Lewis Acid Decorated Hexacyanodiborane(6) Dianion.

First examples of diborane(6) dianions decorated with weakly coordination B(C6F5)3 (BCF) groups and SiEt3 + moieties have been synthesized demonstrating the synthetic potential of the [B2(CN)6]2- dianion. [B2{CNB(C6F5)3}6]2- (1) was isolated as potassium and tetrabutylammonium salt. 1 is a rare example for a weakly coordinating dianion and it was used for the stabilization of the carbocation [Ph3C]+ and the oxonium acid [H(OEt2)2]+. Reaction of [Ph3C]21 with HSiEt3 resulted in the silylated neutral diborane(6) [B2{CNB(C6F5)3}4(CNSiEt3)2] (2) in which two BCF groups have been selectively replaced by SiEt3 + substituents, underscoring the stability and chemical versatility of the [B2(CN)6]2- dianion. The chemical properties and physicochemical data of 1 and 2 provide insight into electronic, coordinating, and steric properties of theses novel diborane(6) compounds.

Metal-Free B-B Dehydrocoupling Reaction of a Simple Borane Adduct: Convenient Access to a Nucleophilic Diborane(4).

The selective formation of homonuclear bonds is of key importance in synthetic chemistry. Especially, dehydrocoupling reactions are attractive as ecologically and economically friendly alternatives to established reductive bond forming reactions, since they do not require the use of stoichiometric amounts of a reducing reagent and produce only valuable dihydrogen as by-product. Here, we report on a metal-free B-B dehydrocoupling reaction that starts directly from a simple, easily accessible BH3 adduct, providing convenient access to a new nucleophilic dihydridodiborane in excellent yield. The dihydridodiborane in turn activates dihydrogen, allowing to obtain quantitatively the dideuteridodiborane from the dihydridodiborane by D2 activation. On the basis of detailed quantum-chemical calculations, the mechanism of this unprecedented reaction is elucidated. Some key points that are essential for metal-free dehydrocoupling are disclosed, paving the way for their systematic evaluation and application.

Catalyst-Free Regioselective Diborylation of Aryllithium with Tetra(o-tolyl)diborane(4).

A catalyst-free 1,2-diborylation of aryllithium with tetra(o-tolyl)diborane(4) has been achieved, giving a series of 1,2-diborylaryl lithium species in excellent yields under mild reaction conditions, which leads to 1,2-di(tolyl)borylarenes in 60-91 % yields upon treatment with the hydride-abstracting reagent. In these transformations, one sp2 C-H of arene is activated and both boryl units are utilized to build two new (sp2 )C-B bonds. This represents a new strategy for selective arene diborylation. Density functional theory (DFT) calculations suggest that an aromatic nucleophilic substitution is a key step in the formation of the products.

Stereoselective Unsymmetrical 1,1-Diborylation of Alkynes with a Neutral sp2 -sp3 Diboron Reagent.

The incorporation of two distinct boryl groups at the same carbon center in organic molecules has attracted growing research interest due to its potential for facilitating controlled, precise synthesis through stepwise dual carbon-boron bond transformations. Here we report a method to access unsymmetrical 1,1-diborylalkene (UDBA) stereoselectively via the reaction of readily available alkynes with a neutral sp2 -sp3 diboron reagent (NHC)BH2 -Bpin (NHC=N-heterocyclic carbene). Attributing to the chemically easily distinguishable nature of the sp2 and sp3 boryl moieties, controllable stepwise derivatization of the resultant UDBAs is realized. This process leads to various multifunctionalized olefins and organoborons, such as acylboranes, which are difficult to prepare by other methods.

Halide-Coupled Double Electron Transfer with Electron-Rich Diboranes.

The ditriflato-diborane B2 (µ-hpp)2 (OTf)2 (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate) acts as a stable surrogate of the elusive dication [B2 (hpp)2 ]2+ , being both electrophilic (vacant boron p orbitals) and nucleophilic (filled B-B bond orbital). This combination of seemingly contrasting behaviors could be used to develop a metallomimetic diborane chemistry, with Lewis σ-basic and π-acidic substrates being bound and reduced at the diborane. Here, we report on a novel reaction type within this general theme, in which double electron transfer from the diboron unit to the boron-bound organic substrate is coupled with halide transfer in the other direction. Novel diborylated dienamines are synthesized in this way. The scope of this unprecedented reaction motif and the reaction pathways are elucidated.

