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Telluronium salts [Ar2 MeTe]X were synthesized, and their Lewis acidic properties towards a number of Lewis bases were addressed in solution by physical and theoretical means. Structural X-ray diffraction analysis of 21 different salts revealed the electrophilicity of the Te centers in their interactions with anions. Telluroniums' propensity to form Lewis pairs was investigated with OPPh3 . Diffusion-ordered NMR spectroscopy suggested that telluroniums can bind up to three OPPh3 molecules. Isotherm titration calorimetry showed that the related heats of association in 1,2-dichloroethane depend on the electronic properties of the substituents of the aryl moiety and on the nature of the counterion. The enthalpies of first association of OPPh3 span -0.5 to -5â kcal mol-1 . Study of the affinity of telluroniums for OPPh3 by state-of-the-art DFT and ab-initio methods revealed the dominant Coulombic and dispersion interactions as well as an entropic effect favoring association in solution. Intermolecular orbital interactions between [Ar2 MeTe]+ cations and OPPh3 are deemed insufficient on their own to ensure the cohesion of [Ar2 MeTe â Bn ]+ complexes in solution (B=Lewis base). Comparison of Grimme's and Tkatchenko's DFT-D4/MBD-vdW thermodynamics of formation of higher [Ar2 MeTe â Bn ]+ complexes revealed significant molecular size-dependent divergence of the two methodologies, with MBD yielding better agreement with experiment.
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The mechanism of isomerization of the known 2-phenyl,pyridine (phpy) derivatives [Ru(phpy-κC,N) (MeCN-trans-N)(terpy)]PF6, 2, to [Ru(phpy-κC,N)(MeCN-trans-C)(terpy)]PF6 (terpy = 2,2';6',2â³-terpyridine), 3, at temperatures >50 °C has been investigated both by 1H NMR spectroscopy and by DFT calculations. The photoisomerization of 2 to 3 by UV light occurred also quantitatively in MeCN after 20 h at room temperature. A similar behavior to that of 2 could be established for the related compound [Ru(3-acridine-2'-C5H4N-κC,N)(MeCN-trans-N)(2,2';6',2â³-terpyridine)]PF6, 6 (acridine = dibenzo[b,e]pyridine or 2,3-benzoquinoline), that was obtained from the reaction between [Ru(3-acridine-2'-C5H4N-κC,N) (MeCN)4]PF6, 4, and terpy in MeOH/MeCN at 60 °C for 24 h. Similar to 2, the isomerization of 6 to [Ru(3-acridine-2'-C5H4N-κC,N)(MeCN-trans-C) (terpy)]PF6, 7, could be induced thermally (48 h at 60 °C in pure MeOH) or photochemically under UV radiation in MeCN at room temperature. A compound closely related to 7 but in which MeCN was replaced by H2O was described earlier (Tanaka et al. Inorg. Chem. 2012, 51, 5386-539). The presence of water on this compound had a dramatic effect as far as the coordination of terpy was concerned as its isomerization to a compound related to 6 (in which H2O instead of MeCN is coordinated to Ru) occurred indeed photochemically via irradiation with visible light.
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Organofluorines have a broad range of industrial applications, such as pharmaceuticals, liquid crystal displays (LCDs), solar cells, textiles, and construction coatings, and are used in peptidomimetics, surfactants, refrigerants, anesthetics, and agrochemicals. Among them are versatile monofluoroalkenes that play a crucial role in medicinal and synthetic chemistry. The synthetic strategies for this class of molecules are limited, and prior efforts frequently suffered from poor atom- and step-economies. As a surrogate pathway for traditional cross-coupling transformations, transition metal (TM)-catalyzed C-H direct α-fluoroalkenylation overcomes these obstacles and provides straightforward techniques to access monofluoroalkenes. Nevertheless, substrate scope is still a challenge for catalysis, where gem-bromofluoroalkene synthons are applicable with electronically biased substrates such as azoles, while gem-difluoroalkene-based strategies are limited to substrates containing N-based directing groups. Herein, we review the cutting-edge fluoroalkenylation research for direct synthesis of monofluoroalkenes achieved during the last decade (2013-2023). This review is divided into two main parts: the first part discusses TM-catalyzed direct α-fluoroalkenylation via the merging of C-H activation and C(sp2)-Br cleavage strategies using gem-bromofluoroalkenes, and the second part describes the same reaction, albeit with C(sp2)-F cleavage of highly explored gem-difluoroolefins. Our review surveys all previously reported monofluoroalkenes in this research area, including their preparation techniques, stereoselectivity, and yield percentages. Furthermore, optimal conditions, reactant scope, mechanistic investigations, synthetic applications, benefits, and drawbacks of each presented methodology are critically discussed.
