RESUMO
The precise preparation of monodisperse nanomaterials is among the most fundamental tasks in inorganic synthesis and materials science. Achieving this goal by galvanic exchange is hardly predictable and often results in major structural changes and polydisperse mixtures. Taking advantage of the enhanced stability imparted by ambiphilic carbenes, we report and rationalize the absolute templating, the complete exchange of metals in a template, of group 11 clusters across the entire coinage metal family by means of galvanic exchange. We further delineate that these species provide a molecular model for better understanding the reduction of CO2 at M(111) coinage metal surfaces.
RESUMO
Many organic and main-group compounds, usually acids or bases, can accelerate chemical reactions when used in substoichiometric quantities, a process known as organocatalysis. In marked contrast, very few of these compounds are able to activate carbon monoxide, and until now, none of them could catalyze its chemical transformation, a classical task for transition metals. Herein we report that a stable singlet ambiphilic carbene activates CO and catalytically promotes the carbonylation of an o-quinone into a cyclic carbonate. These findings pave the way for the discovery of metal-free catalyzed carbonylation reactions.
RESUMO
A systematic study is presented on the physical and photophysical properties of isoelectronic and isostructural Cu, Ag, and Au complexes with a common amide (N-carbazolyl) and two different carbene ligands (i.e., CAAC = (5 R,6 S)-2-(2,6-diisopropylphenyl)-6-isopropyl-3,3,9-trimethyl-2-azaspiro[4.5]decan-2-ylidene, MAC = 1,3-bis(2,6-diisopropylphenyl)-5,5-dimethyl-4-keto-tetrahydropyridylidene). The crystal structures of the (carbene)M(I)(N-carbazolyl) (MCAAC) and (MAC)M(I)(N-carbazolyl) (MMAC) complexes show coplanar carbene and carbzole ligands and C-M-N bond angles of â¼180°. The electrochemical properties and energies for charge transfer (CT) absorption and emission compounds are not significantly affected by the choice of metal ion. All six of the (carbene)M(Cz) complexes examined here display high photoluminescence quantum yields of 0.8-1.0. The compounds have short emission lifetimes (τ = 0.33-2.8 µs) that fall in the order Ag < Au < Cu, with the lifetimes of (carbene)Ag(Cz) roughly a factor of 10 shorter than for (carbene)Cu(Cz) complexes. Detailed temperature-dependent photophysical measurements (5-325 K) were carried out to determine the singlet and triplet emission lifetimes (τfl and τph, respectively) and the energy difference between the singlet and triplet excited state, Δ ES1-T1. The τfl values range between 20 and 85 ns, and the τph values are in the 50-200 µs regime. The emission at room temperature is due exclusively to E-type delayed fluorescence or TADF (i.e., T1âΔS1âS0+hν ). The emission rate at room temperature is fully governed by Δ ES1-T1, with the silver complexes giving Δ ES1-T1 values of 150-180 cm-1 (18-23 meV), whereas the gold and copper complexes give values of 570-590 cm-1 (70-73 meV).
