Trapping of a Terminal Intermediate in the Boron-Mediated Dinitrogen Reduction: Mono-, Tri-, and Tetrafunctionalized Hydrazines in Two Steps from N2.

The addition of chlorotrimethylsilane to a boron-mediated, transition-metal-free N2 activation reaction leads to the isolation of multiple potassium boryl(silyl)hydrazido species, likely trapping products of a terminal dinitrogen complex of boron. One of these silylated N2 species can be protonated or methylated, providing access to mono- to tetrafunctionalized hydrazines in two steps from N2 and in the absence of transition metals.

C-H Bond Activation by Iridium(III) and Iridium(IV) Oxo Complexes.

Oxidation of an iridium(III) oxo precursor enabled the structural, spectroscopic, and quantum-chemical characterization of the first well-defined iridium(IV) oxo complex. Side-by-side examination of the proton-coupled electron transfer thermochemistry revealed similar driving forces for the isostructural oxo complexes in two redox states due to compensating contributions from H+ and e- transfer. However, C-H activation of dihydroanthracene revealed significant hydrogen tunneling for the distinctly more basic iridium(III) oxo complex. Our findings complement the growing body of data that relate tunneling to ground state properties as predictors for the selectivity of C-H bond activation.

Experimental and Computational Study of a Confirmed Borylene-to-Diborene Dimerization.

While the dimerization of heavier group 13 carbene analogues to the corresponding alkene analogues is known and relatively well understood, the dimerization of dicoordinate borylenes (LRB:, L = neutral donor; R = anionic substituent) to the corresponding diborenes (LRB═BRL) has never been directly observed. In this study we present the first example of a formal borylene-to-diborene dimerization through abstraction of a labile phosphine ligand from the tricoordinate hydroborylene precursor (CAAC)(Me3P)BH (CAAC = cyclic alkyl(amino)carbene) by bulky Lewis-acidic dihaloboranes (BX2Y, X = Cl, Br, Y = aryl, boryl), generating the corresponding dihydrodiborene (CAAC)HB═BH(CAAC) and (Me3P)BX2Y as the byproduct. An in-depth experimental and computational mechanistic analysis shows that this seemingly simple process (2 LL'BH + 2 BX2Y → LHB═BHL + 2 L'BX2Y) is in fact based on a complex sequence of finely tuned processes, involving the one-electron oxidation of and PMe3 abstraction from the borylene precursor by BX2Y, multiple halide transfers between (di)boron intermediates and BX2Y/[BX3Y]-, and multiple one-electron redox processes between diboron intermediates and the borylene precursor, which make the reaction ultimately autocatalytic in [(CAAC)(Me3P)BH]•+. The findings suggest that [LBXR]• boryl radicals are more likely coupling partners than dicoordinate LRB: borylenes in the reductive coupling of base-stabilized LBX2R boranes to LRB═BRL diborenes.

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.

A Journey from Benzoborirene to Benzoborole-Supported 1,2-Diimine and Antiaromatic Borolediide.

The reaction of benzoborirene with one equivalent of isocyanides leads to benzene-fused boretes bearing one imine function, while the reaction with two equivalents of isocyanide affords 2,3-dihydro-2,3-diiminoboroles with perfect regioselectivity. The isocyanide double insertion products represent a novel type of 1,2-diimine with a benzoborole backbone. The reduction chemistry of the benzoborole-supported 1,2-diimine was investigated. Single- and two-electron reduction allow for the isolation and full characterization of a radical anion and a dianion, respectively. In stark contrast to the ordinary boroles, which should turn aromatic by accepting two electrons, the antiaromatic character of the benzoborole backbone is highlighted upon reduction, thus presenting a rare example of antiaromatic borole dianion. Detailed quantum chemical calculations provide a rationale for the observed regioselectivity and the electronic structure of the reduced borole diimine species.

Stabilizing Doubly Deprotonated Diazomethane: Isolable Complexes with CN22- and CN2- Radical Ligands.

