Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 119
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
Nat Chem ; 2020 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-32929247

RESUMO

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.

2.
Chem Asian J ; 2020 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-32207211

RESUMO

We present herein an in-depth study of complexes in which a molecule containing a boron-boron triple bond is bound to tellurate cations. The analysis allows the description of these salts as true π complexes between the B-B triple bond and the tellurium center. These complexes thus extend the well-known Dewar-Chatt-Duncanson model of bonding to compounds made up solely of p block elements. Structural, spectroscopic and computational evidence is offered to argue that a set of recently reported heterocycles consisting of phenyltellurium cations complexed to diborynes bear all the hallmarks of π-complexes in the π-complex/metallacycle continuum envisioned by Joseph Chatt. Described as such, these compounds are unique in representing the extreme of a metal-free continuum with conventional unsaturated three-membered rings (cyclopropenes, azirenes, borirenes) occupying the opposite end.

3.
Angew Chem Int Ed Engl ; 59(14): 5531-5535, 2020 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-31840333

RESUMO

Herein we present the first solid-state structures of tetraiododiborane(4) (B2 I4 ), which was long believed to exist in all phases as discrete molecules with planar, tricoordinate boron atoms, like the lighter tetrahalodiboranes(4) B2 F4 , B2 Cl4 , and B2 Br4 . Single-crystal X-ray diffraction, solid-state NMR, and IR measurements indicate that B2 I4 in fact exists as two different polymeric forms in the solid state, both of which feature boron atoms in tetrahedral environments. DFT calculations are used to simulate the IR spectra of the solution and solid-state structures, and these are compared with the experimental spectra.

4.
Chemistry ; 2019 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-31663648

RESUMO

The reactivity of a diruthenium tetrahydride complex towards three selected dihydroboranes was investigated. The use of [DurBH2 ] (Dur=2,3,5,6-Me4 C6 H) and [(Me3 Si)2 NBH2 ] led to the formation of bridging borylene complexes of the form [(Cp*RuH)2 BR] (Cp*=C5 Me5 ; 1 a: R=Dur; 1 b: R=N(SiMe3 )2 ) through oxidative addition of the B-H bonds with concomitant hydrogen liberation. Employing the more electron-deficient dihydroborane [3,5-(CF3 )2 -C6 H3 BH2 ] led to the formation of an anionic complex bearing a tetraarylated chain of four boron atoms, namely Li(THF)4 [(Cp*Ru)2 B4 H5 (3,5-(CF3 )2 C6 H3 )4 ] (4), through an unusual, incomplete threefold dehydrocoupling process. A comparative theoretical investigation of the bonding in a simplified model of 4 and the analogous complex nido-[1,2(Cp*Ru)2 (µ-H)B4 H9 ] (I) indicates that there appear to be no classical σ-bonds between the boron atoms in complex I, whereas in the case of 4 the B4 chain better resembles a network of three B-B σ bonds, the central bond being significantly weaker than the other two.

5.
Artigo em Inglês | MEDLINE | ID: mdl-31625661

RESUMO

Boron's unique position in the Periodic Table, that is, at the apex of the line separating metals and nonmetals, makes it highly versatile in chemical reactions and applications. Contemporary demand for renewable and clean energy as well as energy-efficient products has seen boron playing key roles in energy-related research, such as 1) activating and synthesizing energy-rich small molecules, 2) storing chemical and electrical energy, and 3) converting electrical energy into light. These applications are fundamentally associated with boron's unique characteristics, such as its electron-deficiency and the availability of an unoccupied p orbital, which allow the formation of a myriad of compounds with a wide range of chemical and physical properties. For example, boron's ability to achieve a full octet of electrons with four covalent bonds and a negative charge has led to the synthesis of a wide variety of borate anions of high chemical and electrochemical stability-in particular, weakly coordinating anions. This Review summarizes recent advances in the study of boron compounds for energy-related processes and applications.