Neutral and Anionic Diboron Compounds Bearing Electron-Precise B-B Bond.

Electron-precise B-B bonded compounds are valuable reagents in organic syntheses, which can be used as key starting material for the synthesis of functionalized organoboranes. Bis(pinacolato)diborane(4) B2 pin2 and its derivatives are among the most studied diboron species. However, their B-B bonds usually need to be activated by transition metal catalysts or bases for further transformations. Recently, many well-designed/reactive electron-precise B-B bonded compounds have been developed, which could facilitate direct reactions with small molecules, unsaturated substrates, and electrophiles. This review highlights the synthesis, structure, and reactivity of neutral and anionic B-B bonded compounds.

Synthesis, Reactivity and Coordination Chemistry of Group 9 PBP Boryl Pincer Complexes: [(PBP)M(PMe3)n] (M = Co, Rh, Ir; n = 1, 2).

The unsymmetrical diborane(4) derivative [(d(CH2P(iPr)2)abB)-Bpin] (1) proved to be a versatile PBP boryl pincer ligand precursor for Co(I) (2a, 4a), Rh(I) (2-3b) and Ir(I/III) (2-3c, 5-6c) complexes, in particular of the types [(d(CH2P(iPr)2)abB)M(PMe3)2] (2a-c) and [(d(CH2P(iPr)2)abB)M-PMe3] (2b-c). Whilst similar complexes have been obtained before, for the first time, the coordination chemistry of a homologous series of PBP pincer complexes, in particular the interconversion of the five- and four-coordinate complexes 2a-c/3a-c, was studied in detail. For Co, instead of the mono phosphine complex 2a, the dinitrogen complex [(d(CH2P(iPr)2)abB)Co(N2)(PMe3)] (4a) is formed spontaneously upon PMe3 abstraction from 2a in the presence of N2. All complexes were comprehensively characterised spectroscopically in solution via multinuclear (VT-)NMR spectroscopy and structurally in the solid state through single-crystal X-ray diffraction. The unique properties of the PBP ligand with respect to its coordination chemical properties are addressed.

On the Reactivity of a NHC Nickel Bis-Boryl Complex: Reductive Elimination and Formation of Mono-Boryl Complexes.

The synthesis of the first terminal mono-boryl complexes of nickel, which are not stabilized by a pincer ligand, is reported. The reaction of the nickel bis-boryl complex cis-[Ni(i Pr2 ImMe )2 (Bcat)2 ] 1 (cat=1,2-O2 C6 H4 ) with the small donor ligand PMe3 led to a complete ligand exchange at nickel with reductive elimination of B2 cat2 and formation of the bis-NHC adduct [B2 cat2 ⋅ (i Pr2 ImMe )2 ] 3 and [Ni(PMe3 )4 ] 2 as the metal-containing species. Electrophilic attack of MeI on complex 1 or ligand dismutation of 1 with trans-[Ni(i Pr2 ImMe )2 Br2 ] led to loss of only one boryl ligand of 1 and afforded the nickel mono-boryl complexes trans-[Ni(i Pr2 ImMe )2 (Bcat)Br] 4 a and trans-[Ni(i Pr2 ImMe )2 (Bcat)I] 4 b.

Reactions of Tetra(o-tolyl)diborane(4) with Organic Azides: Formation of Fluorescent Boron-Fused Hexazenes.

The reaction of tetra(o-tolyl)diborane(4) with organic azides afforded three different compounds, diborylamines, diboryltriazenes, and B2 -hexazenes having a bicyclic B2 N6 ring system. The reaction with aryl azides gave diborylamines, while the reaction with 1 equiv. of alkyl azides furnished diboryltriazenes. In the case of the reaction with an excess amount of primary alkyl azide, a new heterocyclic B2 -hexazenes were obtained. The formation of the B2 N6 structure could be explained by one general reaction mechanism via the diboryltriazene intermediate according to the control experiments and DFT calculations. The B2 -hexazenes exhibited a strong fluorescence with a remarkably high fluorescent quantum yield of up to 96 %.