Transition metal complexes with a doubly deprotonated diazomethane (CNN2-) ligand have been proposed as fleeting intermediates in nitrogen transfer reactions. However, in contrast to isoelectronic azide (N3-), well-defined examples are unknown. We here report the synthesis and characterization of isolable complexes with terminal and bridging CNN2- ligands, stabilized by platinum(II) pincer fragments. Bonding within the allenic dimetallanitrilimine core (Pt-N═N═C-Pt) was probed by oxidation of the bridging ligand. Enhanced reactivity toward [3 + 2]-cycloaddition with CO2 was obtained. Photofragmentation favors N-NC over NN-C bond cleavage as a route to cyanide and a transient metallonitrene complex.

Rhenium-Mediated Conversion of Dinitrogen and Nitric Oxide to Nitrous Oxide.

Reductive splitting of N2 is an attractive strategy towards nitrogen fixation beyond ammonia at ambient conditions. However, the resulting nitride complexes often suffer from thermodynamic overstabilization hampering functionalization. Furthermore, oxidative nitrogen atom transfer of N2 derived nitrides remains unknown. We here report a ReIV pincer platform that mediates N2 splitting upon chemical reduction or electrolysis with unprecedented yield. The N2 derived ReV nitrides undergo facile nitrogen atom transfer to nitric oxide, giving nitrous oxide nearly quantitatively. Experimental and computational results indicate that outer-sphere ReN/NO radical coupling is facilitated by the activation of the nitride via initial coordination of NO.

Nitrogen Atom Transfer Catalysis by Metallonitrene C-H Insertion: Photocatalytic Amidation of Aldehydes.

C-H amination and amidation by catalytic nitrene transfer are well-established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C-H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd-N) with a diradical nitrogen ligand that is singly bonded to PdII . Despite the subvalent nitrene character, selective C-H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N3 SiMe3 . Based on these results, a photocatalytic protocol for aldehyde C-H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C-H nitrogen atom transfer offers facile access to primary amides after deprotection.

1-Aza-2,4-disilabicyclo[1.1.0]butanes with Superelongated C-N σ-Bonds.

Two silylene molecules oxidatively react under formal [1 + 2 + 1]-cycloaddition to the C≡N bond of nitriles to yield 1-aza-2,4-disilabicyclo[1.1.0]butanes (L)(Cl)Si[µ-η1,2-NC(p-RC6H4)]Si(Cl)(L) (L = PhC(NtBu)2, R = CF3 (2), F (3), Cl (4), Br (5)). The strongly folded bicyclic SiCNSi cores in 2-5 feature inverted bridgehead carbon atoms and superelongated C-N bonds [1.745(12) to 1.801(2) Å], exceeding the lengths of C-N single bonds in known silaaziridines by up to 23%. Detailed bonding analysis discloses C-N bonding interactions, sharing far-reaching similarities with the central C-C bond in [1.1.1]propellane.

Probing the Boundaries between Lewis-Basic and Redox Behavior of a Parent Borylene.

The parent borylene (CAAC)(Me3 P)BH, 1 (CAAC=cyclic alkyl(amino)carbene), acts both as a Lewis base and one-electron reducing agent towards group 13 trichlorides (ECl3 , E=B, Al, Ga, In), yielding the adducts 1-ECl3 and increasing proportions of the radical cation [1]•+ for the heavier group 13 analogues. With boron trihalides (BX3 , X=F, Cl, Br, I) 1 undergoes sequential adduct formation and halide abstraction reactions to yield borylboronium cations and shows an increasing tendency towards redox processes for the heavier halides. Calculations confirm that 1 acts as a strong Lewis base towards EX3 and show a marked increase in the B-E bond dissociation energies down both group 13 and the halide group.

Selective Route to Stable Silicon-Boron Radicals and Their Corresponding Cations.

