RESUMO
Our growing interest in the design of pnictogen-based strategies for anion transport has prompted an investigation into the properties of three simple triarylcatecholatostiboranes (1-3) of the general formula (o-C6Cl4O2)SbAr3 with Ar = Ph (1), o-tolyl (2), and o-xylyl (3) for the complexation and transport of hydroxide across phospholipid bilayers. A modified hydroxypyrene-1,3,6-trisulfonic acid (HPTS) assay carried out in artificial liposomes shows that 1 and 2 are potent hydroxide transporters while 3 is inactive. These results indicate that the steric hindrance imposed by the three o-xylyl groups prevents access by the hydroxide anion to the antimony center. Supporting this interpretation, 1 and 2 quickly react with TBAOH·30 H2O ([TBA]+ = [nBu4N]+) to form the corresponding hydroxoantimonate salts [nBu4N][1-OH] and [nBu4N][2-OH], whereas 3 resists hydroxide coordination and remains unperturbed. Moreover, the hydroxide transport activities of 1 and 2 are correlated to the +V oxidation state of the antimony atom as the parent trivalent stibines show no hydroxide transport activity.
RESUMO
This study, which aims to identify atypical platforms for the reduction of dioxygen, describes the reaction of O2 with two distibines, namely, 4,5-bis(diphenylstibino)-2,7-di-tert-butyl-9,9-dimethylxanthene and 4,5-bis(diphenylstibino)-2,7-di-tert-butyl-9,9-dimethyldihydroacridine, in the presence of an ortho-quinone such as phenanthraquinone. The reaction proceeds by oxidation of the two antimony atoms to the + V state in concert with reductive cleavage of the O2 molecule. As confirmed by 18O labeling experiments, the two resulting oxo units combine with the ortho-quinone to form an α,α,ß,ß-tetraolate ligand that bridges the two antimony(V) centers. This process, which has been studied both experimentally and computationally, involves the formation of asymmetric, mixed-valent derivatives featuring a stibine as well as a catecholatostiborane formed by oxidative addition of the quinone to only one of the antimony centers. Under aerobic conditions, the catecholatostiborane moiety reacts with O2 to form a semiquinone/peroxoantimony intermediate, as supported by NMR spectroscopy in the case of the dimethyldihydroacridine derivative. These intermediates swiftly evolve into the symmetrical bis(antimony(V)) α,α,ß,ß-tetraolate complexes via low barrier processes. Finally, the controlled protonolysis and reduction of the bis(antimony(V)) α,α,ß,ß-tetraolate complex based on the 9,9-dimethylxanthene platform have been investigated and shown to regenerate the starting distibine and the ortho-quinone. More importantly, these last reactions also produce two equivalents of water as the product of O2 reduction.
RESUMO
Motivated by the discovery of main group Lewis acids that could compete or possibly outperform the ubiquitous organoboranes, several groups, including ours, have engaged in the chemistry of Lewis acidic organoantimony compounds as new platforms for anion capture, sensing, and transport. Principal to this approach are the intrinsically elevated Lewis acidic properties of antimony, which greatly favor the addition of halide anions to this group 15 element. The introduction of organic substituents to the antimony center and its oxidation from the + III to the + V state provide for tunable Lewis acidity and a breadth of applications in supramolecular chemistry and catalysis. The performances of these antimony-based Lewis acids in the domain of anion sensing in aqueous media illustrate the favorable attributes of antimony as a central element. At the same time, recent advances in anion binding catalysis and anion transport across phospholipid membranes speak to the numerous opportunities that lie ahead in the chemistry of these unique main group compounds.
RESUMO
We report the results of a computational investigation into fluoride binding by a series of pentavalent pnictogen Lewis acids: pnictogen pentahalides (PnX5), tetraphenyl pnictogeniums (PnPh4+), and triphenyl pnictogen tetrachlorocatecholates (PnPh3Cat). Activation strain and energy decomposition analyses of the Lewis adducts not only clearly delineate the electrostatic and orbital contributions to these acid-base interactions but also highlight the importance of Pauli repulsion and molecular flexibility in determining relative Lewis acidity among the pnictogens.
RESUMO
As part of our interest in unusual bonding situations, we are now targeting complexes featuring metalâcarbon dative bonds. Here, we report on the formation of such linkages in a series of Group 10 complexes featuring a triarylphosphine ligand functionalized at the γ position by a carbenium ion. Through combined synthetic, spectroscopic, and computational studies, we show that the MâCcarbenium interaction present in these complexes scales with the basicity of the donor, confirming its dative nature.
Assuntos
Carbono , Metais , Carbono/química , LigantesRESUMO
With the discovery of late transition metal platforms that support clean photoreductive halogen eliminations, we now describe an indazol-3-ylidene gold trichloride complex ([7]+ ) decorated at the 4-position by a xanthylium unit. This orange complex features a low energy band in the visible part of the spectrum, assigned to the charge transfer excitation of the indazol-3-ylidene/xanthylium donor/acceptor dyad. Green-light irradiation of this complex in the presence of a chlorine trap elicits the clean photoelimination of chlorine radicals, producing the corresponding gold(I) complex. This visible-light-induced photoreduction is very efficient, reaching quantum yields close to 10 %. A neutral analog of [7]+ featuring an anthryl group rather than a xanthylium unit proved to be perfectly photostable, supporting the importance of the xanthylium-based photoredox unit present in [7]+ .
RESUMO
Telluronium cations have long been known to engage their counteranions via secondary interactions. Yet, this property has rarely been exploited for anion binding. Motivated by such an application, we have now synthesized a bis-telluronium dication ([3]2+) that was obtained as a tetrafluoroborate salt by reaction of 2,7-di-tert-butyl-9,9-dimethylxanthene-4,5-diboronic acid with phenoxatellurine difluoride and BF3·OEt2. As confirmed by the formation of Te-(µ-BF4)-Te bridges in the structure of [3][BF4]2, [3]2+ functions as a bidentate Lewis acid toward anions. [3][BF4]2 has also been converted into the more exposed [3][BArF24]2 ([BArF24]- = [B(3,5-(CF3)2C6H3)4]-). The latter, which readily ionizes Ph3CCl, displays a chloride anion binding constant that exceeds that of a monofunctional model compound by almost 4 orders of magnitude. The unique properties of this new bis-telluronium dication are further highlighted by its ability to activate Ph3PAuCl and cis-(Ph3P)2PtCl2, leading to catalytic systems highly active in the cycloisomerization of propargylamide or enyne substrates.
RESUMO
Our long-standing interest in atypical bonding situations has recently led us to target complexes in which a metallobasic gold(I) center is hydrogen-bonded to a nearby OH functionality. Here, we report on the synthesis and characterization of two neutral gold(I) indazol-3-ylidene complexes bearing a carbinol or silanol group at the 4-position. As indicated by X-ray diffraction, 1H NMR spectroscopy, IR spectroscopy, and extensive computational modeling, the OH group of these derivatives is engaged in a bona fide Au···H-O interaction. In addition to shedding light on an elusive bonding situation, these results also indicate that increasing the acidity of the OH functionality is not necessarily beneficial to the stability of the Au(I)···H-O interaction.
RESUMO
Our efforts in the chemistry of gold complexes featuring ambiphilic phosphine-carbenium L/Z-type ligand have led us to consider the reduction of the carbenium moiety as a means to modulate the gold-carbenium interaction present in these complexes. Here, it was shown that the one-electron reduction of [(o-Ph2 P(C6 H4 )Acr)AuCl]+ (Acr=9-N-methylacridinium) produces a neutral stable radical, the structure of which showed a marked increase in the Au-Acr distance. Related structural changes were observed for the phosphine oxide analogue [(o-Ph2 P(O)(C6 H4 )Acr]+ , the reduction of which interfered with the P=Oâcarbenium interaction. These structural effects, driven by a reduction-induced change in the electronic and electrostatic characteristics of the compounds, showed that the charge and accepting properties of the carbenium unit can be modulated. These results highlight the redox-noninnocence of carbenium Z-type ligand, a feature that can be exploited to induce specific conformational changes.
RESUMO
As part of our efforts in the chemistry of main group platforms that support anion sensing and transport, we are now reporting the synthesis of anitmony-based bidentate Lewis acids featuring the o-C6F4 backbone. These compounds can be easily accessed by reaction of the newly synthesized o-C6F4(SbPh2)2 (5) with o-chloranil or octafluorophenanthra-9,10-quinone, affording the corresponding distiboranes 6 and 7 of general formula o-C6F4(SbPh2(diolate))2 with diolate = tetrachlorocatecholate for 6 and octafluorophenanthrene-9,10-diolate for 7, respectively. While 6 is very poorly soluble, its octafluorophenanthrene-9,10-diolate analog 7 readily dissolves in CH2Cl2 and undergoes swift conversion into the corresponding fluoride chelate complex [7-µ2-F]- which has been isolated as a [nBu4N]+ salt. The o-C6H4 analog of 7, referred to as 8, has also been prepared. Although less Lewis acidic than 7, 8 also forms a very stable fluoride chelate complex ([8-µ2-F]-). Altogether, our experiental results, coupled with computational analyses and fluoride anion affinity calculations, show that 7 and 8 are some of the strongest antimony-based fluoride anion chelators prepared to date. Another notable aspect of this work concerns the use of the octafluorophenanthrene-9,10-diolate ligand and its ablity to impart advantageous solubility and Lewis acidity properties.
RESUMO
As part of our continuing interest in the chemistry of cationic antimony Lewis acids as ligands for late transition metals, we have now investigated the synthesis of platinum complexes featuring a triarylstibine ligand substituted by an o-[(dimethylamino)methyl]phenyl group referred to as ArN. More specifically, we describe the synthesis of the amino stibine ligand Ph2SbArN (L) and its platinum dichloride complex [LPtCl]Cl which exists as a chloride salt and which shows weak coordination of the amino group to the antimony center. We also report the conversion of [LPtCl]Cl into a tricationic complex [LHPt(SMe2)]3+ which has been isolated as a tris-triflate salt after reaction of [LPtCl]Cl with SMe2, HOTf and AgOTf. Finally, we show that [LHPt(SMe2)][OTf]3 acts as a catalyst for the cyclization of 2-allyl-2-(2-propynyl)malonate.
RESUMO
Searching for a connection between the two-electron redox behavior of Group-14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(o-(Ph2 P)C6 H4 )2 GeIV Cl2 ]PtII Cl2 and [(o-(Ph2 P)C6 H4 )2 ClGeIII ]PtIII Cl3 , two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o-(Ph2 P)C6 H4 )2 ClGeIII ]PtI Cl with quantum yields of 1.7 % and 3.2 % for the GeIV -PtII and GeIII -PtIII isomers, respectively. Conversion of the GeIV -PtII isomer into the platinum germyl complex is a rare example of a light-induced transition-metal/main-group-element bond-forming process. Finally, transient-absorption-spectroscopy studies carried out on the GeIII -PtIII isomer point to a ligand arene-Cl. charge-transfer complex as an intermediate.
RESUMO
The development of catalysts for the oxygen reduction reaction is a coveted objective of relevance to energy research. This study describes a metal-free approach to catalyzing the reduction of O2 into H2O2, based on the use of redox-active carbenium species. The most active catalysts uncovered by these studies are the bifunctional dications 1,8-bis(xanthylium)-biphenylene ([3]2+) and 4,5-bis(xanthylium)-9,9-dimethylxanthene ([4]2+) which promote the reaction when in the presence of decamethylferrocene and methanesulfonic acid. Electrochemical studies carried out with [4]2+ suggest the intermediacy of an organic peroxide that, upon protonation, converts back into the starting dication while also releasing H2O2. Kinetic studies point to the second protonation event as being rate-determining.
RESUMO
With the view of developing selective transmembrane anion transporters, a series of phosphonium boranes of general formula [p-RPh2 P(C6 H4 )BMes2 ]+ have been synthesized and evaluated. The results demonstrate that variation of the R group appended to the phosphorus atom informs the lipophilicity of these compounds, their Lewis acidity, as well as their transport activity. Anion transport experiments in POPC-based large unilamellar vesicles show that these main-group cations are highly selective for the fluoride anion, which is transported more than 20 times faster than the chloride anion. Finally, this work shows that the anion transport properties of these compounds are extremely sensitive to the steric crowding about the boron atom, pointing to the crucial involvement of the Groupâ 13 element as the anion binding site.
RESUMO
With the intent to demonstrate that the charge of Z-type ligands can be used to modulate the electrophilic character and catalytic properties of coordinated transition metals, we are now targeting complexes bearing polycationic antimony-based Z-type ligands. Toward this end, the dangling phosphine arm of ((o-(Ph2 P)C6 H4 )3 )SbCl2 AuCl (1) was oxidized with hydrogen peroxide to afford [((o-(Ph2 P)C6 H4 )2 (o-Ph2 PO)C6 H4 )SbAuCl2 ]+ ([2 a]+ ) which was readily converted into the dicationic complex [((o-(Ph2 P)C6 H4 )2 (o-Ph2 PO)C6 H4 )SbAuCl]2+ ([3]2+ ) by treatment with 2â equiv AgNTf2 . Both experimental and computational results show that [3]2+ possess a strong AuâSb interaction reinforced by the dicationic character of the antimony center. The gold-bound chloride anion of [3]2+ is rather inert and necessitates the addition of excess AgNTf2 to undergo activation. The activated complex, referred to as [4]2+ [((o-(Ph2 P)C6 H4 )2 (o-Ph2 PO)C6 H4 )SbAuNTf2 ]2+ readily catalyzes both the polymerization and the hydroamination of styrene. This atypical reactivity underscores the strong σ-accepting properties of the dicationic antimony ligand and its activating impact on the gold center.
RESUMO
Controlling the reactivity of transition metals using secondary, σ-accepting ligands is an active area of investigation that is impacting molecular catalysis. Herein we describe the phosphine gold complexes [(o-Ph2 P(C6 H4 )Acr)AuCl]+ ([3]+ ; Acr=9-N-methylacridinium) and [(o-Ph2 P(C6 H4 )Xan)AuCl]+ ([4]+ ; Xan=9-xanthylium) where the electrophilic carbenium moiety is juxtaposed with the metal atom. While only weak interactions occur between the gold atom and the carbenium moiety of these complexes, the more Lewis acidic complex [4]+ readily reacts with chloride to afford a trivalent phosphine gold dichloride derivative (7) in which the metal atom is covalently bound to the former carbocationic center. This anion-induced AuI /AuIII oxidation is accompanied by a conversion of the Lewis acidic carbocationic center in [4]+ into an X-type ligand in 7. We conclude that the carbenium moiety of this complex acts as a latent Z-type ligand poised to increase the Lewis acidity of the gold center, a notion supported by the carbophilic reactivity of these complexes.
RESUMO
In search of ligand platforms, which can be used to remotely control the catalytic activity of a transition metal, we have investigated the coordination noninnocence of ambiphilic L2/Z-type ligands containing a trifluorostiborane unit as a Lewis acid. The known dichlorostiboranyl platinum complex (( o-(Ph2P)C6H4)2SbCl2)PtCl (1) reacts with TlF in the presence of acetonitrile (MeCN) and cyclohexyl isocyanide (CyNC) to afford the trifluorostiborane platinum complexes 2 ((( o-(Ph2P)C6H4)2SbF3)Pt-NCMe) and 3 ((( o-(Ph2P)C6H4)2SbF3)Pt-CNCy), respectively. Formation of these complexes, which results from a redistribution of the halide ligands about the dinuclear core, affects the nature of the Pt-Sb bond. The latter switches from covalent in 1 to polar covalent (or dative) in 2 and 3 where the trifluorostiborane moiety engages the platinum center in a Pt â Sb interaction. The polarity of the Pt-Sb bond can be modulated further by abstraction of an antimony-bound fluoride ligand using B(C6F5)3. These reactions afford the cationic complexes [(( o-(Ph2P)C6H4)2SbF2)Pt-NCMe]+ ([5]+) and [(( o-(Ph2P)C6H4)2SbF2)Pt-CNCy]+ ([6]+) which have been isolated as [BF(C6F5)3]- salts. These complexes possess a highly Lewis acidic difluorostibonium moiety, which exerts an intense draw on the electron density of the platinum center. As a result, the latter becomes significantly more electrophilic. In the case of [5]+, which contains a labile acetonitrile ligand, this increased electrophilicity translates into increased carbophilicity as reflected by the ability of this complex to promote enyne cyclization reactions. These results demonstrate that the coordination noninnocence of antimony Z-ligands can be used to adjust the catalytic activity of an adjoining metal center.
RESUMO
Borinic acids have typically not been considered as hydrogen bond donor groups in molecular recognition. Described herein is a bifunctional borane/borinic acid derivative (2) in which the two functionalities are connected by a 1,8-biphenylenediyl backbone. Anion binding studies reveal that 2 readily binds a fluoride anion by formation of a unique B-Fâ â â H-O-B hydrogen bond. This hydrogen bond is characterized by a short H-F distance of 1.79(3)â Å and a large coupling constant (1 JHF ) of 57.2â Hz. The magnitude of this interaction, which has also been investigated computationally, augments the fluoride anion binding properties of 2, thus making it compatible with aqueous environments.
RESUMO
The development of groupâ 15 Lewis acids is an area of active investigation that has led to numerous advances in anion sensing and catalysis. While phosphorus has drawn considerable attention, emerging research shows that organoantimony(III) reagents may also act as potent Lewis acids. Comparison of the properties of SbPh3 , Sb(C6 F5 )3 , and SbArF 3 with those of their tetrachlorocatecholate analogues SbPh3 Cat, Sb(C6 F5 )3 Cat, and SbArF 3 Cat (Cat=o-O2 C6 Cl4 , ArF =3,5-(CF3 )2 C6 H3 ) demonstrates that the Lewis acidity of electron deficient organoantimony(III) reagents can be readily enhanced by oxidation to the +V state-as verified by binding studies, organic reaction catalysis, and computational studies. The results are rationalized by explaining that oxidation of the antimony center leads to a lowering of the accepting σ* orbital and a deeper carving of the associated σ-hole.
RESUMO
With the view of developing self-activating electrophilic catalysts, we are now investigating complexes with a Lewis acidic moiety in the immediate vicinity of the transition metal center. Toward this end, we have synthesized a platinum complex in which the metal is connected to a Lewis acidic bis(triflato)stiboranyl ligand. This complex, ((o-(Ph2P)C6H4)2SbOTf2)PtCl (2), which was obtained by treatment of ((o-(Ph2P)C6H4)2SbCl2)PtCl (1) with 2 equiv of AgOTf, is surprisingly air stable. Yet, it promptly reacts with cyclohexylisocyanide to afford the dicationic chlorostibine complex [((o-(Ph2P)C6H4)2SbCl)PtCNCy]2+ ([3]2+) as a bis-triflate salt. Formation of [3]2+ occurs through abstraction of the platinum-bound chloride ligand by the adjacent Lewis acidic antimony center. This halide migration reaction leads to activation of the platinum center. In turn, 2 behaves as a self-activating catalyst in reactions involving alkynes and readily mediates both enyne cyclization and intramolecular hydroarylation reactions, at room temperature, without addition of a chloride abstracting reagent. These results demonstrate that the coordination non-innocence of antimony ligands can be exploited for the purpose of electrophilic catalysis.