RESUMO
Diastereoselective coordination of racemic secondary phosphines (PHRR') to Cu(I) precursors containing chiral bis(phosphines) (diphos*) was explored as a potential route to P-stereogenic phosphido complexes. Reaction of [Cu(NCMe)4][PF6] with chiral bis(phospholanes) gave [Cu(diphos*)2][PF6] (diphos* = ( R, R)-Me-DuPhos (1), ( R, R)-Et-DuPhos (2), or ( R, R)-Me-FerroLANE) (3)) or the mono(chelates) [Cu(diphos*)(NCMe) n][PF6] (diphos* = ( R, R)- i-Pr-DuPhos, n = 2 (4); diphos* = ( R, R)-Me-FerroLANE, n = 1 (5)). Treatment of [Cu(NCMe)4][PF6] with diphos* and PHMe(Is) (Is = 2,4,6-( i-Pr)3C6H2) gave mixtures of diastereomers of [Cu(( R, R)- i-Pr-DuPhos)(PHMe(Is))(NCMe)][PF6] (6) and [Cu(( R, R)-Me-FerroLANE)(PHMe(Is))][PF6] (7); two of the three expected isomers of the bis(secondary phosphine) complexes [Cu(( R, R)- i-Pr-DuPhos)(PhHP(CH2) nPHPh)][PF6] ( n = 2 (8); n = 3 (9)) were formed preferentially in related reactions. Reaction of the halide-bridged dimers [Cu(( R, R)- i-Pr-DuPhos)(X)]2 or [Cu(( R, R)-Me-FerroLANE)(I)]2 with PHMe(Is) gave the labile adducts Cu(( R, R)- i-Pr-DuPhos)(PHMe(Is))(X) (X = Cl (10), Br (11), I (12)) and Cu(( R, R)-Me-FerroLANE)(PHMe(Is))(I) (13). Complexes 1, 6, and 8-11 were structurally characterized by X-ray crystallography. Variable temperature NMR studies of 6 and 8 showed that the secondary phosphine ligands underwent reversible dissociation. Deprotonation of 6 or 7 generated the P-stereogenic phosphido complexes Cu(diphos*)(PMeIs) (diphos* = ( R, R)- i-Pr-DuPhos (14) or ( R, R)-Me-FerroLANE) (17)), observed by 31P NMR spectroscopy, but decomposition also occurred. Density functional theory calculations were used to characterize the diastereomers of thermally unstable 17 and the inversion barrier in a model copper-phosphido complex. These observations provided structure-property relationships which may be useful in developing catalytic asymmetric reactions involving secondary phosphines and P-stereogenic copper phosphido intermediates.
RESUMO
The concept of isomerism is essential to chemistry and allows defining molecules with an identical composition but different connectivity (bonds) between their atoms (constitutional isomers) and/or a different arrangement in space (stereoisomers). The reaction of phosphanyl ketenes, (NHP)-P=C=O (NHP=N-heterocyclic phosphenium) with N-heterocyclic carbenes (NHCs) leads to phosphaheteroallenes (NHP)-O-P=C=NHC in which the PCO unit has been isomerized to OPC. Based on the isolation of several intermediates and DFT calculations, a mechanism for this fundamental isomerisation process is proposed.
RESUMO
An air-stable (amino)(amido)radical was synthesized by reacting a cyclic (alkyl)(amino)carbene with carbazoyl chloride, followed by one-electron reduction. We show that an adjacent radical center weakens the amide bond. It enables the amino group to act as a strong acceptor under steric contraint, thus enhancing the stabilizing capto-dative effect.
Assuntos
Amidas , Lagartos , Animais , Oxirredução , Cloretos , ElétronsRESUMO
Luminescent complexes of heavy metals such as iridium, platinum, and ruthenium play an important role in photocatalysis and energy conversion applications as well as organic light-emitting diodes (OLEDs). Achieving comparable performance from more-earth-abundant copper requires overcoming the weak spin-orbit coupling of the light metal as well as limiting the high reorganization energies typical in copper(I) [Cu(I)] complexes. Here we report that two-coordinate Cu(I) complexes with redox active ligands in coplanar conformation manifest suppressed nonradiative decay, reduced structural reorganization, and sufficient orbital overlap for efficient charge transfer. We achieve photoluminescence efficiencies >99% and microsecond lifetimes, which lead to an efficient blue-emitting OLED. Photophysical analysis and simulations reveal a temperature-dependent interplay between emissive singlet and triplet charge-transfer states and amide-localized triplet states.
RESUMO
An efficient and selective Cu-catalysed hydrohydrazination of terminal alkynes with parent hydrazine is reported. The methodology tolerates a broad range of functional groups, allows for the synthesis of symmetrical and unsymmetrical azines, and can be extended to hydrazine derivatives and amines.
RESUMO
Contrary to recent reports, the dehydrocoupling of pinacol borane and 9-borabicyclononane with a variety of amines, alcohols and thiols can be achieved under mild conditions without catalyst. This process involves the formation of Lewis acid-base adducts featuring a hydridic B-H in close proximity to an acidic Nu-H.