RESUMEN
A one-step, two-component visible light-mediated CoCl2·6H2O-catalyzed oxidative acylation of alkenes by aldehydes to synthesize α,ß-epoxy ketone has been achieved in water at room temperature. The photocatalytic activity of Co(II) presented a remarkable achievement for synthesis of α,ß-epoxy ketones from aldehydes and olefins, with a wide substrate compatibility including aromatic, heteroaromatic and aliphatic aldehydes, styrenes with both electron-donating and withdrawing groups, α-substituted styrenes, stilbene, acrylates, and even the challenging unactivated aliphatic alkenes. Mechanistic studies including radical trapping experiments, intermediate detection by GCMS, Hammett analysis, and DFT studies unveil the nature of the photocatalytic pathway.
RESUMEN
A series of boron difluoro bis(diiminate) complexes have been prepared and used to obtain triflate substituted fluoroborane complexes. The corresponding well-defined bis(borenium) cations were subsequently synthesized and structurally authenticated. We are also presenting the first experimental and theoretical study of bis(borenium) cations that are derivative of cationic borinic acid.
RESUMEN
Noninvasive control over the reversible generation of singlet oxygen (1O2) has found the enormous practical implications in the field of biomedical science. However, metal-free pure organic emitters, connected with a photoswitch, capable of generating "on-demand" 1O2 via triplet harvesting remain exceedingly rare; therefore, the utilization of these organic materials for the reversible control of singlet oxygen production remains at its infancy. Herein, an ambient triplet mediated emission in quinoline-dithienylethene (DTE)-core-substituted naphthalene diimide (cNDI) derivative is unveiled via delayed fluorescence. The quinoline-DTE-cNDI triad displayed enhanced photoswitching efficiency via double FRET mechanism. It was found to have direct utilization in controlled photosensitized organic transformations via efficient generation of singlet oxygen (yield ΦΔ ~ 0.73). The designed molecule exhibits a long-lived emission (τ â¼ 1.1 µs) and very small singlet-triplet splitting (ΔSET) of 0.13 eV empowering it to display delayed fluorescence. Comprehensive steady state and time-resolved emission spectroscopy (TRES) analyses along with DFT calculations offer detailed understandings into the excited-state manifolds of organic compound and energy transfer (ET) pathways involved in 1O2 generation.
RESUMEN
An earth-abundant Co(II) salt-catalyzed mild and affordable synthetic route has been developed for the synthesis of industrially relevant 1,4-dicarbonyl compounds (or γ-diketones) via oxidative coupling between aryl alkenes and ketones (both cyclic and acyclic) using TBHP and DBU as the oxidant and base, respectively. 1,4-Dicarbonyl compounds are known to be synthesized using expensive metal catalysts, dual catalysts, or low-cost metal complexes combined with an additive or ligand template, which further needs to be synthesized. Herein, we report the synthesis of 1,4-dicarbonyl compounds using cobalt(II) acetate as a catalyst without any expensive co-catalyst or ligand templates. This methodology has a broad substrate scope with significant yields and good functional group tolerance. Generation of unsymmetrical 1,4-dicarbonyls at room temperature and its versatile synthetic expansion to produce synthetically and biologically valuable heterocyclic compounds are salient features of this novel methodology. In addition, various controlled experiments such as primary kinetic isotope effect study, Hammett analysis with variation of the nature of the substituents on the styrene ring, and theoretical calculations (density functional theory) unravel the mechanistic intricacies involved in this new, simple, and atom-economic methodology.