6.
Chem Sci ; 10(31): 7375-7378, 2019 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-31489159

RESUMO

A set of diboryldiborenes are prepared by the mild, catalyst-free, room-temperature diboration of the B-B triple bonds of doubly base-stabilized diborynes. Two of the product diboryldiborenes are found to be air- and water-stable in the solid state, an effect that is attributed to their high crystallinity and extreme insolubility in a wide range of solvents.

7.
Chemistry ; 25(59): 13566-13571, 2019 Oct 22.
Artigo em Inglês | MEDLINE | ID: mdl-31433081

RESUMO

The steric and electronic properties of aryl substituents in monoaryl borohydrides (Li[ArBH3 ]) and dihydroboranes were systematically varied and their reactions with [Ru(PCy3 )2 HCl(H2 )] (Cy: cyclohexyl) were studied, resulting in bis(σ)-borane or terminal borylene complexes of ruthenium. These variations allowed for the investigation of the factors involved in the activation of dihydroboranes in the synthesis of terminal borylene complexes. The complexes were studied by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and density functional theory (DFT) calculations. The experimental and computational results suggest that the ortho-substitution of the aryl groups is necessary for the formation of terminal borylene complexes.

8.
Chem Commun (Camb) ; 55(65): 9677-9680, 2019 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-31347619

RESUMO

The scandium Cp/COT hybrid sandwich compound [(η5-C5H5)Sc(η8-C8H8)] is resistant to metallation via conventional alkyllithium and lithium amide bases. In this work, clean, selective, stoichiometric and high-yielding mono- and dimetallation is accomplished using tandem trans-metal-trapping (TMT) involving LiTMP and iBu2AlTMP with deprotonation occurring selectively at the Cp and Cp/COT rings respectively, providing the first examples of selective metallation of a sandwich complex featuring a group 3 element.

9.
Angew Chem Int Ed Engl ; 58(13): 4405-4409, 2019 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-30719809

RESUMO

The lability of B=B, B-P, and B-halide bonds is combined in the syntheses of the first diiododiborenes. In a series of reactivity tests, these diiododiborenes undergo cleavage of all six of their central bonds in different ways, leading to products of B=B hydrogenation and dihalogenation as well as halide exchange.

10.
Dalton Trans ; 48(11): 3547-3550, 2019 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-30758372

RESUMO

Reaction of AsCl3 with Pt(0) complexes [Pt(PCy3)2], [Pt(PCy3)(IMes)] and [Pt(IMes)2] (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) resulted in oxidative addition of As-Cl bonds at the Pt centres to form complexes of the form trans-[PtCl(AsCl2)L2]. Two of these compounds were characterised by X-ray diffraction, making them the first structurally characterised examples of AsX2 ligands (X = halogen). AsBr3 also underwent oxidative addition to [Pt(PCy3)2], forming trans-[PtBr(AsBr2)(PCy3)2] in situ, as judged by 31P NMR spectroscopy. This reaction was unselective, yielding several products, of which a Pt3As2 cluster could be identified by single-crystal X-ray diffraction.

11.
Angew Chem Int Ed Engl ; 58(6): 1842-1846, 2019 Feb 04.
Artigo em Inglês | MEDLINE | ID: mdl-30549204

RESUMO

A new structural class of boron-based diradicals is prepared by Lewis base addition to and reduction of singly cyclic (alkyl)(amino)carbene (CAAC) stabilised diborylalkenes. The diradicals feature a perpendicular olefinic bridge preventing delocalization between the B(CAAC) π systems, making the coupling between the spin centres very weak. DFT calculations indicate that the compounds are ground-state (open-shell) singlets, with triplet states negligibly higher in energy, thus making the triplet states easily populated thermally.

