary comparison of 4f versus 5f coordination chemistry, electronic structure, and bonding. Reported herein is new chemistry of selenium analogues of dithiophosphinate actinide extractants. Ln III and An III/IV complexes with the diselenophosphinate [Se 2 PPh 2 ] À anion have been synthesized, structurally and spectroscopically characterized, and quantum chemical calculations performed on model compounds in which the phenyl rings have been replaced by methyl groups. The complexes [Ln III (Se 2 PPh 2) 3 (THF) 2 ] (Ln ¼ La (1), Ce (2), Nd (3)), [La III (Se 2 PPh 2) 3 (MeCN) 2 ] (4), [Pu III (Se 2 PPh 2) 3 (THF) 2 ] (5), [Et 4 N][M III (Se 2 PPh 2) 4 ] (M ¼ Ce (6), Pu (7)), and [An IV (Se 2 PPh 2) 4 ] (An ¼ U (8), Np (9)), represent the first f-element diselenophosphinates. In conjunction with the calculated models, complexes 1-9 were utilized to examine two important factors: firstly, bonding trends/differences between trivalent 4f and 5f cations of near identical ionic radii; secondly, bonding trend differences across the 5f series within the An IV oxidation state. Analysis of both experimental and computational data supports the conclusion of enhanced covalent bonding contributions in Pu III-Se versus Ce III-Se bonding, while differences between U IV-Se and Np IV-Se bonding is satisfactorily accounted for by changes in the strength of ionic interactions as a result of the increased positive charge density on Np IV compared to U IV ions. These findings improve understanding of soft donor ligand binding to the f-elements, and are of relevance to the design and manipulation of f-element extraction processes.