Direct Spectroscopic Identification of BN-Arynes and Subtle Steric Effects on Nitrogen Fixation.

1,2-Azaborinines are the BN analogues of arynes through exchange of the formal CC triple bond by an isoelectronic BN bond. The BN-arynes are an underexplored class of reactive intermediates. Dibenzo[c,e][1,2]azaborinine (10,9-BN-phenanthryne) 1 was inferred as reactive intermediate by trapping reactions. Here it is shown that 1 can be generated in the gas phase by thermolysis from the pyridine adduct of 9-azido-9-borafluorene by cleavage of the dative bond with pyridine and dinitrogen extrusion. The ionization potential of 1 is 8.2 eV with ionization resulting from the π HOMO. Under cryogenic matrix isolation conditions, 9-azido-9-borafluorene photolysis results in isomerization to the dinitrogen adduct of 1 without involvement of a triplet borylnitrene intermediate. Photochemical nitrogen extrusion from 1 ⋅ N2 is not possible and nitrogen fixation is irreversible under cryogenic conditions. In contrast, 2,4,7,9-tetra-tert-butyldibenzo[c,e][1,2]azaborinine can be photogenerated from the corresponding azidoborole precursor under cryogenic matrix isolation conditions, and nitrogen fixation is precluded due to steric hindrance. The BN stretching vibration at about 1750 cm-1 is much weaker than in typical linear diaryl iminoboranes.

trans-Hydroalkynylation of Internal 1,3-Enynes Enabled by Cooperative Catalysis.

A cooperative catalyst system involving a Pd(0)/Senphos complex, tris(pentafluorophenyl)borane, copper bromide, and an amine base, is demonstrated to catalyze trans-hydroalkynylation of internal 1,3-enynes. For the first time, a Lewis acid catalyst is shown to promote the reaction involving the emerging outer-sphere oxidative reaction step. The resulting cross-conjugated dieneynes are versatile synthons for organic synthesis, and their characterization reveals distinct photophysical properties depending on the positioning of the donor/acceptor substituents along the conjugation path.

Mechanism of Pd/Senphos-Catalyzed trans-Hydroboration of 1,3-Enynes: Experimental and Computational Evidence in Support of the Unusual Outer-Sphere Oxidative Addition Pathway.

The reaction mechanism of the Pd/Senphos-catalyzed trans-hydroboration reaction of 1,3-enynes was investigated using various experimental techniques, including deuterium and double crossover labeling experiments, X-ray crystallographic characterization of model reaction intermediates, and reaction progress kinetic analysis. Our experimental data are in support of an unusual outer-sphere oxidative addition mechanism where the catecholborane serves as a suitable electrophile to activate the Pd0-bound 1,3-enyne substrate to form a Pd-η3-π-allyl species, which has been determined to be the likely resting state of the catalytic cycle. Double crossover labeling of the catecholborane points toward a second role played by the borane as a hydride delivery shuttle. Density functional theory calculations reveal that the rate-limiting transition state of the reaction is the hydride abstraction by the catecholborane shuttle, which is consistent with the experimentally determined rate law: rate = k[enyne]0[borane]1[catalyst]1. The computed activation free energy ΔG‡ = 17.7 kcal/mol and KIE (kH/kD = 1.3) are also in line with experimental observations. Overall, this work experimentally establishes Lewis acids such as catecholborane as viable electrophilic activators to engage in an outer-sphere oxidative addition reaction and points toward this underutilized mechanism as a general approach to activate unsaturated substrates.

C-Boron Enolates Enable Palladium Catalyzed Carboboration of Internal 1,3-Enynes.

A new family of carbon-bound boron enolates, generated by a kinetically controlled halogen exchange between chlorocatecholborane and silylketene acetals, is described. These C-boron enolates are demonstrated to activate 1,3-enyne substrates in the presence of a Pd0 /Senphos ligand complex, resulting in the first examples of a carboboration reaction of an alkyne with enolate-equivalent nucleophiles. Highly substituted dienyl boron building blocks are produced in excellent site-, regio-, and diastereoselectivity by the described catalytic cis-carboboration reaction.

A BN-Doped Cycloparaphenylene Debuts.

The first example of a BN-doped cycloparaphenylene BN-[10]CPP was synthesized and characterized. Its reactivity and photophysical properties were evaluated in direct comparison to its carbonaceous analogues Mes-[10]CPP and [10]CPP. While the photophysical properties of BN-[10]CPP remains similar to its carbonaceous analogues, the electronic structure changes associated with the introduction of a 1,2-azaborine BN heterocycle into a CPP scaffold enables facile and selective late-stage functionalizations that cannot be accomplished with carbonaceous CPPs. Specifically, Ir-catalyzed hydrogenation of BN-[10]CPP selectively reduces the BN heterocyclic ring, which upon hydrolysis produces a rare example of a macrocyclic paraphenylene 6 incorporating the versatile ketone functionality within the macrocyclic ring.

Effect of π-System Extension on the Ionization Energy of the Planar Blatter Radical: Experimental and Theoretical Studies.

Fusion of benzene, naphthalene, and phenalene rings with the D ring of the planar Blatter radical leads to extension of the π-system and increased spin delocalization. The effect of this π-extension and the position of the ring fusion on the electronic structure of the radicals was investigated by UV-photoelectron spectroscopy and DFT CAM-B3LYP/6-311G(d,p) method. The experimental data obtained for 3 out of 8 derivatives were correlated with DFT-derived ionization energies.

UV-photoelectron spectroscopy of stable radicals: the electronic structure of planar Blatter radicals as materials for organic electronics.

The electronic structure of Blatter radicals and a series of C(10)-substituted derivatives of 2-phenyl-3H-[1,2,4]triazino[5,6,1-kl]phenoxazin-3-yl (planar Blatter radicals) containing H, F, Cl, Br, CN, CF3 and OMe substituents was investigated by gas phase UV-photoelectron spectroscopy. The energy of the SOMO of the radicals, determined to be about 6.5 eV, was correlated with their electrochemical oxidation potentials, E0/+11/2, relative to the Fc/Fc+ couple in CH2Cl2 giving the correction of 6.60(1) eV. The optical band gap Eoptg ∼ 1.7 eV of the radicals yielded the electronic transport gap, Eelg, of about 2.1 eV, which is similar to the electronic parameters of pentacene. The radicals were analyzed by EPR spectroscopy and single crystal XRD methods, and all experimental data were compared to DFT computational results obtained at the CAM-B3LYP/6-311G(d,p) level of theory.

Cation-π binding ability of BN indole.

A BN indole-containing aromatic scaffold has been synthesized and the cation-π binding ability characterized by nuclear magnetic resonance (NMR) monitored titrations. The resulting chemical shifts were analyzed using a non-linear curve fitting procedure and the extracted association constants (Ka's) compared with the natural indole scaffold. Computations were also performed to support our findings. This work shows that incorporation of a B-N bond in place of a C-C bond in an aromatic system slightly lowers the cation-π binding ability of the arene's π-system with simple cations.

Syntheses and structures of benzo-bis(1,3,2-diazaboroles) and acenaphtho-1,3,2-diazaboroles.

Colorless crystalline 2,6-dibromo-4,8-dimethyl-1,3,5,7-tetraphenylbenzobis(diazaborole) 4 resulted from the cyclocondensation of 3,6-dimethyl-1,2,4,5-tetraphenylaminobenzene 3d with two equivalents of boron tribromide in the presence of calcium hydride. Synthesis of the dark-red crystalline 2-bromo-N,N'-bis(diisopropylphenyl)acenaphtho-1,3,2-diazaborole 7 was effected by the cyclocondensation of 1,2-bis(N-2',6'-diisopropylphenylimino)acenaphthene (5) and boron tribromide with subsequent sodium amalgam reduction of the initially formed burgundy red diazaborolium salt 6. Compounds 4, 6 and 7 are characterised by elemental analyses, 1H, 11B and 13C NMR spectroscopy, as well as by single X-ray diffraction studies. The electronic structures of 4, 6 and 7 are subject to DFT calculations.

Spectroscopic Studies on Hydrazine-Boranes, Key Compounds for Chemical Hydrogen Storage.