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The performance of six newly synthesized benzo[h]quinoline-derived acetonitrilo pentamethylcyclopentadienyl iridium(III) tetrakis(3,5-bis-trifluoromethylphenyl)borate salts bearing different substituents -X (-OMe, -H, -Cl, -Br, -NO2 and -(NO2 )2 ) on the heterochelating ligand were evaluated in the dehydro-O-silylation of benzyl alcohol and the monohydrosilylation of 4-methoxybenzonitrile by Et3 SiH, two reactions involving the electrophilic activation of the Si-H bond. The benchmark shows a direct dependence of the catalytic efficiency with the electronic effect of -X, which is confirmed by theoretical assessment of the intrinsic silylicities Π of hydridoiridium(III)-silylium adducts and by the theoretical evaluation of the propensity of hydridospecies to transfer the hydrido ligand to the activated substrate. The revisited analysis of the Ir-Si-H interactions shows that the most cohesive bond in hydridoiridium(III)-silylium adducts is the Ir-H one, while the Ir-Si is a weak donor-acceptor dative bond. The Si H interaction in all the cases is noncovalent in nature and dominated by electrostatics confirming the heterolytic cleavage of the hydrosilane's Si-H bond in this key catalytically relevant species.
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Exploration of new organometallic systems based on polyhedral boron clusters has the potential to solve challenging chemical problems such as the stabilization of reactive intermediates and transition-state-like species postulated for E-H (E = H, B, C, Si) bond activation reactions. We report on facile and clean B-H activation of a hydroborane by a new iridium boron cluster complex. The product of this reaction is an unprecedented and fully characterized transition metal-stabilized boron cation or borenium. Moreover, this intermediate bears an unusual intramolecular B···H interaction between the hydrogen originating from the activated hydroborane and the cyclometallated metal-bonded boron atom of the boron cluster. This B···H interaction is proposed to be an arrested insertion of hydrogen into the Bcage-metal bond and the initiation step for iridium "cage-walking" around the upper surface of the boron cluster. The "cage-walking" process is supported by the hydrogen-deuterium exchange observed at the boron cluster, and a mechanism is proposed on the basis of theoretical methods with a special focus on the role of noncovalent interactions. All new compounds were isolated and fully characterized by NMR spectroscopy and elemental analysis. Key compounds were studied by single crystal X-ray diffraction and X-ray photoelectron spectroscopy.
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Noncovalent interactions (NCIs) have long interested a vast community of chemists who investigated their "canonical categories" derived from descriptive crystallography, e.g., H-bonds, π-π interactions, halogen/chalcogen/tetrel bonds, cation-π and C-H-π interactions, metallophilic interactions in the broad sense, etc. Recent developments in theoretical chemistry have enabled the treatment of noncovalent interactions under new auspices: dispersion-force-inclusive density functionals have emerged, which are reliable for modeling small to large molecular systems. It is possible to perform the full analysis of the contributions of London, Debye, and Keesom forces, i.e., the main components of van der Waals forces, by the DFT-D and ab initio methods at a reasonable computational cost. Our research has been focusing for now 15 years on the role of NCIs in the cohesion of organometallic complexes. NCIs are not only effective in Werner's secondary coordination sphere but also in the metal's primary one. The stabilization of electron-unsaturated transition metal complexes by hemichelation, metal-metal donor-acceptor complexes, and self-aggregation of cationic Rh(I) chromophores have indeed outlined the significance of the London dispersion force as an attractive force operating throughout the whole molecule or molecular assembly. The recent outburst of interest in C-H bond functionalization led us to address the broader question of reaction and catalyst engineering: although one can now satisfactorily analyze bonding and molecular cohesion in transition-metal-based organometallic systems, can modern theoretical methods guide reactivity exploration and the engineering of novel catalytic systems? We addressed this question by investigating the ambiphilic metal-ligand activation/concerted metalation-deprotonation mechanism involved in transition-metal-catalyzed directed C-H bond functionalization. This endeavor was initiated having in scope the construction of a rationale for the transposition of 4-5d metal chemistry to earth-abundant 3d metals. In this base-assisted mechanism of C-H bond metalation, agostic interactions are necessary but not sufficient because C-H bond breaking actually relies on the attractive NCI coding of a proton-transfer step and the minimization of metal-H repulsion. This Account introduces the recent shift of our research toward the construction of an NCI-inclusive paradigm of chemical reactivity engineering based on experimental efforts propped up by state-of-the-art theoretical tools.
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The pentamethylcyclopentadienyl N-heterocyclic carbene nickel complex [Ni(η5 -C5 Me5 )Cl(IMes)] (IMes=1,3-dimesitylimidazol-2-ylidene) efficiently catalyses the anti-Markovnikov hydroboration of alkenes with catecholborane in the presence of a catalytic amount of potassium tert-butoxide, and joins the very exclusive club of nickel catalysts for this important transformation. Interestingly, the regioselectivity can be reversed in some cases by using pinacolborane instead of catecholborane. Mechanistic investigations involving control experiments, 1 H and 11 Bâ NMR spectroscopy, cyclic voltammetry, piezometric measurements and DFT calculations suggest an initial reduction of the NiII precursor to a NiI active species with the concomitant release of H2 . The crucial role of the alkoxo-catecholato-borohydride species resulting from the reaction of potassium tert-butoxide with catecholborane in the formation of an intermediate nickel-hydride species that would then be reduced to the NiI active species, is highlighted.
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To figure out the possible role of 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) as well as to provide reference thermochemical data in solution, the formation of Lewis acid-base complexes between HFIP (Lewis acid) and a series of 8 different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) was examined by isothermal titration calorimetry (ITC) experiments and static density functional theory augmented with Dispersion (DFT-D) calculations. Measured ITC association enthalpy values (ΔHa ) lie between -9.3 and -14â kcal mol-1 . Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems compared to the ITC data with ΔHa values ranging from -8.5 to -12.7â kcal mol-1 . An additional set of calculations combining implicit and explicit solvation by chlorobenzene of the reactants, pointed out the relatively low interference of the solvent with the HFIP-base complexation: its main effect is to slightly enhance the Gibbs energy of the HFIP-Lewis base association. It is speculated that the interactions of bulk HFIP with Lewis bases therefore may significantly intervene in catalytic processes not only via the dynamic microstructuring of the medium but also more explicitly by affecting bonds' polarization at the Lewis bases.
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The CMD/AMLA mechanisms of cyclopalladation and the parent fictitious but challenging cyclonickelation of N,N-dimethylbenzylamine have been investigated by joint DFT-D and DLPNO-CCSD(T) methods assisted by QTAIM-based noncovalent interaction plots (NCI plots) and interacting quantum atoms (IQA) analyses, and the local energy decomposition (LED) procedure. Bader charges, NCI plots, IQA and the LED analyses clearly suggest that coulombic interactions play an important role and somewhat govern the whole process that is sensitive to the charge borne by the metal centre. It is found that replacement of acetate by acetamidate used as a ligand and a base significantly lowers the barrier to the formation of the key agostic intermediate. The latter shows a peculiar polarization by its immediate ligand environment where a significant electrostatic CHO interaction with the neighboring carboxylato ligand competes with the strong propensity of the latter to bind the metal center, which is stronger in the agostic intermediate when the carboxylato ligand is the acetate and when the metal is Ni. It is also shown that the hereby idealized cyclonickelation is disfavored as compared to cyclopalladation owing to enhanced electrostatic repulsion in almost all stages of the CMD mechanism.
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The reaction of H3 SiR (R=Ph, nBu) with cationic η5 -C5 Me5 - (Cp*) and benzo[h]quinolinyl-based iridacycle [1 b]+ gives rise to new [(IrH)âSiRH2 ]+ adducts. In the presence of THF these adducts readily undergo elimination of H2 gas at subambient temperature to form THF-stabilized metallacyclic IrIII silylene complexes, which were characterized in situ by NMR spectroscopy, trapped in minute amounts by reactive crystallization, and structurally characterized by XRD. Theoretical investigations (static DFT-D reaction-energy profiling, ETS-NOCV) support the promoting role of THF in the H2 elimination step and the consolidation of the Ir-to-Si interaction in the spontaneous (ΔG<0) formation of Ir silylenes in the presence of THF. Mechanistic insights indicate that the Ir silylene species arising from the [1 b]+ /phenylsilane system are relevant catalytic species in the hydrodefluorination of fluoroalkanes.
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A new way of introducing a N-heterocyclic carbene cap onto cyclodextrins has been devised. The benzimidazolium intermediates were found to behave as receptors towards cavity matching anions. The corresponding C1 - and C2 -symmetrical regioisomeric carbene gold(I) complexes have been tested in a benchmark asymmetric cycloisomerization of 1,6-enynes. Up to 50 % ee was achieved for the enantioselective cycloisomerization of N-allyl-4-methyl-N-(3-phenylprop-2-yn-1-yl)benzenesulfonamide.
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Herein we disclose the synthesis of original chiral scaffolds-ortho-orientated terphenyls presenting two atropisomeric Ar-Ar axes. These unusual structures were built up by using the C-H activation approach, and remarkably, both chiral axes were controlled with excellent stereoselectivity in a single transformation. During the reaction, not only does atroposelective functionalization of a biaryl precursor occur to establish one stereogenic axis, but an unprecedented atropo-stereoselective C-H arylation also takes place to generate the second stereogenic element. These enantiomerically pure ortho-terphenyls show an original tridimensional structure and thus constitute a unique foundation for building up a library of enantiomerically pure bidentate ligands, such as the new ligands S/N-Biax and diphosphine BiaxPhos.
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Stereoselective functionalization of aliphatic C-H bonds presents a great challenge. Following this target, we disclose herein an original strategy towards direct arylation of aliphatic chains at ß-methylene position based on a use of amide-sulfoxide bicoordinating directing group. Although moderate to high chiral induction (up to 9:1â d.r.) is achieved, diastereomerically pure compounds may be afforded by simple separation of diastereomeric products by silica gel chromatography. Accordingly, this reaction allows preparation of a large scope of high-value scaffolds in synthetically useful yields while recyclable character of our chiral auxiliary brings an additional benefit. A potential of this methodology to build up original molecules by sequential diarylation and expedient (two step) synthesis of a biologically active compound are further disclosed. Finally a first example of stereoselective direct acetoxylation of aliphatic chains is reported.
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The computation of metal-silyl interaction energies indicates the existence of situations in which the silyl group behaves as a Z-type ligand according to the Green method of covalent-bond classification. There is a scale of relative intrinsic silylicity Π, defined as the ratio of the intrinsic silyl-to-triflate interaction energy of a silyltriflate as a reference compound relative to the silyl-to-metal interaction of given complex, that can reveal in a straightforward manner the propensity of SiR3 groups to behave chemically as metal-bound "silylium" ions, namely, [SiR3 ]+ . Emblematic cases, either taken from the Cambridge Structural Database (CSD) or constructed for the purpose of this study, were also investigated from the viewpoints of extended transition-state natural orbitals for chemical valence (ETS-NOCV) and quantum theory of atoms in molecules (QTAIM) analyses. It is shown in the case of POBMUP-which is the iridium 1,3-bis[(di-tert-butylphosphino)oxy]benzene (POCOP) complex isolated by Brookhart etâ al.-how slight variations of molecular charge and structure can drastically affect the relative intrinsic silylicity of the SiEt3 group that is weakly bonded to the hydrido-iridium motif.
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The combination of an iridium(III) metallacycle and 1,3,5-trimethoxybenzene catalyses rapidly and selectively the reduction of esters to aldehydes at room temperature with high yields through hydrosilylation followed by hydrolysis. The ester reduction involves the trapping of transient silyl cations by the 1,3,5-trimethoxybenzene co-catalyst, supposedly by formation of an arenium intermediate whose role was addressed by DFT calculations.
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An original and recyclable chiral bidentate aniline-sulfoxide-based directing group has been developed. This auxiliary allows challenging stereoselective Pd-catalyzed direct functionalization of small cycloalkanes through C-aryl and C-alkyl bond formation. Although moderate diastereoselectivities are observed, both optically pure enantiomers of the highly functionalized products can be obtained separately by simple silica gel chromatography and cleavage of the chiral auxiliary. This strategy was further applied to the preparation of enantiomerically pure 1,2,3-trisubstituted cyclopropane carboxylic acid derivatives, with three stereogenic centers and bearing both alkyl and aromatic substituents. These molecular scaffolds are not yet reported in the literature. The synthetic utility of this approach is validated by the chiral auxiliary being readily cleaved and recovered posteriori to the C-H activation step, without deterioration of its optical purity. Finally, an unprecedented palladacycle intermediate generated through C-H activation of the cyclopropane moiety has been isolated and fully characterized. Initial DFT calculations shed additional light on the reactivity of this original intermediate.
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Self-aggregation in water of anti-cancer agents such as oxaliplatin (1) or its palladium-containing parent (2) is suspected to be the main reason for the exceptional resistance of concentrated infusions of these complexes to hydrolysis; this hypothesis, i.e. the self-association of metal chelates, was investigated in a systematic manner by experimental and theoretical means. (1)H diffusion-ordered NMR spectroscopy (DOSY NMR) and UV-visible absorption titration were inconclusive as to the formation of a dimer of 1 in water or DMSO. Further isothermal titration calorimetry (ITC) methods allowed the accurate determination of the enthalpy of formation of only the homodimer [2]2 and putative heterodimer [1·2] together with an estimation of the formation constants, which indicate that dimer formation is not a spontaneous process in solution, whereas electrospray ESI mass spectroscopy tends to suggest the contrary in the gas phase. A dispersion-corrected DFT method, i.e. DFT-D (BLYP-D3), was used to model the aggregation in solution (COSMO) and to investigate the assisting role of London force in the cohesion of bimolecular aggregates. The concordance of experimental and theoretical thermodynamic parameters was judged reasonably even though the treatment of solvation by conventional continuum models does not account for specific interactions of the solute with molecules of solvent; nonetheless these results outline the importance of dispersion, a.k.a. London force. The role of the latter was further stressed by computing the affinities of 1 and 2 for the lipophilic cavity of cucurbit[7]uril in modeled water (COSMO-RS), which were preliminarily determined experimentally by ITC methods using pure water as solvent. From our investigations carried out in pure water the connection between the notorious chemical stability of "concentrated" infusions of 1 in aqueous media and the formation of oligomers remains unsettled.
Assuntos
Antineoplásicos/química , Compostos Organoplatínicos/química , Calorimetria , Estrutura Molecular , Oxaliplatina , Soluções , TermodinâmicaRESUMO
Hemichelation is emerging as a new mode of coordination where non-covalent interactions crucially contribute to the cohesion of electron-unsaturated organometallic complexes. This study discloses an unprecedented demonstration of this concept to a Groupâ 9 metal, that is, Rh(I). The syntheses of new 14-electron Rh(I) complexes were achieved by choosing the anti-[(η(6):η(6)-fluorenyl){Cr(CO)3}2] anion as the ambiphilic hemichelating ligand, which was treated with [{Rh(nbd)Cl}2] (nbd=norbornadiene) and [{Rh(CO)2Cl}2]. The new T-shaped Rh(I) hemichelates were characterized by analytical and structural methods. Investigations using the methods of the DFT and electron-density topology analysis (NCI region analysis, QTAIM theory) confirmed the closed-shell, non-covalent and attractive characters of the interaction between the Rh(I) center and the proximal Cr(CO)3 moiety. This study shows that, by appropriate tuning of the electronic properties of the ambiphilic ligand, truly coordination-unsaturated Rh(I) complexes can be synthesized in a manageable form.
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A rational method of synthesis of stable neutral T-shaped 14 electron Pd and Pt complexes is proposed. It takes advantage of the ambiphilic character of the tricarbonyl(η(6)-indenyl)chromium anion, of which the main property is to behave as a hemichelating ligand, that is a nonconventional heteroditopic ligand capable of chelating a metal center by way of covalent and noncovalent bonding, thus preserving its unsaturated valence shell. The reaction of the in situ formed tricarbonyl(η(6)-2-methylindenyl)chromium anion with a series of Pd and Pt metallacycles afforded new air-stable and persistent synfacial heterobimetallic complexes in which the metallacycle binds the indenyl fragment via its metal in an η(1) fashion, leaving the fourth coordination site at the chelated metal virtually vacant. The structures of eight of these novel complexes are disclosed, and their bonding features are investigated by an array of theoretical methods based on the density functional theory (NBO, EDA, ETS-NOCV, AIM, NCI region analysis). Theory shows that the formation of these unusual structures of bimetallic synfacial η(1)-indenyl-Pd/Pt complexes is driven thermodynamically by attractive Coulombic occlusion of the fourth vacant coordination site at Pd/Pt centers by the Cr(CO)3 moiety.
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Highly fluxional, solution-persistent, and formally electron-deficient (32e(-)) binuclear Pd(II)-C(0) complexes of 2-methyl-1H-indene were synthesized and structurally characterized by X-ray diffraction analysis. DFT investigations combined with a number of theoretical analyses of the bond framework suggest that the polar intermetallic interaction possesses no major covalent character. Instead of bearing a static metal-metal bond as suggested by structural X-ray diffraction analysis, the complexes display in solution significant fluxionality through haptotropy, i.e., a formal "oscillation" of the Pd(η(3)-allyl) moiety between two limiting η(1)-indenyl configurations.