Herein, we report on a facile and selective one-pot synthetic route to silicon-boron radicals. Reduction of Br2BTip (Tip = 2,4,6-iPrC6H2) with KC8 in the presence of LSi-R affords LSi(tBu)-B(Br)Tip (1) and LSi(N(TMS)2)-B(Br)Tip (2) [L = PhC(NtBu)2]. These first examples of silicon-boron isolated radical species feature spin density on the silicon and boron atoms. 1 and 2 exhibit extraordinary stability to high temperatures under inert conditions in solution and air stability in the solid state. Both radicals have been isolated and fully characterized by electron paramagnetic resonance spectroscopy, SQUID magnetometry, mass spectrometry, cyclic voltammetry, single-crystal X-ray structure analysis, and density functional theory calculations. Moreover, compound 1 exhibits one-electron transfer when treated with 1 equiv of AgSO3CF3 and [Ph3C]+[B(C6F5)4]-, respectively, resulting in the corresponding cations [LSi(tBu)-B(Br)Tip]+[CF3SO3]- (3) and [LSi(tBu)-B(Br)Tip]+[B(C6F5)4]- (4). Compounds 3 and 4 have been characterized with multinuclear NMR and mass spectrometry.

A Stable N-Heterocyclic Silylene with a 1,1'-Ferrocenediyl Backbone.

The N-heterocyclic silylene [{Fe(η5 -C5 H4 -NDipp)2 }Si] (1DippSi, Dipp=2,6-diisopropylphenyl) shows an excellent combination of pronounced thermal stability and high reactivity towards small molecules. It reacts readily with CO2 and N2 O, respectively affording (1DippSiO2 )2 C and (1DippSiO)2 as follow-up products of the silanone 1DippSiO. Its reactions with H2 O, NH3 , and FcPH2 (Fc=ferrocenyl) furnish the respective oxidative addition products 1DippSi(H)X (X=OH, NH2 , PHFc). Its reaction with H3 BNH3 unexpectedly results in B-H, instead of N-H, bond activation, affording 1DippSi(H)(BH2 NH3 ). DFT results suggest that dramatically different mechanisms are operative for these H-X insertions.

Examination of Protonation-Induced Dinitrogen Splitting by in Situ EXAFS Spectroscopy.

The splitting of dinitrogen into nitride complexes emerged as a key reaction for nitrogen fixation strategies at ambient conditions. However, the impact of auxiliary ligands or accessible spin states on the thermodynamics and kinetics of N-N cleavage is yet to be examined in detail. We recently reported N-N bond splitting of a {Mo(µ2:η1:η1-N2)Mo}-complex upon protonation of the diphosphinoamide auxiliary ligands. The reactivity was associated with a low-spin to high-spin transition that was induced by the protonation reaction in the coordination periphery, mainly based on computational results. Here, this proposal is evaluated by an XAS study of a series of linearly N2 bridged Mo pincer complexes. Structural characterization of the transient protonation product by EXAFS spectroscopy confirms the proposed spin transition prior to N-N bond cleavage.

Disilane Cleavage with Selected Alkali and Alkaline Earth Metal Salts.

The industry-scale production of methylchloromonosilanes in the Müller-Rochow Direct Process is accompanied by the formation of a residue, the direct process residue (DPR), comprised of disilanes Men Si2 Cl6-n (n=1-6). Great research efforts have been devoted to the recycling of these disilanes into monosilanes to allow reintroduction into the siloxane production chain. In this work, disilane cleavage by using alkali and alkaline earth metal salts is reported. The reaction with metal hydrides, in particular lithium hydride (LiH), leads to efficient reduction of chlorine containing disilanes but also induces disproportionation into mono- and oligosilanes. Alkali and alkaline earth chlorides, formed in the course of the reduction, specifically induce disproportionation of highly chlorinated disilanes, whereas highly methylated disilanes (n>3) remain unreacted. Nearly quantitative DPR conversion into monosilanes was achieved by using concentrated HCl/ether solutions in the presence of lithium chloride.

Synthesis of Functional Monosilanes by Disilane Cleavage with Phosphonium Chlorides.

The Müller-Rochow direct process (DP) for the large-scale production of methylchlorosilanes Men SiCl4-n (n=1-3) generates a disilane residue (Men Si2 Cl6-n , n=1-6, DPR) in thousands of tons annually. This report is on methylchlorodisilane cleavage reactions with use of phosphonium chlorides as the cleavage catalysts and reaction partners to preferably obtain bifunctional monosilanes Mex SiHy Clz (x=2, y=z=1; x,y=1, z=2; x=z=1, y=2). Product formation is controlled by the reaction temperature, the amount of phosphonium chloride employed, the choice of substituents at the phosphorus atom, and optionally by the presence of hydrogen chloride, dissolved in ethers, in the reaction mixture. Replacement of chloro by hydrido substituents at the disilane backbone strongly increases the overall efficiency of disilane cleavage, which allows nearly quantitative silane monomer formation under comparably moderate conditions. This efficient workup of the DPR thus not only increases the economic value of the DP, but also minimizes environmental pollution.