Hydrazine-boranes (H2NNH2·BH3 and H3B·NH2NH2·BH3) have been proposed for the storage of hydrogen, but these compounds have not created scope for extensive research works as ammonia- and methylamine-boranes have made these last decades. In the exciting research devoted to energy storage with environmentally friendly processes, hydrazine-borane, hydrazine-bisborane, and their simply substituted derivatives could provide a satisfactory response for hydrogen production and recyclability of the formed products. To date, knowledge of the physical and chemical properties of these compounds is still scarce. In this paper, the electronic structure of various hydrazine-boranes complexes is studied by ultraviolet-photoelectron spectroscopy (UV-PES), which is the experimental technique giving direct access to the energy of occupied molecular orbitals. Thus, UV-PE spectra were registered and first ionization energies were determined. Understanding of different types of interactions between nitrogen lone pairs and their variations by complexation has been our essential goal in these studies. In particular, clear stabilization of all molecular orbital energies is noted when complexation with borane takes place. Evolution of the σBN bond during the hydrogen release process upon thermal activation has also been studied experimentally by UV-PES and supported by quantum chemical calculations.

A BN anthracene mimics the electronic structure of more highly conjugated systems.

9a,9-BN anthracene was synthesized using a simple three-step sequence involving intramolecular electrophilic borylation of 2-benzylpyridines. The same procedure can be applied to yield a number of substituted 9a,9-BN anthracenes. Spectroscopic characterization of the parental compound (UV-photoelectron spectroscopy, UV-vis absorption/emission) shows an electronic structure more similar to that of a larger conjugated system rather than anthracene, the direct all-carbon analogue.

Isoselenocyanates versus Isothiocyanates and Isocyanates.

Alkyl and aryl isoselenocyanates are well known intermediates in the synthesis of various organoselenium compounds, but the knowledge of the physicochemical properties of simple unsaturated derivatives is still fragmentary. Vinyl-, 2-propenyl-, and cyclopropyl isoselenocyanates have been prepared by reaction of selenium in powder with the corresponding isocyanides. The isoselenocyanates of this series, with a variable distance between the N═C═Se group and the unsaturated or pseudounsaturated group, have been studied by UV-photoelectron spectroscopy and quantum-chemical calculations. For each of these three isoselenocyanates, the exploration of conformers and geometrical optimization always converge toward only one local minimum. The vinyl and cyclopropyl derivatives are characterized by similar order of magnitude of interactions between the NCSe group and the substituent, while for allylic compound two noninteracting moieties should be considered. The same conclusions were obtained for vinylic and cyclopropylic sulfur and oxygen derivatives. Thus the type and extent of interactions between the N═C═X (X = O, S, Se) group and an unsaturated (vinyl, allyl, or cyclopropyl) moiety are now clarified.

Electronic structure of BN-aromatics: Choice of reliable computational tools.

The importance of having reliable calculation tools to interpret and predict the electronic properties of BN-aromatics is directly linked to the growing interest for these very promising new systems in the field of materials science, biomedical research, or energy sustainability. Ionization energy (IE) is one of the most important parameters to approach the electronic structure of molecules. It can be theoretically estimated, but in order to evaluate their persistence and propose the most reliable tools for the evaluation of different electronic properties of existent or only imagined BN-containing compounds, we took as reference experimental values of ionization energies provided by ultra-violet photoelectron spectroscopy (UV-PES) in gas phase-the only technique giving access to the energy levels of filled molecular orbitals. Thus, a set of 21 aromatic molecules containing B-N bonds and B-N-B patterns has been merged for a comparison between experimental IEs obtained by UV-PES and various theoretical approaches for their estimation. Time-Dependent Density Functional Theory (TD-DFT) methods using B3LYP and long-range corrected CAM-B3LYP functionals are used, combined with the ΔSCF approach, and compared with electron propagator theory such as outer valence Green's function (OVGF, P3) and symmetry adapted cluster-configuration interaction ab initio methods. Direct Kohn-Sham estimation and "corrected" Kohn-Sham estimation are also given. The deviation between experimental and theoretical values is computed for each molecule, and a statistical study is performed over the average and the root mean square for the whole set and sub-sets of molecules. It is shown that (i) ΔSCF+TDDFT(CAM-B3LYP), OVGF, and P3 are the most efficient way for a good agreement with UV-PES values, (ii) a CAM-B3LYP range-separated hybrid functional is significantly better than B3LYP for the purpose, especially for extended conjugated systems, and (iii) the "corrected" Kohn-Sham result is a fast and simple way to predict IEs.