RESUMEN
Novel isomorphous tetranuclear complexes, [(dppf)Cu(µ3 ,η2 : 2 : 2 -E2 {CpMo(CO)2 }2 ]BF4 [E=P (1), As (4), Sb (5), (dppf=1,1'-bis-(diphenylphosphino)-ferrocene)] and [(dppf)Cu(µ3 ,η2 : 2 : 2 -PE{CpMo(CO)2 }2 ]BF4 [E=As (2), Sb(3)] were synthesized from the reactions between [(dppf)Cu(MeCN)2 ][BF4 ] and tetrahedral molybdenum complexes containing unsubstituted homo- and hetero-diatomic group-15 elements [(µ,η2 : 2 -E2 {CpMo(CO)2 }2 ] [E=P (A), As (D), Sb (E)] and [(µ,η2 : 2 -PE{CpMo(CO)2 }2 ] [E=As (B), Sb (C)], respectively. In all these products, the {Mo2 E2 } or {Mo2 PE} moieties coordinate the Cu(I) center via a rare side-on η2 -coordination mode. The X-ray structure analyses of [(dppf)Cu(µ3 ,η2 : 2 : 1 -PSb{CpMo(CO)2 }2 ][BF4 ] demonstrate, for the first time, the utilization of an η1 -coordination mode for the ligand complex C to coordinate to the Cu(I) center. All the products were characterized by X-ray crystallography, NMR and IR spectroscopy, mass spectrometry and elemental analysis. Electrochemical studies also revealed the formation of 1-5, and, further, to understand the structure and bonding of the products, theoretical calculations using density functional theory (DFT) were conducted.
RESUMEN
Photochromic fluorescent molecules dramatically extend their fields of applications ranging from optical memories, bioimaging, photoswitches, photonic devices, anti-counterfeiting technology and many more. Here, we have logically designed and synthesized a triazole appended bis-(dithienylethene)-naphthalenediimide based photo-responsive material, 5, which demonstrated fluorescence enhancement property upon photocyclization (ΦF =0.42), with high photocyclization (44â s, ksolution =0.0355â s-1 , ksolid =0.0135â s-1 ) and photocycloreversion (160â s, ksolution =0.0181â s-1 , ksolid =0.0085â s-1 ) rate and decent photoreaction quantum yield (Φoâc =0.93 and Φcâo =0.11). The open isomer almost converted to the closed isomer at photo-stationary state (PSS) with distinct color change from colorless to blue with 92.85 % conversion yield. A reversible noninvasive modulation of fluorescence through efficient photoinduced electron transfer (PET) process was observed both in solution as well as in solid state. The fluorescence modulation through PET process was further corroborated with thermodynamic calculations using the Rehm-Weller equation and quantum chemical studies (DFT). The thermally stable compound 5 exhibits high fatigue resistance property (up to 50â cycles) both in solution and solid state. Furthermore, the compound 5 was successfully applied as erasable ink and in deciphering secret codes (Quick Response/bar code) portending potential promising application in anti-counterfeiting.
RESUMEN
The C2-symmetric photochromic molecule 3, containing dithienylethene (DTE) and ferrocene units connected by an alkyne bridge, represents a unique probe where a metal (Hg2+) binds with the central DTE moiety. Both photoisomerized states of 3 (open, 3o; closed, 3c) are found to interact with Hg2+ ion by the S atoms of the DTE core; however, the binding constants (from a UV-vis study) and DFT calculations suggest that the open isomer (3o) binds with the metal ion more strongly than that of the closed isomer (3c). Notably, the course of metal binding does not perturb the inherent photoisomerization properties of the DTE core and the photoswitchability persists even in the metal-coordinated form of 3, however, with a comparatively slower rate. The quantum yields for photocyclization (Φoâc) and photocycloreversion (Φcâo) in the free form are 0.56 and 0.007, respectively, whereas the photocyclization quantum yield in the Hg2+ complexed species is 0.068, 8.2 times lower than the photocyclization quantum yield (Φoâc) of free 3o. Thus, the rate of photoisomerization can be modulated by a suitable metal coordination to the DTE core. The dynamics of photoswitchability in the metal-coordinated form of DTE has been explored by experimental means (UV-vis and electrochemical studies) as well as quantum chemical calculations.
RESUMEN
A unique C2 symmetric azine bridged bi-ferrocenyl receptor (4) has been modelled and synthesized. In this work, we are able to synthetically regulate conjugation of the dibenzylidenehydrazine fluorophore unit to unexpectedly reveal metal-coordination driven intramolecular twisting. The present probe shows a dramatic turn-on fluorescence response with 91 fold increment of quantum yield along with 17 nm blue shift upon binding with Hg2+ ions selectively with a limit of detection as low as 15 nM. Upon Hg2+ recognition, the ferrocene/ferrocinium redox peak was anodically shifted by ΔE1/2 = 78 mV, indicating the formation of a new complex species. A plausible binding mode of Hg2+ ions with compound 4 has been proposed based on 1H NMR titration, a high-resolution mass spectrometry (HRMS) study and a density functional theory (DFT) study along with the Job's plot analysis. Interestingly, DFT calculations have revealed that the reason for fluorescence enhancement after coordination to Hg2+ ions is not due to conventional restricted C[double bond, length as m-dash]N isomerization or interrupted N-N single bond rotation rather it is due to the increase of the π â π* transition at the expense of the n â π* (aromatic) transition of the free ligand. Furthermore, TD-DFT calculations of the first excited singlet state of 4 and [4·Hg2+] revealed the involvement of the aromatic π electrons with the vacant site of Hg2+ ions which may be further attributed to the fluorescence enhancement phenomenon. In addition, receptor 4 was successfully applied for the detection of Hg2+ ions in real samples.
RESUMEN
The field of diborinane is sparsely explored area, and not many compounds are structurally characterized. The room-temperature reaction of [{Cp*RuCl(µ-Cl)}2] (Cp* = η5-C5Me5) with Na[BH3(SCHS)] yielded ruthenium dithioformato [{Cp*Ru(µ,η3-SCHS)}2], 1, and 1-thioformyl-2,6-tetrahydro-1,3,5-trithia-2,6-diborinane complex, [(Cp*Ru){(η2-SCHS)CH2S2(BH2)2}], 2. To investigate the reaction pathway for the formation of 2, we carried out the reaction of [(BH2)4(CH2S2)2], 3, with 1 that yielded compound 2. To the best of our knowledge, it appears that compound 2 is the first example of a ruthenium diborinane complex where the central six-membered ring [CB2S3] adopts the chair conformation. Furthermore, room temperature reaction of 1 with [BH3·thf] resulted in the isolation of agostic-bis(σ-borate) complex, [Cp*Ru(µ-H)2BH(S-CHâS)], 4. Thermolysis of 4 with trace amount of tellurium powder led to formation of bis(bridging-boryl) complex, [{Cp*Ru(µ,η2-HBS2CH2)}2], 5, via dimerization of 4 followed by dehydrogenation. Compound 5 can be considered as a bis(bridging-boryl) species, in which the boryl units are connected to two ruthenium atoms. Theoretical studies and chemical bonding analyses demonstrate the reason for exceptional reactivity and stability of these complexes.
RESUMEN
The synergic property of the CO ligand, in general, can stabilize metal complexes at lower oxidation states. Utilizing this feature of the CO ligand, we have recently isolated and structurally characterized a highly fluxional molybdenum complex [{Cp*Mo(CO)2}2{µ-η2:η2-B2H4}] (2; Cp* = η5-C5Me5) comprising the diborane(4) ligand. Compound 2 represents a rare class of bimetallic diborane(4) complex corresponding to a singly bridged C s structure. In an attempt to isolate the tungsten analogue of 2, [{Cp*W(CO)2}2{µ-η2:η2-B2H4}], we have isolated a rare vertex-fused cluster, [(Cp*W)3WB9H18] (5). Having a structural likeness with the dimolybdenum alkyne complex [{CpMo(CO)2}2C2H2], we have further explored the chemistry of 2 with CO gas that yielded a homoleptic trimolybdenum complex, [(Cp*Mo)3(µ-H)2(µ3-H)(µ-CO)2B4H4] (4). In an attempt to replace the 16-electron {Cp*MoH(CO)2} moiety in 4 with isolobal fragment {W(CO)5}, we treated the intermediate, obtained from the reaction of Cp*MoCl4 and LiBH4, with the monometal carbonyl fragment {W(CO)5·THF}. The reaction indeed yielded two bimetallic clusters, [(Cp*Mo)2B4H8W(CO)4] (7) and [(Cp*Mo)2B4H6W(CO)5] (8), that seem to have been generated by the replacement of one {BH} or {BH3} vertex from [(Cp*Mo)2B5H9], respectively. All of the compounds have been characterized by various spectroscopic analyses and single-crystal X-ray diffraction studies. Electron-counting rules and molecular orbital analyses provided further insight into the electronic structure of all of these molecules.
RESUMEN
Among the series of stable closo-borate dianions, [B n H n ]2-, the X-ray crystallographic structure of [B7H7]2- was determined only in 2011. To explore its chemistry and stability, we have isolated and structurally characterized two new transition metal complexes of the heptaborane, [(Cp2M)2B9H11] (Cp = η5-C5H5; M = Zr or Hf). The structures of [(Cp2M)2B9H11] contain a pentagonal bipyramidal B7 core, coordinated by two {Cp2M} and two {BH2} units equatorially. Structural and spectroscopic characterizations and DFT calculations show that [(Cp2M)2B9H11] complexes are substantially more stable than the parent dianion, in either [B7H7]2- or ( n Bu4N)2[B7H7]. Our theoretical study and chemical bonding analyses reveal that the surprising stability of the two new heptaborane metal complexes is due to multi-center covalent bonds related to the two exo-{Cp2M} units, as well as electrostatic interactions between the {Cp2M} units and the B7 core. The facile syntheses of the heptaborane metal-complexes will allow further exploration of their chemistry.
RESUMEN
The reaction of [(Cp*Mo)2 (µ-Cl)2 B2 H6 ] (1) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)2 }2 {µ-η2 :η2 -B2 H4 }] (2). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged Cs structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum-alkyne complex [{CpMo(CO)2 }2 C2 H2 ]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO)4 ] fragment, [{Cp*Mo(CO)2 }2 B2 H2 W(CO)4 ] (3) was isolated upon treatment with [W(CO)5 â thf]. Compound 3 shows the intriguing presence of [B2 H2 ] with a short B-B length of 1.624(4)â Å. We isolated the tungsten analogues of 3, [{Cp*W(CO)2 }2 B2 H2 W(CO)4 ] (4) and [{Cp*W(CO)2 }2 B2 H2 Mo(CO)4 ] (5), which provided direct proof of the existence of the tungsten analogue of 2.
RESUMEN
A unique turn-on fluorescent device based on a ferrocene-aminonaphtholate derivative specific for Hg2+ cation was developed. Upon binding with Hg2+ ion, the probe shows a dramatic fluorescence enhancement (the fluorescence quantum yield increases 58-fold) along with a large red shift of 68 nm in the emission spectrum. The fluorescence enhancement with a red shift may be ascribed to the combinational effect of CâN isomerization and an extended intramolecular charge transfer (ICT) mechanism. The response was instantaneous with a detection limit of 2.7 × 10-9 M. Upon Hg2+ recognition, the ferrocene/ferrocenium redox peak was anodically shifted by ΔE1/2 = 72 mV along with a "naked eye" color change from faint yellow to pale orange for this metal cation. Further, upon protonation of the imine nitrogen, the present probe displays a high fluorescence output due to suppression of the CâN isomerization process. Upon deprotonation using strong base, the fluorescence steadily decreases, which indicates that H+ and OH- can be used to regulate the off-on-off fluorescence switching of the present probe. Density functional theory studies revealed that the addition of acid leads to protonation of the imine N (according to natural bond orbital analysis), and the resulting iminium proton forms a strong H-bond (2.307 Å) with one of the triazole N atoms to form a five-membered ring, which makes the molecule rigid; hence, enhancement of the ICT process takes place, thereby leading to a fluorescence enhancement with a red shift. The unprecedented combination of H+, OH-, and Hg2+ ions has been used to generate a molecular system exhibiting the INHIBIT-OR combinational logic operation.
RESUMEN
The syntheses and structural characterization of hypo-electronic di-molybdenum triple-decker sandwich clusters are reported. Thermolysis of [Ru3(CO)12] with an in situ generated intermediate obtained from the reaction of [Cp*MoCl4] with [LiBH4·THF] yielded an electron deficient triple-decker sandwich complex, [(Cp*Mo)2{µ-η(6):η(6)-B4H4Ru2(CO)6}], . In an effort to generate analogous triple-deckers containing group-16 elements, we isolated [(Cp*Mo)2{µ-η(6):η(6)-B4H4ERu(CO)3}] (: E = Te; : E = S; : E = Se). These clusters show a high metal coordination number and cross cluster Mo-Mo bond. The formal cluster electron count of these compounds is four or three skeletal electron pairs less than required for a canonical closo-structure of the same nuclearity. Therefore, these compounds represent a novel class of triple-decker sandwich complex with 22 or 24 valence-electrons (VE), wherein the "chair" like hexagonal middle ring is composed of B, Ru and chalcogen. One of the key differences among the synthesized triple-decker molecules is the puckering nature of the middle ring [B4RuE], which increases in the order S < Se < Ru(CO)3 < Te. In addition, Fenske-Hall and quantum-chemical calculations with DFT methods at the BP86 level of theory have been used to analyze the bonding of these novel complexes. The studies not only explain the electron unsaturation of the molecules, but also reveal the reason for the significant puckering of the middle deck. All the compounds have been characterized by IR, (1)H, (11)B, and (13)C NMR spectroscopy in solution and the solid state structures were established by crystallographic analysis.
RESUMEN
In an effort to synthesize supraicosahedral iridaboranes, pyrolysis of [Cp*IrCl2]2 with excess [BH3·] was carried out, and this synthesis afforded the isomeric iridaborane [(Cp*Ir)2B6H6] clusters 1 and 2. The geometry of 1 was determined to be dodecahedral, i.e., similar to that of [B8H8](2-), whereas 2 was found to exhibit a cluster shape that can be derived from a nine-vertex tricapped trigonal prism by removing one of the capped vertices. The calculation of a large HOMO-LUMO gap further rationalized the isocloso structures for these isomers.
RESUMEN
In an attempt to synthesize a zero valent germanium compound, we have carried out the reaction of [(Cp*RuCO)(GeCl2)]2, 1 with potassium metal that led to the formation of a metallagermoxane [(Cp*Ru(CO)2Ge)4(µ-O)6], 2. Compound 2 is the first example of a tetrametallagermoxane with an exo-{Cp*Ru(CO)2} fragment. DFT calculations were used to examine the key intermediates associated with the formation of 2.
RESUMEN
This work describes the synthesis, structural characterizations, and electronic structures of a series of novel homometallic cubane clusters [(Cp*Ru)2{Ru(CO)2}2BH(µ3-E)(µ-H)B(µ-H)3M], (2, M = Cp*Ru, E = CO; 3, M = Ru(Cp*Ru)2(µ-CO)3(µ-H)BH), E = BH), [(Cp*Ru)3(µ3-CO)(BH)3(µ3-H)3], 4, and [(Cp*Ru)2(µ3-CO){Ru(CO)3}2(BH)2(µ-H)B], 5 (Cp* = η(5)-C5Me5). These cubane clusters have been isolated from a thermally driven reaction of diruthenium analogue of pentaborane(9) [(Cp*RuH)2B3H7], 1, and [Ru3(CO)12]. Structural and spectroscopic studies revealed the existence of triply bridged hydrogen (µ3-H) atoms that participate as a vertex in the cubane core formation for compounds 2, 3, and 4. In addition, the crystal structure of these clusters clearly confirms the presence of an electron precise borane ligand (borylene fragment) which is triply bridged to the trimetallic units. Bonding of these novel complexes has been studied computationally by DFT methods, and the studies demonstrate that the cubane clusters 2 and 3 possess 60 cluster valence electrons (cves) with six metal-metal bonds. All the new compounds have been characterized in solution by mass spectrometry; IR; and (1)H, (11)B, and (13)C NMR studies, and the structural types were unequivocally established by crystallographic analysis of compounds 2-5.
RESUMEN
Building upon previous studies on the synthesis of bis(sigma)borate and agostic complexes of ruthenium, the chemistry of nido-[(Cp*Ru)2 B3 H9] (1) with other ligand systems was explored. In this regard, mild thermolysis of nido-1 with 2-mercaptobenzothiazole (2-mbzt), 2-mercaptobenzoxazole (2-mbzo) and 2-mercaptobenzimidazole (2-mbzi) ligands were performed which led to the isolation of bis(sigma)borate complexes [Cp*RuBH3 L] (2 a-c) and ß-agostic complexes [Cp*RuBH2 L2] (3 a-c; 2 a, 3 a: L=C7 H4 NS2 ; 2 b, 3 b: L=C7 H4 NSO; 2 c, 3 c: L=C7 H5 N2 S). Further, the chemistry of these novel complexes towards various diphosphine ligands was investigated. Room temperature treatment of 3 a with [PPh2 (CH2 )n PPh2 ] (n=1-3) yielded [Cp*Ru(PPh2 (CH2 )n PPh2 )-BH2 (L2)] (4 a-c; 4 a: n=1; 4 b: n=2; 4 c: n=3; L=C7 H4 NS2). Mild thermolysis of 2 a with [PPh2 (CH2)n PPh2 ] (n=1-3) led to the isolation of [Cp*Ru(PPh2 (CH2)n PPh2 )(L)] (L=C7 H4 NS2 5 a-c; 5 a: n=1; 5 b: n=2; 5 c: n=3). Treatment of 4 a with terminal alkynes causes a hydroboration reaction to generate vinylborane complexes [Cp*Ru(R-C=CH2 )BH(L2)] (6 and 7; 6: R=Ph; 7: R=COOCH3; L=C7 H4 NS2). Complexes 6 and 7 can also be viewed as η-alkene complexes of ruthenium that feature a dative bond to the ruthenium centre from the vinylinic double bond. In addition, DFT computations were performed to shed light on the bonding and electronic structures of the new compounds.
RESUMEN
A combined experimental and quantum chemical study of Group 7 borane, trimetallic triply bridged borylene and boride complexes has been undertaken. Treatment of [{Cp*CoCl}2 ] (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) with LiBH4 â thf at -78 °C, followed by room-temperature reaction with three equivalents of [Mn2 (CO)10 ] yielded a manganese hexahydridodiborate compound [{(OC)4 Mn}(η(6) -B2 H6 ){Mn(CO)3 }2 (µ-H)] (1) and a triply bridged borylene complex [(µ3 -BH)(Cp*Co)2 (µ-CO)(µ-H)2 MnH(CO)3 ] (2). In a similar fashion, [Re2 (CO)10 ] generated [(µ3 -BH)(Cp*Co)2 (µ-CO)(µ-H)2 ReH(CO)3 ] (3) and [(µ3 -BH)(Cp*Co)2 (µ-CO)2 (µ-H)Co(CO)3 ] (4) in modest yields. In contrast, [Ru3 (CO)12 ] under similar reaction conditions yielded a heterometallic semi-interstitial boride cluster [(Cp*Co)(µ-H)3 Ru3 (CO)9 B] (5). The solid-state X-ray structure of compound 1 shows a significantly shorter boron-boron bond length. The detailed spectroscopic data of 1 and the unusual structural and bonding features have been described. All the complexes have been characterized by using (1) H, (11) B, (13) Câ NMR spectroscopy, mass spectrometry, and X-ray diffraction analysis. The DFT computations were used to shed light on the bonding and electronic structures of these new compounds. The study reveals a dominant B-H-Mn, a weak B-B-Mn interaction, and an enhanced B-B bonding in 1.
RESUMEN
An unprecedented, 22-valence-electron triple-decker sandwich complex [(Cp*Mo)2{µ-η(6):η(6)-B4H4Ru2(CO)6}], 2, has been prepared. In an effort to generate analogous triple-deckers with group 6 metal carbonyl fragments in the middle deck, we have isolated [(Cp*MoCO)2(µ-H)2B4H4], 3, that provides the first direct evidence for the missing link between [(Cp*MoCl)2B3H7] and [(Cp*Mo)2B5H9] clusters.