Achieving Control over the Reduction/Coupling Dichotomy of N2 by Boron Metallomimetics.

We report a detailed computational and experimental study of the fixation and reductive coupling of dinitrogen with low-valent boron compounds. Consistent with our mechanistic findings, the selectivity toward nitrogen fixation or coupling can be controlled through either steric bulk or the reaction conditions, allowing for the on-demand synthesis of nitrogen chains. The electronic structure and intriguing magnetic properties of intermediates and products of the reaction of dinitrogen with borylenes are also elucidated using high-level computational approaches.

Metallomimetic Chemistry of Boron.

The study of main-group molecules that behave and react similarly to transition-metal (TM) complexes has attracted significant interest in recent decades. Most notably, the attractive idea of replacing the all-too-often rare and costly metals from catalysis has motivated efforts to develop main-group-element-mediated reactions. Main-group elements, however, lack the electronic flexibility of TM complexes that arises from combinations of empty and filled d orbitals and that seem ideally suited to bind and activate many substrates. In this review, we look at boron, an element that despite its nonmetal nature, low atomic weight, and relative redox staticity has achieved great milestones in terms of TM-like reactivity. We show how in interelement cooperative systems, diboron molecules, and hypovalent complexes the fifth element can acquire a truly metallomimetic character. As we discuss, this character is powerfully demonstrated by the reactivity of boron-based molecules with H2, CO, alkynes, alkenes and even with N2.

2,2'-Bipyridyl as a Redox-Active Borylene Abstraction Agent.

2,2'-Bipyridyl is shown to spontaneously abstract a borylene fragment (R-B:) from various hypovalent boron compounds. This process is a redox reaction in which the bipyridine is reduced and becomes a dianionic substituent bound to boron through its two nitrogen atoms. Various transition metal-borylene complexes and diboranes, as a well as a diborene, take part in this reaction. In the latter case, our results show an intriguing example of the homolytic cleavage of a B═B double bond.

Heterodiatomic Multiple Bonding in Group†13: A Complex with a Boron-Aluminum π†Bond Reduces CO2.

Heterodiatomic multiple bonds have never been observed within Group 13. Herein, we disclose a method that generates [(CAAC)PhB=AlCp3t ] (1), a complex featuring π bonding between boron and aluminum through the association of singlet fragments. We present the properties of this multiple bond as well as the reactivity of the complex with carbon dioxide, which yields a boron CO complex via an unusual metathesis reaction.

A Boradiselenirane and a Boraditellurirane: Isolable Heavy Analogs of Dioxiranes and Dithiiranes.

The isolation of BE2 heterocycles (E = Te, Se, S) from the reaction of a manganese borylene complex with elemental chalcogens is reported. The BTe2 and BSe2 cycles-a boraditellurirane and a boradiselenirane, respectively-are the first analogs of dioxiranes based on heavy chalcogens. While the BTe2 unit is still found datively bound to manganese, the Se and S analogs were isolated in their free forms. All heterocycles have been shown to transfer a chalcogen atom, allowing for the isolation of novel borachalcones and their dimerization products.

Theoretical Calculations for Highly Selective Direct Heteroarylation Polymerization: New Nitrile-Substituted Dithienyl-Diketopyrrolopyrrole-Based Polymers.

Direct Heteroarylation Polymerization (DHAP) is becoming a valuable alternative to classical polymerization methods being used to synthesize π-conjugated polymers for organic electronics applications. In previous work, we showed that theoretical calculations on activation energy (Ea) of the C⁻H bonds were helpful to rationalize and predict the selectivity of the DHAP. For readers' convenience, we have gathered in this work all our previous theoretical calculations on Ea and performed new ones. Those theoretical calculations cover now most of the widely utilized electron-rich and electron-poor moieties studied in organic electronics like dithienyl-diketopyrrolopyrrole (DT-DPP) derivatives. Theoretical calculations reported herein show strong modulation of the Ea of C⁻H bond on DT-DPP when a bromine atom or strong electron withdrawing groups (such as fluorine or nitrile) are added to the thienyl moiety. Based on those theoretical calculations, new cyanated dithienyl-diketopyrrolopyrrole (CNDT-DPP) monomers and copolymers were prepared by DHAP and their electro-optical properties were compared with their non-fluorinated and fluorinated analogues.

Main-Group Metallomimetics: Transition Metal-like Photolytic CO Substitution at Boron.

The carbon monoxide adduct of an unhindered and highly reactive CAAC-bound arylborylene, [(CAAC)B(CO)Ar] (CAAC = cyclic (alkyl) (amino)carbene), has been prepared using a transfer reaction from the linear iron borylene complex [(PMe3) (CO)3Fe=BAr]. [(CAAC)B(CO)Ar] is a source of the dicoordinate [(CAAC)ArB:] borylene that can be liberated by selective photolytic CO extrusion and that, although highly reactive, is sufficiently long-lived to react intermolecularly. Through trapping of the borylene generated in this manner, we present, among others, the first metal-free borylene(I) species containing a nitrogen-based donor, as well as a new boron-containing radical.

Synthesis and Reduction of Sterically Encumbered Mesoionic Carbene-Stabilized Aryldihaloboranes.

Sterically hindered, in situ generated 1,3,4-substituted 1,2,3-triazol-5-ylidene mesoionic carbenes (MICs) were employed to stabilize a number of aryl- and heteroaryldihaloboranes, as well as the first MIC-supported diborane. Reduction of borane adducts of the 1-(2,6-diisopropylphenyl)-3-methyl-4-tert-butyl-1,2,3-triazol-5-ylidene ligand with KC8 in non-coordinating solvents led to intramolecular C-H- and, C-C-activation at an isopropyl residue of the supporting ligand. DFT calculations showed that each of these activation reactions proceeds via a different isomer of a borylene intermediate.

The First Boron-Tellurium Double Bond: Direct Insertion of Heavy Chalcogens into a Mn=B Double Bond.

The base-stabilized borylene [Cp(OC)2 Mn=BtBu(IMe)] readily reacts with elemental chalcogens in an insertion reaction that yields borachalcone complexes [Cp(OC)2 Mn-E=BtBu(IMe)] (E=S, Se, Te). The tellurium example features the first double bond between boron and tellurium, making Te the heaviest main-group element to make multiple bonds with boron. This unprecedented interaction has been fully investigated both experimentally and computationally.

Synthesis of Carboxylate Cp*Zr(IV) Species: Toward the Formation of Novel Metallocavitands.

With the intent of generating metallocavitands isostructural to species [(CpZr)3(µ(3)-O)(µ(2)-OH)3(κO,O,µ(2)-O2C(R))3](+), the reaction of Cp*2ZrCl2 and Cp*ZrCl3 with phenylcarboxylic acids was carried out. Depending on the reaction conditions, five new complexes were obtained, which consisted of Cp*2ZrCl(κ(2)-OOCPh) (1), (Cp*ZrCl(κ(2)-OOCPh))2(µ-κ(2)-OOCPh)2 (2), [(Cp*Zr(κ(2)-OOCPh))2(µ-κ(2)-OOCPh)2(µ(2)-OH)2]·Et2O (3·Et2O), [[Cp*ZrCl2](µ-Cl)(µ-OH)(µ-O2CC6H5)[Cp*Zr]]2(µ-O2CC6H5)2 (4), and [Cp*ZrCl4][(Cp*Zr)3(κ2-OOC(C6H4Br)3(µ3-O)(µ2-Cl)2(µ2-OH)] [5](+)[Cp*ZrCl4](-). The structural characterization of the five complexes was carried out. Species 3·Et2O exhibits host-guest properties where the diethyl ether molecule is included in a cavity formed by two carboxylate moieties. The secondary interactions between the cavity and the diethyl ether molecule affect the structural parameters of the complex, as demonstrated be the comparison of the density functional theory models for 3 and 3·Et2O. Species 5 was shown to be isostructural to the [(CpZr)3(µ(3)-O)(µ(2)-OH)3(κO,O,µ(2)-O2C(R))3](+) metallocavitands.

Reducing CO2 to methanol using frustrated Lewis pairs: on the mechanism of phosphine-borane-mediated hydroboration of CO2.

The full mechanism of the hydroboration of CO2 by the highly active ambiphilic organocatalyst 1-Bcat-2-PPh2-C6H4 (Bcat = catecholboryl) was determined using computational and experimental methods. The intramolecular Lewis pair was shown to be involved in every step of the stepwise reduction. In contrast to traditional frustrated Lewis pair systems, the lack of steric hindrance around the Lewis basic fragment allows activation of the reducing agent while moderate Lewis acidity/basicity at the active centers promotes catalysis by releasing the reduction products. Simultaneous activation of both the reducing agent and carbon dioxide is the key to efficient catalysis in every reduction step.

Transition-metal-free catalytic reduction of carbon dioxide.

Metal-free systems, including frustrated Lewis pairs (FLPs) have been shown to bind CO2. By reducing the Lewis acidity and basicity of the ambiphilic system, it is possible to generate active catalysts for the deoxygenative hydroboration of carbon dioxide to methanol derivatives with conversion rates comparable to those of transition-metal-based catalysts.

A highly active phosphine-borane organocatalyst for the reduction of CO2 to methanol using hydroboranes.

In this work, we report that organocatalyst 1-Bcat-2-PPh2-C6H4 ((1); cat = catechol) acts as an ambiphilic metal-free system for the reduction of carbon dioxide in presence of hydroboranes (HBR2 = HBcat (catecholborane), HBpin (pinacolborane), 9-BBN (9-borabicyclo[3.3.1]nonane), BH3·SMe2 and BH3·THF) to generate CH3OBR2 or (CH3OBO)3, products that can be readily hydrolyzed to methanol. The yields can be as high as 99% with exclusive formation of CH3OBR2 or (CH3OBO)3 with TON (turnover numbers) and TOF (turnover frequencies) reaching >2950 and 853 h(-1), respectively. Furthermore, the catalyst exhibits "living" behavior: once the first loading is consumed, it resumes its activity on adding another loading of reagents.

Rapid, iterative syntheses of unsymmetrical di- and triarylboranes from crystalline aryldifluoroboranes.

A one-pot procedure to synthesise aryldifluoroboranes, ArBF2, from bench-stable arylsilanes is presented. These ArBF2 react conveniently with aryllithium reagents to form unsymmetrical ArAr'BF and BArAr'Ar'' in high yield. Examples of all three classes of borane have been characterised crystallographically, allowing for elucidation of geometric and crystal packing trends in crystalline ArBF2.

Transition-metal-carbene-like intermolecular insertion of a borylene into C-H bonds.

We demonstrate that, in analogy to transition-metal carbene chemistry, [(OC)5Mo[double bond, length as m-dash]BN(SiMe3)2] facilitates intermolecular transfer of the borylene [:BN(SiMe3)2], which ultimately undergoes insertion into C-H bonds under very mild conditions. The one-pot multiple functionalization of the cyclopentadienyl rings of tungstenocene dihydride is demonstrated using this approach.

One-pot, room-temperature conversion of dinitrogen to ammonium chloride at a main-group element.

The industrial reduction of dinitrogen (N2) to ammonia is an energy-intensive process that consumes a considerable proportion of the global energy supply. As a consequence, species that can bind N2 and cleave its strong N-N bond under mild conditions have been sought for decades. Until recently, the only species known to support N2 fixation and functionalization were based on a handful of metals of the s and d blocks of the periodic table. Here we present one-pot binding, cleavage and reduction of N2 to ammonium by a main-group species. The reaction-a complex multiple reduction-protonation sequence-proceeds at room temperature in a single synthetic step through the use of solid-phase reductant and acid reagents. A simple acid quench of the mixture then provides ammonium, the protonated form of ammonia present in fertilizer. The elementary reaction steps in the process are elucidated, including the crucial N-N bond cleavage process, and all of the intermediates of the reaction are isolated.

Synthesis of unsymmetrical B2E2 and B2E3 heterocycles by borylene insertion into boradichalcogeniranes.

We report the selective insertion of a range of borylene fragments into the E-E bonds (E = S, Se, Te) of cyclic boron dichalcogenides. This method provides facile synthetic access to a variety of symmetrical and unsymmetrical four- and five-membered rings.

The reductive coupling of dinitrogen.

The coupling of two or more molecules of dinitrogen (N2) occurs naturally under the radiative conditions present in the ionosphere and may be achieved synthetically under ultrahigh pressure or plasma conditions. However, the comparatively low N-N single-bond enthalpy generally renders the catenation of the strongly triple-bonded N2 diatomic unfavorable and the decomposition of nitrogen chains a common reaction motif. Here, we report the surprising organoboron-mediated catenation of two N2 molecules under near-ambient conditions to form a complex in which a [N4]2- chain bridges two boron centers. The reaction entails reductive coupling of two hypovalent-boron-bound N2 units in a single step. Both this complex and a derivative protonated at both ends of the chain were characterized crystallographically.

Nitrogen fixation and reduction at boron.

Currently, the only compounds known to support fixation and functionalization of dinitrogen (N2) under nonmatrix conditions are based on metals. Here we present the observation of N2 binding and reduction by a nonmetal, specifically a dicoordinate borylene. Depending on the reaction conditions under which potassium graphite is introduced as a reductant, N2 binding to two borylene units results in either neutral (B2N2) or dianionic ([B2N2]2-) products that can be interconverted by respective exposure to further reductant or to air. The 15N isotopologues of the neutral and dianionic molecules were prepared with 15N-labeled dinitrogen, allowing observation of the nitrogen nuclei by 15N nuclear magnetic resonance spectroscopy. Protonation of the dianionic compound with distilled water furnishes a diradical product with a central hydrazido B2N2H2 unit. All three products were characterized spectroscopically and crystallographically.