The Least Stable Isomer of BN Naphthalene: Toward Predictive Trends for the Optoelectronic Properties of BN Acenes.

The least stable isomer of the parental BN naphthalene series has been synthesized in a simple four-step sequence. Its experimental electronic structure characterization via UV-PES, cyclic voltammetry, and UV-vis spectroscopy in direct comparison with three other known BN naphthalene isomers has established two guiding principles for predicting the electronic structures of BN acene compounds: (1) Orientational BN isomers have similar HOMO-LUMO gaps. (2) For each pair of orientational BN isomers, the more thermodynamically stable compound has the lower HOMO energy. Furthermore, we demonstrate that BN/CC isosterism in the context of BN-9,1-Naph can impact crystal packing to favor a cofacial π-stack motif.

A Benefit of Using the IDSCRF- over UFF-Radii Cavities and Why Joint Correlations of NMR Chemical Shifts Can Be Advantageous: Condensed Pyridines as an IEF-PCM/GIAO/DFT Case Study.

Herein, an advantage of the use of IDSCRF- over UFF-radii-based solute cavities in GIAO/DFT calculations is presented for the 13C and especially 15N NMR chemical shifts made for several bicyclic aromatic nitrogen heterocycles in CDCl3 solution treated within the classical IEF-PCM solvation scheme. Successful application of the IDSCRF-radii in the non 1:1 joint multinuclear 1H/13C and particularly 1H/13C/15N correlations of the measured δH,C(,N) values to those obtained theoretically is also documented for a series of test systems (-268 ≤ δN ≤ -72 ppm). The experimentally yet unknown δN's were found in this way for the title compounds via a trinuclear eq 1 determined for an optimally chosen value of the multiplication factor of initial raw δH data (mH = 10). Such a simultaneous analysis of the δH,C(,N) data is proposed as a novel method to study the solution structure of the other similar conformationally homogeneous (bio)organic compounds. The issue of small spurious imaginary vibrational frequencies computed for a few molecular systems using the Gaussian 09 default UFF-radii is briefly considered as well.

The Electronic Structure of Some Cyanohydrins-A†Spectroscopically Under-Investigated Family of Compounds.

Cyanohydrins are usually formed by addition of hydrogen cyanide to aldehydes or ketones while the elimination of HCN from cyanohydrins is easily observed upon heating. The low thermal stability of these highly boiling compounds leads to difficult studies in the gas phase where partial or complete decomposition is usually observed. Consequently, the reported physicochemical properties of such compounds in the gas phase are still scarce. Keeping with this, four simple cyanohydrins, the glycolonitrile and methyl, vinyl and ethynyl derivatives, have been selected. These are possible candidates for the Interstellar Medium, where the corresponding aldehydes and HCN have been detected, and could have played an important role in prebiotic chemistry, as already proposed for some of them. Three well-suited spectroscopic techniques, namely, UV photoelectron, infrared, and Raman spectroscopies, in tandem with quantum calculations, have been chosen for the structure analysis. Photoelectron spectroscopy, successfully performed with gaseous compounds, provides the first comparative study on cyanohydrins in the gas phase.

Two BN isosteres of anthracene: synthesis and characterization.