12.
Angew Chem Int Ed Engl ; 58(11): 3268-3278, 2019 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-30353633

RESUMO

A number of recently discovered nucleophilic boron compounds, such as boryl anions and borylenes, are breaking the rules regarding boron and boron-containing compounds and their reputation as Lewis acids/electrophiles. In a similar fashion, the B-H bonding pair electrons in boranes also show nucleophilicity which is ascribed to the lower electronegativity of boron relative to that of hydrogen. However, this nucleophilicity of the B-H bond has received far less attention. Explorations of the nucleophilicity of the B-H bonding pair electrons have led to the formation of B-H-B bonded units and B-H⋅⋅⋅H-Y dihydrogen bonds, based on which new chemistry has been uncovered, including the elucidation of the mechanism of formation of aminodiborane (ADB), the diammoniate of diborane (DADB), and lithium or sodium salts of octahydrotriborates (B3 H8 - ), as well as the development of more convenient and straightforward synthetic routes to these reagents. Moreover, the recognition of the nucleophilic properties of the B-H bonding pair electrons will also help to more deeply understand the different mechanisms operating in hydroboration reactions.

13.
J Am Chem Soc ; 140(39): 12580-12591, 2018 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-30180566

RESUMO

Cyclic (alkyl)(amino)carbenes (CAACs) and N-heterocyclic carbenes (NHCs) are widely used as stabilizing ligands in transition metal and main group element chemistry. Variations in their stabilizing properties have been cursorily explained in the literature by the greater π-donating and σ-accepting properties of CAACs relative to NHCs and their differing steric demands; however, a more precise understanding, in particular a disentanglement of steric and electronic effects, is lacking. The recently reported compounds (E)(L)BB(L)(E) (L = NHC (I)/CAAC (II) and E = SPh) present a unique opportunity to investigate the differences between NHC and CAAC donors, as both forms are stable but differ considerably in their geometrical and electronic properties. The NHC systems possess a singlet ground state with a planar central SBBS unit, while their CAAC counterparts show a triplet ground state with a twisted SBBS unit. Steric effects were found to be important in this case; however, it remained unclear how the different forms of twisting in I and II depend on the interplay of steric and electronic effects. In the present work we disentangle both effects. Our investigations explain all of these effects by MO considerations and show that for this kind of system the size of the singlet-triplet gaps are the key determinants of the differences. The different sizes of the S-T gaps result from variations in the antibonding effects within the highest occupied (HOMOs) and lowest unoccupied molecular orbitals (LUMOs). Our explanation seems to contradict the general scientific consensus about variations in the HOMO and LUMO of these two classes of cyclic carbenes; however, comparisons to the Kekulé biradicaloids recently presented by Bertrand and co-workers indicate the generality of our approach.

14.
J Am Chem Soc ; 140(40): 13056-13063, 2018 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-30222320

RESUMO

The reaction of the tetrahalodiboranes(4) B2F4, B2Cl4, and B2Br4 with a Lewis basic platinum(0) complex led to the isolation of the cis-bis(difluoroboryl) complex cis-[(Cy3P)2Pt(BF2)2] (1) and the novel borylborato complexes trans-[(Cy3P)2Pt{B(X)-BX3}] (2, X = Cl; 3, X = Br), respectively. The trans influence of the borylborato group was found to be one of the strongest ever observed experimentally. Furthermore, the reactivity of little-explored diaryldifluorodiboranes(4) F2B-BMes2 and the new derivative F2B-BAn2 (An = 9-anthryl) toward a range of platinum(0) complexes was investigated. Reactions with relatively nonbulky platinum(0) complexes led to the formation of unsymmetrical cis-bis(boryl) complexes cis-[(R3P)2Pt(BF2)(BMes2)] (6, R = Me; 7, R = Et) as well as the first example of a fourfold-unsymmetrical bis(boryl) complex, [(Me3P)(Cy3P)Pt(BF2)(BMes2)] (12). The use of a more bulky Pt complex provided access to the unprecedented dinuclear bis(boryl) complexes [{( iPr3P)Pt}2(µ-BF2)(µ-BAr2)] (8, Ar = Mes; 9, Ar = An), which feature two different µ2-bridging boryl ligands.