Thienyl-Substituted Diboranes(4): Electronic Stabilization of Radicals Versus Increased Reactivity towards Bond Activation.

Low-valent main group chemistry involves a balancing act between steric and electronic stabilization of the electron-rich low oxidation state main group centers and their desired reactivity. Herein we show that the combination of sterically shielding mesityl and rotationally flexible 2-thienyl groups, the latter having the potential to be either electronically stabilizing or activating, at a diborane(4) provides a platform for both radical anion stabilization and unusual bond activation and rearrangement reactions. The addition of a Lewis base to a 1,2-dimesityl-1,2-dithienyldiborane(4) (1) results in direct and unprecedented C-H borylation of one thienyl substituent with cleavage of the B-B bond. The facile one-electron reduction of 1 yields a stable diboron radical anion through delocalization of its unpaired electron over the entire planar 1,2-dithienyldiboron framework, as evidenced by EPR spectroscopy and DFT calculations. The two-electron reduction of 1 with magnesium anthracene under more forcing conditions results in B-B bond cleavage and replacement of one thienyl sulfur atom by a mesitylboron moiety, leading to the formation of a magnesium complex of an η5 -diborafulvene dianion. Salt metathesis of the latter with [(η6 -p-cymene)RuCl2 ] affords a mixed ruthenium sandwich complex of an η5 -borylborole dianion. Calculations highlight both the structural and electronic changes in the boron-substituted heterocyclic C4 B dianion upon switching coordination from magnesium (diborafulvene dianion) to ruthenium (borylborole dianion).

Bistriazoles Connected Through a B-B Bridge, Synthesized by Highly Selective Dipolar Cycloaddition Reactions of a Diazido-diborane(4).

In this work we report the first cycloaddition reactions between a diazido diborane(4) and terminal alkynes, providing unique access to bis-1,2,3-triazoles connected by a B-B bridge. The catalyst-free reactions are highly selective, yielding exclusively the thermodynamically disfavored bis-1,4-triazoles. The reactions are enabled by the high thermal stability of the diazido-diborane [B(hpp)(N3 )]2 (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidinate). Due to the tetra-coordinate boron atoms in this reagent, the reactions are tolerant with respect to the introduction of Lewis-basic groups at the alkyne. The scope and limitations of the new reactions are discussed.

Reversible Dissociation for Effective Storage of Diborane Gas within the UiO-66-NH2 Metal-Organic Framework.

There is an acute need for materials that can store the toxic and highly reactive diborane gas at room temperature. In this work, the interfacial chemistry leading to safe and reversible storage of diborane (B2H6) in the UiO-66-NH2 metal-organic framework (MOF) was investigated via in situ transmission infrared (IR) spectroscopy, temperature-programmed desorption (TPD), and electronic structure calculations. The infrared spectrum of B2H6 adsorbed within UiO-66-NH2 indicates hydrogen bonding with the µ3-OH groups of the MOF nodes and chemisorption at the -NH2 groups of the MOF linkers. The conversion of physisorbed to chemisorbed diborane, as observed through a spectroscopically unique intermediate species, occurred over a broad temperature regime from 80 to 410 K. During B2H6-TPD studies, both the weakly and strongly bound species were found to desorb exclusively as molecular B2H6. Infrared spectroscopic studies, performed during diborane adsorption and reaction, combined with electronic structure calculations, revealed that chemisorption occurred via a reversible dissociation reaction involving a "half-open" B2H6 intermediate and resulted in the formation of two NH2-bound BH3 units, which leave the MOF as B2H6 via recombinative desorption. The close spacing of -NH2 groups in the UiO-66-NH2 MOF is key to enabling high-temperature chemisorptive storage of B2H6, and the spatial arrangement of the amine groups has a significant effect on the dissociation energy profile. This work demonstrates that reversible dissociation of B2H6 on precisely engineered, nucleophile-rich materials represents a promising pathway to diborane stabilization and long-term storage.

Directed Synthesis and Chemistry of Unsymmetric Dicationic Diboranes and Their Use in Frustrated Lewis Pair-like Chemistry.

The chemistry of dicationic diboranes with two BII atoms that are engaged in direct B-B bonding is by enlarge unexplored, although these molecules have intriguing properties due to their combined Lewis acidic and electron-donor properties. Unsymmetric dicationic diboranes are extremely rare, but especially attractive due to their polarized B-B bond. In this work we report the directed synthesis of several stable unsymmetric dicationic diboranes by reaction between the electron-rich ditriflato-diborane B2 (hpp)2 (OTf)2 (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidinate) and phosphino-pyridines, establishing B-N and B-P bonds with the diborane concomitant with triflate elimination. In the case of 2-((ditertbutylphosphino)methyl)pyridine, the B-N bond is formed instantly, but the B-P bond formation requires (due to steric constraints) several days at ambient conditions for completion, creating an intermediate that could be used for frustrated Lewis pair (FLP)-like chemistry. Here we test its reaction with an aldehyde, and propose a new type of FLP-like chemistry.

Tetraaryldiborane(4) Can Emit Dual Fluorescence Responding to the Structural Change around the B-B Bond.

We report the successful synthesis of tetramesityldiborane(4) (Mes4 B2 ) through the reductive coupling of a dimesitylborinium ion. Owing to the steric protection conferred by the mesityl groups, Mes4 B2 shows exceptional chemical stability and remains intact in water. Single-crystal X-ray analysis revealed that Mes4 B2 has an orthogonal geometry, where the B-B center is completely hidden by the mesityl groups. Remarkably, Mes4 B2 emits dual fluorescence at 460 and 620 nm, both in solution and in the solid state. Theoretical calculations showed that Mes4 B2 in the excited S1 state adopts a twisted or planar geometry, which is responsible for the shorter- or longer-wavelength fluorescence, respectively. The intensity ratio of the dual fluorescence is sensitive to the viscosity of the medium, which suggests that Mes4 B2 has potential as a ratiometric viscosity sensor.

Controlled Synthesis of Oligomers Containing Main-Chain B(sp2 )-B(sp2 ) Bonds.

A number of novel alkynyl-functionalized diarylbis(dimethylamino)diboranes(4) are prepared by salt metathesis, and the appended alkynyl groups are subjected to hydroboration. Their reactions with monohydroboranes lead to discrete boryl-appended diborane(4) species, while dihydroboranes induce their catenation to oligomeric species, the first known examples of well-characterized macromolecular species with B-B bonds. The oligomeric species were found to comprise up to ten repeat units and are soluble in common organic solvents. Some of the oligomeric species have good air stability and all were characterized by NMR and vibrational spectroscopy and size-exclusion chromatography techniques.

Diphosphino-Functionalized 1,8-Naphthyridines: a Multifaceted Ligand Platform for Boranes and Diboranes.

A 1,8-naphthyridine diphosphine (NDP) reacts with boron-containing Lewis acids to generate complexes featuring a number of different naphthyridine bonding modes. When exposed to diborane B2 Br4 , NDP underwent self-deprotonation to afford [NDP-B2 Br3 ]Br, an unsymmetrical diborane comprised of four fused rings. The reaction of two equivalents of monoborane BBr3 and NDP in a non-polar solvent provided the simple phosphine-borane adduct [NDP(BBr3 )2 ], which then underwent intramolecular halide abstraction to furnish the salt [NDP-BBr2 ][BBr4 ], featuring a different coordination mode from that of [NDP-B2 Br3 ]Br. Direct deprotonation of NDP by KHMDS or PhCH2 K generates mono- and dipotassium reagents, respectively. The monopotassium reagent reacts with one or half an equivalent of B2 (NMe2 )2 Cl2 to afford NDP-based diboranes with three or four amino substituents.

Polycationic Redox-Active Cyclophanes with Integrated Electron-Rich Diboron Units.

Cationic cyclophanes are widely used in a variety of applications in supramolecular chemistry and materials science. In this work the authors systematically study the integration of electron-rich diboron units with BII atoms into polycationic cyclophanes with viologen-like electron-acceptor units. They also report a first hexacationic cage-compound in which three diboron units connect two tris(4-pyridyl)triazine acceptor units. Moreover, di- and tetracationic open-structure compounds, in which one diboron unit connects two bispyridyl groups, were synthesized and the properties compared to those of the corresponding closed structures (cyclophanes). The combination of diboron electron-donor units and bi- or oligopyridyl electron-acceptor units leads to intriguing optical and redox properties.

On the Rate of Interaction of Sodium Borohydride with Platinum (IV) Chloride Complexes in Alkaline Media.

In this work, sodium borohydride was used as a strong reductant of traces of platinum complex ions. The investigations of the kinetics of redox reaction between platinum(IV) chloride complex ions and sodium borohydride were carried out. For the first time, the kinetic experiments were carried out in a basic medium (pH~13), which prevents NaBH4 from decomposition and suppresses the release of hydrogen to the environment. The rate constants of Pt(IV) reduction to Pt(II) ions under different temperatures and concentrations of chloride ions conditions were determined. In alkaline solution (pH~13), the values of enthalpy and entropy of activation are 29.6 kJ/mol and -131 J/mol K. It was also found that oxygen dissolved in the solution strongly affects kinetics of the reduction process. Using collected results, the reduction mechanism was suggested. For the first time, the appearance of diborane as an intermediate product during Pt(IV) ions reduction was suggested. Moreover, the influence of oxygen present in the reacting solution on the rate of reduction reaction was also shown.

Predicting Dinitrogen Coupling with a Series of Small Molecules Catalyzed by a Pincer Complex.

Due to consumption of more than 2% of the world's annual energy supply by Haber-Bosch process and the strongest triple bond (N≡N) in nature, directly coupling N2 with small molecules is particularly important and challenging, let alone in a catalytic fashion. Here we first demonstrate that a NNN-type pincer phosphorus complex could act as a catalyst to couple dinitrogen with a series of small molecules including carbon dioxide, formaldehyde, N-ethylidenemethylamine, and acetonitrile in the presence of diborane(4) under a mild condition by theoretical calculations. N2 fixation proceeds via a stepwise mechanism involving initial N2 activation by diborane(4), followed by intramolecular isomerization to a key intermediate (zwitterion). Such a zwitterion can be used to couple a series of small molecules with activation barriers of 23.5-25.2 kcal mol-1 . All these findings could be particularly useful for main group chemistry aimed at N2 activation.

Engineering Challenges of Solution and Slurry-Phase Chemical Hydrogen Storage Materials for Automotive Fuel Cell Applications.

We present the research findings of the DOE-funded Hydrogen Storage Engineering Center of Excellence (HSECoE) related to liquid-phase and slurry-phase chemical hydrogen storage media and their potential as future hydrogen storage media for automotive applications. Chemical hydrogen storage media other than neat liquid compositions will prove difficult to meet the DOE system level targets. Solid- and slurry-phase chemical hydrogen storage media requiring off-board regeneration are impractical and highly unlikely to be implemented for automotive applications because of the formidable task of developing solid- or slurry-phase transport systems that are commercially reliable and economical throughout the entire life cycle of the fuel. Additionally, the regeneration cost and efficiency of chemical hydrogen storage media is currently the single most prohibitive barrier to implementing chemical hydrogen storage media. Ideally, neat liquid-phase chemical hydrogen storage media with net-usable gravimetric hydrogen capacities of greater than 7.8 wt% are projected to meet the 2017 DOE system level gravimetric and volumetric targets. The research presented herein is a collection of research findings that do not in and of themselves warrant a dedicated manuscript. However, the collection of results do, in fact, highlight the engineering challenges and short-comings in scaling up and demonstrating fluid-phase ammonia borane and alane compositions that all future materials researchers working in hydrogen storage should be aware of.