The synthesis of two parental BN anthracenes, 1 and 2, was developed, and their electronic structure and reactivity behavior were characterized in direct comparison with all-carbon anthracene. Gas-phase UV-photoelecton spectroscopy studies revealed the following HOMO energy trend: anthracene, -7.4 eV; BN anthracene 1, -7.7 eV; bis-BN anthracene 2, -8.0 eV. The λmax of the lower energy band in the UV-vis absorption spectrum is as follows: anthracene, 356 nm; BN anthracene 1, 359 nm; bis-BN anthracene 2, 357 nm. Thus, although the HOMO is stabilized with increasing BN incorporation, the HOMO-LUMO band gap remains unchanged across the anthracene series. The emission λmax values for the three investigated anthracene compounds are at 403 nm. The pKa values of the N-H proton for BN anthracene 1 and bis-BN anthracene 2 were determined to be approximately 26. BN anthracenes 1 and 2 do not undergo heat- or light-induced cycloaddition reactions or Friedel-Crafts acylations. Electrophilic bromination of BN anthracene 1 with Br2, however, occurs regioselectively at the 9-position. The reactivity behavior and regioselectivity of bromination of BN anthracenes are consistent with the electronic structure of these compounds; i.e., (1) the lower HOMO energy levels for BN anthracenes stabilize the molecules against cycloaddition and Friedel-Crafts reactions, and (2) the HOMO orbital coefficients are consistent with the observed bromination regioselectivity. Overall, this work demonstrates that BN/CC isosterism can be used as a molecular design strategy to stabilize the HOMO of acene-type structures while the optical band gap is maintained.

UV-photoelectron spectroscopy of BN indoles: experimental and computational electronic structure analysis.

We present a comprehensive electronic structure analysis of two BN isosteres of indole using a combined UV-photoelectron spectroscopy (UV-PES)/computational chemistry approach. Gas-phase He I photoelectron spectra of external BN indole I and fused BN indole II have been recorded, assessed by density functional theory calculations, and compared with natural indole. The first ionization energies of these indoles are natural indole (7.9 eV), external BN indole I (7.9 eV), and fused BN indole II (8.05 eV). The computationally determined molecular dipole moments are in the order: natural indole (2.177 D) > fused BN indole II (1.512 D) > external BN indole I (0.543 D). The λmax in the UV-vis absorption spectra are in the order: fused BN indole II (292 nm) > external BN indole I (282 nm) > natural indole (270 nm). The observed relative electrophilic aromatic substitution reactivity of the investigated indoles with dimethyliminium chloride as the electrophile is as follows: fused BN indole II > natural indole > external BN indole I, and this trend correlates with the π-orbital coefficient at the 3-position. Nucleus-independent chemical shifts calculations show that the introduction of boron into an aromatic 6π-electron system leads to a reduction in aromaticity, presumably due to a stronger bond localization. Trends and conclusions from BN isosteres of simple monocyclic aromatic systems such as benzene and toluene are not necessarily translated to the bicyclic indole core. Thus, electronic structure consequences resulting from BN/CC isosterism will need to be evaluated individually from system to system.

New reactions of N-tert-butylimines; formation of N-heterocycles by methyl radical elimination on flash vacuum thermolysis of N-benzylidene- and N-(2-pyridylmethylidene)-tert-butylamines.

Thermal reactions of N-benzylidene- and N-(2-pyridylmethylidene)-tert-butylamines (5 and 13) under FVT conditions have been investigated. Unexpectedly, at 800 °C, compound 5 yields 1,2-dimethylindole and 3-methylisoquinoline. In the reaction of 13 at 800 °C, 3-methylimidazo[1,5-a]pyridine was obtained as the major product. Mechanisms of these reactions have been proposed on the basis of DFT calculations. Furthermore, UV-photoelectron spectroscopy combined with FVT has been applied for direct monitoring and characterization of the thermolysis products in situ.

Methyliminopropadienone CH3-N═C═C═C═O: photoelectron spectrum and electronic structure.

N-Methyliminopropadienone MeN═C═C═C═O 1a was generated by flash vacuum thermolysis of three 5-(aminomethylene)-1,3-dioxane-4,6-diones (Meldrum's acid derivatives). Online monitoring of the reactions permitted the recording of the UV-photoelectron spectra and the determination of the first two ionization energies of 1a as 9.0 and 12.4 eV. The first ionization energy (and the calculated highest occupied molecular orbital energy) of 1a are more comparable with those of N-methylketenimine than with ketene. In contrast, the calculated lowest unoccupied molecular orbital energy is significantly lower than those of both ketene and N-methylketenimine, thereby making iminopropadienones powerful electrophiles. Calculated charge densities indicate that electrophiles should attack at C3 or O and nucleophiles at C2 or C4 in broad agreement with experimental observations.