15.
Chemistry ; 24(45): 11795-11802, 2018 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-29920807

RESUMO

The reaction of a pentamethylcyclopentadienyl-substituted dialane with a variety of Lewis bases results in unexpected disproportionation of the dialane into AlI and AlIII species. Use of a transition-metal Lewis base allows for the formation of metal-only Lewis pairs. Furthermore, the synthesis of a Lewis base bis-adduct was successful with the Lewis base 4-dimethylaminopyridine.

16.
Angew Chem Int Ed Engl ; 57(32): 10091-10095, 2018 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-29897648

RESUMO

B(sp2 )-B(sp3 ) diborane species based on bis(catecholato)diboron and N-heterocyclic carbenes (NHCs) underwent catechol/bromide exchange selectively at the sp3 -hybridized boron atom. The reduction of the resulting 1,1-dibromodiborane adducts led to reductive coupling and isolation of doubly NHC-stabilized 1,2-diboryldiborenes. These compounds are the first examples of molecules exhibiting π-electron delocalization over an all-boron chain.

17.
Angew Chem Int Ed Engl ; 57(33): 10752-10755, 2018 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-29785795

RESUMO

Diaryldihalodiboranes(4) were reacted with bis(amidinato)- and bis(guanidinato)silylenes to generate the first neutral diborane-centered radicals. These formally non-aromatic 5π electron systems are stable in the solid state as well as in solution and were characterized by solid-state structure determination, high-resolution mass spectrometry, and EPR spectroscopy. The reactivity of one of these radicals with the oxidant 1,4-benzoquinone led to ring-opening and B-O bond formation.

18.
Chem Sci ; 9(8): 2252-2260, 2018 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-29719698

RESUMO

The self-stabilizing, tetrameric cyanoborylene [(cAAC)B(CN)]4 (I, cAAC = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) and its diborene relative, [(cAAC)(CN)B 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 B(CN)(cAAC)] (II), both react with disulfides and diselenides to yield the corresponding cAAC-supported cyanoboron bis(chalcogenides). Furthermore, reactions of I or II with elemental sulfur and selenium in various stoichiometries provided access to a variety of cAAC-stabilized cyanoboron-chalcogen heterocycles, including a unique dithiaborirane, a diboraselenirane, 1,3-dichalcogena-2,4-diboretanes, 1,3,4-trichalcogena-2,5-diborolanes and a rare six-membered 1,2,4,5-tetrathia-3,6-diborinane. Stepwise addition reactions and solution stability studies provided insights into the mechanism of these reactions and the subtle differences in reactivity observed between I and II.

19.
Chemistry ; 24(38): 9692-9697, 2018 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-29667760

RESUMO

A range of double carbene adducts of digallanes(4) are prepared from an existing double digallane adduct, and their halides are subsequently exchanged, establishing the feasibility of both base and halide-exchange reactions from digallane adducts. Furthermore, a range of digallium species are treated with transition-metal Lewis bases, leading alternatively to oxidative addition products, species with monocoordinate Ga+ ligands, and an unusual ditopic metal-only Lewis pair (MOLP). These results underline the manifold and unpredictable chemistry of halogallane species with Lewis bases.

20.
Angew Chem Int Ed Engl ; 57(21): 6347-6351, 2018 05 22.
Artigo em Inglês | MEDLINE | ID: mdl-29537119

RESUMO

Herein we report the discovery that two bottleable, neutral, base-stabilized diborane(5) compounds are able to bind strongly to a number of copper(I) complexes exclusively through their B-B bond. The resulting complexes represent the first known complexes containing unsupported, neutral σB-B diborane ligands. Single-crystal X-ray analyses of these complexes show that the X-Cu moiety (X=Cl, OTf, C6 F5 ) lies opposite the bridging hydrogen atom of the diborane and is near perpendicular to the B-B bond, interacting almost equally with both boron atoms and causing a B-B bond elongation. DFT studies show that σ donation from and π backdonation to the pseudo-π-like B-B bond account for their formation. Astoundingly, these copper σB-B complexes are inert to ligand exchange with pyridine under either heating or photoirradiation.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA