Trans‐selective insertional dihydroboration of a cis‐diborene: synthesis of linear sp3‐sp2‐sp3‐triboranes and subsequent cationization

The reaction of aryl‐ and amino(dihydro)boranes with dibora[2]ferrocenophane 1 leads to the formation 1,3‐trans‐dihydrotriboranes by formal hydrogenation and insertion of a borylene unit into the B=B bond. The aryltriborane derivatives undergo reversible photoisomerization to the cis‐1,2-μ‐H‐3hydrotriboranes, while hydride abstraction affords cationic triboranes, which represent the first doubly base‐stabilized B3H4+ analogues

Palladium Catalysts for Dehydrogenation of Ammonia Borane with Preferential B−H Activation

Cationic Pd(II) complexes catalyzed the dehydrogenation of ammonia borane in the most efficient manner with the release of 2.0 equiv of H_2 in less than 60 s at 25 °C. Most of the hydrogen atoms were obtained from the boron atom of the ammonia borane. The first step of the dehydrogenation reaction was elaborated using density functional theory calculations

Unsymmetrical, cyclic diborenes and thermal rearrangement to a borylborylene

Cyclic diboranes(4) based on a chelating monoanionic benzylphosphine linker were prepared by boron-silicon exchange between arylsilanes and B2Br4. Coordination of Lewis bases to the remaining sp2 boron atom yielded unsymmetrical sp3-sp3 diboranes, which were reduced with KC8 to their corresponding trans-diborenes. These compounds were studied by a combination of spectroscopic methods, X-ray diffraction and DFT calculations. PMe3-stabilized diborene 6 was found to undergo thermal rearrangement to gem-diborene 8. DFT calculations on 8 reveal a polar boron-boron bond, and indicate that the compound is best described as a borylborylene

Facile synthesis of a stable dihydroboryl {BH2}– anion

While the one-electron reduction of (CAACMe)BH2Br (CAACMe = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) yields a hydride-shift isomer of the corresponding tetrahydrodiborane, a further reversible reduction leads to the first stable parent boryl anion, [(CAACMe)BH2]–, which acts as a powerful boron nucleophile

CO2 reduction with protons and electrons at a boron-based reaction center.

Borohydrides are widely used reducing agents in chemical synthesis and have emerging energy applications as hydrogen storage materials and reagents for the reduction of CO2. Unfortunately, the high energy cost associated with the multistep preparation of borohydrides starting from alkali metals precludes large scale implementation of these latter uses. One potential solution to this issue is the direct synthesis of borohydrides from the protonation of reduced boron compounds. We herein report reactions of the redox series [Au(B2P2)] n (n = +1, 0, -1) (B2P2, 9,10-bis(2-(diisopropylphosphino)phenyl)-9,10-dihydroboranthrene) and their conversion into corresponding mono- and diborohydride complexes. Crucially, the monoborohydride can be accessed via protonation of [Au(B2P2)]-, a masked borane dianion equivalent accessible at relatively mild potentials (-2.05 V vs. Fc/Fc+). This species reduces CO2 to produce the corresponding formate complex. Cleavage of the formate complex can be achieved by reduction (ca. -1.7 V vs. Fc/Fc+) or by the addition of electrophiles including H+. Additionally, direct reaction of [Au(B2P2)]- with CO2 results in reductive disproportion to release CO and generate a carbonate complex. Together, these reactions constitute a synthetic cycle for CO2 reduction at a boron-based reaction center that proceeds through a B-H unit generated via protonation of a reduced borane with weak organic acids

Vibrational branching ratios and hyperfine structure of 11^{11}BH and its suitability for laser cooling

The simple structure of the BH molecule makes it an excellent candidate for direct laser cooling. We measure the branching ratios for the decay of the ${\rm A}^{1}\Pi (v'=0)$ state to vibrational levels of the ground state, ${\rm X}^{1}\Sigma^{+}$, and find that they are exceedingly favourable for laser cooling. We verify that the branching ratio for the spin-forbidden transition to the intermediate ${\rm a}^{3}\Pi$ state is inconsequentially small. We measure the frequency of the lowest rotational transition of the X state, and the hyperfine structure in the relevant levels of both the X and A states, and determine the nuclear electric quadrupole and magnetic dipole coupling constants. Our results show that, with a relatively simple laser cooling scheme, a Zeeman slower and magneto-optical trap can be used to cool, slow and trap BH molecules.Comment: 7 pages, 5 figures. Updated analysis of A state hyperfine structure and other minor revision

Formation of N-heterocyclic, donor-stabilized borenium ions

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.Cationic and zwitterionic boryl bromide species and a borenium–boryl bromide cation have been synthesised which represent new N-donor stabilised cationic boron compounds with β-diketiminate ligands. The unexpected borenium–boryl bromide results from a head-to-tail dimerisation of the corresponding zwitterionic boryl bromide accompanied by proton migration. The electronic nature of these new species was studied by DFT calculations

Quadruple bonding between iron and boron in the BFe(CO)3- complex.

While main group elements have four valence orbitals accessible for bonding, quadruple bonding to main group elements is extremely rare. Here we report that main group element boron is able to form quadruple bonding interactions with iron in the BFe(CO)3- anion complex, which has been revealed by quantum chemical investigation and identified by mass-selected infrared photodissociation spectroscopy in the gas phase. The complex is characterized to have a B-Fe(CO)3- structure of C3v symmetry and features a B-Fe bond distance that is much shorter than that expected for a triple bond. Various chemical bonding analyses indicate that the complex involves unprecedented B≣Fe quadruple bonding interactions. Besides the common one electron-sharing σ bond and two Fe→B dative π bonds, there is an additional weak B→Fe dative σ bonding interaction. This finding of the new quadruple bonding indicates that there might exist a wide range of boron-metal complexes that contain such high multiplicity of chemical bonds

Bond Length - Bond Valence Relationships for Carbon - Carbon and Carbon - Oxygen Bonds

In the present study, relationships are developed for determining bond orders (also referred to as bond valences or bond numbers) from published bond lengths for carbon-carbon (C-C) and carbon-oxygen (C-O) bonds. The relationships are based on Pauling’s empirical formula s = exp((Ro-R)/b)), where s is the bond order, R is the corresponding bond length, Ro is the unit valence bond length, and b is a fitting parameter. We use a recently derived relationship for the b parameter in terms of the bonding atoms’ published atomic orbital exponents. The resulting equations were checked against published x-ray diffraction (XRD) data for 176 carbon systems with 540 published C-C bond lengths, and 50 oxygen systems having 72 published C-O bond lengths. The C-C and C-O bond length-valence relationships are shown to have sufficient applicability and accuracy for use in any bonding environment, regardless of physical state or oxidation number

Trimetallaborides as starting points for the syntheses of large metal-rich molecular borides and clusters

Treatment of an anionic dimanganaborylene complex ([{Cp(CO)2Mn}2B]–) with coinage metal cations stabilized by a very weakly coordinating Lewis base (SMe2) led to the coordination of the incoming metal and subsequent displacement of dimethylsulfide in the formation of hexametalladiborides featuring planar four-membered M2B2 cores (M = Cu, Au) comparable to transition metal clusters constructed around four-membered rings composed solely of coinage metals. The analogies between compounds consisting of B2M2 units and M4 (M = Cu, Au) units speak to the often overlooked metalloid nature of boron. Treatment of one of these compounds (M = Cu) with a Lewis-basic metal fragment (Pt(PCy3)2) led to the formation of a tetrametallaboride featuring two manganese, one copper and one platinum atom, all bound to boron in a geometry not yet seen for this kind of compound. Computational examination suggests that this geometry is the result of d10-d10 dispersion interactions between the copper and platinum fragments