Making Use of the Direct Process Residue: Synthesis of Bifunctional Monosilanes.

The industrial production of monosilanes Men SiCl4-n (n=1-3) through the Müller-Rochow Direct Process generates disilanes Men Si2 Cl6-n (n=2-6) as unwanted byproducts ("Direct Process Residue", DPR) by the thousands of tons annually, large quantities of which are usually disposed of by incineration. Herein we report a surprisingly facile and highly effective protocol for conversion of the DPR: hydrogenation with complex metal hydrides followed by Si-Si bond cleavage with HCl/ether solutions gives (mostly bifunctional) monosilanes in excellent yields. Competing side reactions are efficiently suppressed by the appropriate choice of reaction conditions.

Reductive Nitric Oxide Coupling at a Dinickel Core: Isolation of a Key cis-Hyponitrite Intermediate en route to N2 O Formation.

Reductive coupling of nitric oxide (NO) to give N2 O is an important reaction in the global nitrogen cycle. Here, a dinickel(II) dihydride complex 1 that releases H2 upon substrate binding and serves as a masked dinickel(I) scaffold is shown to reductively couple two molecules of NO within the bimetallic cleft. The resulting hyponitrite complex 2 features an unprecedented cis-[N2 O2 ]2- binding mode that has been computationally proposed as a key intermediate in flavodiiron nitric oxide reductases (FNORs). NMR and DFT evidence indicate facile rotational fluxionality of the [N2 O2 ]2- unit, which allows to access an isomer that is prone to N2 O release. Protonation of 2 is now found to trigger rapid N2 O evolution and formation of a hydroxido bridged complex, reminiscent of FNOR reactivity. This work provides fundamental insight into the biologically relevant reductive coupling of two NO molecules and the subsequent trajectory towards N2 O formation at bimetallic sites.

A Terminal Iridium Oxo Complex with a Triplet Ground State.

A terminal iridium oxo complex with an open-shell (S=1) ground state was isolated upon hydrogen atom transfer (HAT) from the respective iridium(II) hydroxide. Electronic structure examinations support large spin delocalization to the oxygen atom. Selected oxo transfer reactions indicate the ambiphilic reactivity of the iridium oxo moiety. Calorimetric and computational examinations of the HAT revealed a bond dissociation free energy for the IrO-H bond that is sufficient for hydrogen atom abstraction towards C-H bonds and small contributions from entropy and spin-orbit coupling to the HAT thermochemistry.

Intercepting the Disilene-Silylsilylene Equilibrium.

The equilibrium between disilenes (R2 Si=SiR2 ) and their silylsilylene (R3 Si-SiR) isomers has previously been inferred but not directly observed, except in the case of the parent system H2 Si=SiH2 . Here, we report a new method to prepare base-coordinated disilenes with hydride substituents. By varying the bulk of the coordinating base and other silicon substituents, we have been able to control the rearrangement of disilene adducts to their silylsilylene tautomers. Remarkably, 1,2 migration of a trimethylsilyl group is preferred over hydrogen migration. A DFT study of the reaction mechanism provides a rationale for the observed reactivity and detailed information on the bonding situation in base-stabilized disilenes.

Oxidative Coupling of Terminal Rhenium Pnictide Complexes.

The isolation of rhenium(V) complexes with terminal phosphide and arsenide ligands was achieved upon decarbonylation of rhenium(III) pnictaethynolates. One-electron oxidation of the pnictide complexes yielded Pn-Pn (Pn=P, As) coupling products, which were spectroscopically and crystallographically characterized. Computational bond analysis suggests that these complexes are best described as {Pn2 }0 complexes that are stabilized by donor-acceptor interactions with the metal and a pyrazole ligand.