Ligand-Induced Intramolecular Redox Diversity in Titanium Complexes with Acenaphthene-1,2-diimine.

A series of the chlorido and alkoxychlorido titanium complexes of the general formula (dpp-Bian)Ti(OiPr)nCl3-n, where dpp-Bian = 1,2-bis[(2,6-iPr2C6H3)imino]acenaphthene n = 0 (2), 1 (3), 2 (4), as well as (dpp-Bian)Ti(OiPr)2 (5) and (dpp-Bian)Ti(OiPr)Cl3 (3-Cl), were isolated and characterized using single-crystal X-ray diffraction analysis and spectroscopic studies combined with density functional theory (DFT) calculations. In the solid state, compounds 2-4 reveal a square-pyramidal geometry at the metal center supported with monoanionic dpp-Bian, whereas 3-Cl with a neutral diimine ligand and 5 bearing a dianionic enebisamide dpp-Bian show, respectively, an octahedral and tetrahedral coordination surrounding the metal ion. Paramagnetic complexes 2-4 exhibit electron paramagnetic resonance spectra in both toluene solution and solid state, confirming the transfer of spin density from the metal ion to the dpp-Bian ligand as the number of alkoxy groups increases. The increase in polarity of the Ti-N bonds in the row 2 < 3 < 4 contributes to enhanced stability of the metal complexes with respect to O-donor molecules. Thus, in tetrahydrofuran (THF), compounds 2 and 3 undergo reversible solvolysis, whereas complex 4 is stable. The charge and spin density distributions as well as molecular orbital energies in 2-4 were analyzed on the basis of DFT calculations which also provided information on the electronic transition energies, absorption band assignments, and thermodynamic parameters of the reactions between the complexes and THF.

Effect of a single methyl substituent on the electronic structure of cobaltocene studied by computationally assisted MATI spectroscopy.

Metallocenes represent archetypical organometallic compounds playing key roles in various fields of fundamental and applied chemistry. Many of their unique properties arise from low ionization energies (IE) which can be tuned by introducing substituents into the rings. Here we report the first mass-analyzed threshold ionization (MATI) spectrum of a methylmetallocene, (Cp')(Cp)Co (Cp' = η5-C5H4Me, Cp = η5-C5H5). The presence of a single Me group allows us to study the "pure" effect of methylation without the mutual influence of substituents. The MATI technique provides an extremely high accuracy in determining the adiabatic IE of (Cp')(Cp)Co which equals 5.2097(6) eV. The effect of a Me group on the IE of cobaltocene appears to be 36% stronger than that in bis(η6-benzene)chromium. The MATI spectrum of (Cp')(Cp)Co shows a rich vibronic structure from which vibrational frequencies of the free ion are determined. This information provides a solid basis for testing the quality of quantum chemical calculations. Various levels of the DFT and coupled cluster computations are used to describe the structural and electronic transformations accompanying the detachment of an elctron from (Cp')(Cp)Co. New aspects of the methyl substituent influence on the potential energy surfaces, as well as on the inhomogeneous changes in charge density and electrostatic potential caused by ionization, are discussed.

X/Y platinum(II) complexes: some features of supramolecular assembly via halogen bonding.

Four series of new luminescent cyclometalated complexes [Pt(C^N)(IPy)Y] (HC^N = 2-phenylpyridine (Hppy), 2-(1-benzofuran-3-yl)pyridine (Hbfpy), methyl-2-phenylquinoline-4-carboxylate (Hmpqc), 2-(1-benzothiophen-3-yl)pyridine (Hbtpy), IPy = 4-iodopyridine, and Y = Cl, Br, I) have been investigated as X/Y 'building blocks' for the construction of a supramolecular network utilizing the I atom in IPy as a halogen bond (XB) donor (the X atom). The σ-hole of the X atom was found to provide non-covalent X⋯Y, X⋯Pt and X⋯π (π system of the metalated chelate ring) interactions for the complexes in the crystal state. NBO analysis confirms donation of the platinum electron density to iodine upon the X⋯Pt interaction. The nature of the X counterpart in XB depends on the nature of the Y atom and the cyclometalating ligand of the Pt(II) complex. DFT calculations show that the HOMO of [Pt(C^N)(IPy)Y] in the S0 state is delocalized over Pt, Y and a C-coordinating fragment of C^N, while the LUMO in most complexes is formed by the Py orbitals of IPy. However, the α-HOMO in the lowest triplet state of [Pt(C^N)(IPy)Y] contains no contribution of the IPy wavefunctions. All Pt(II) complexes exhibited triplet luminescence in solution and in the solid state (Φ up to 0.129), which is determined by the nature of the C^N ligand. The emission profile is independent of the nature of the ligand Y, while the quantum yield decreases from Cl to I. Accordingly, on the basis of DFT calculation, this emission is interpreted as a C^N intraligand charge transfer predominantly. The XB formation did not show an effect on the luminescence of the complexes in the solid phase, however grinding of crystals results in an increase of brightness.

An investigation into the Brønsted acidity of the perfluorinated alkoxy silanes {(F3C)3CO}3SiH and {(F6C5)3CO}2Si(Cl)H.

The perfluorinated alkoxy silanes {(F3C)3CO}3SiH (1) and {(F5C6)3CO}2Si(Cl)H (2) were prepared and fully characterized. Despite the high calculated Brønsted acidities, all attempts to deprotonate 1 and 2 to give the conjugate silanide ions failed due to the exceptionally short and strong Si-H bonds. In the solid state, the Si-H units are not involved in any intermolecular interactions, but instead the crystal packing consists of exceptionally short and strong F⋯F interactions. The cohesive energies are entirely comprised of London dispersion interactions, similarly as in the crystal structures of noble gases.

Praseodymium Metallacrown-Based NMR Probe for Enantioselective Discrimination of Mandelate Anions in Water.

Recently, the enhanced interest in water-soluble aminohydroximate Ln(III)-Cu(II) metallacrowns (MC) is largely due to their fascinating structural chemistry, diverse properties and ease of synthesis. We examined the water-soluble praseodymium(III) alaninehydroximate complex Pr(H2O)4[15-MCCu(II)Alaha-5]·3Cl (1) as a highly effective chiral lanthanide shift reagent for NMR analysis of the biologically relevant (R/S)-mandelate (MA) anions in aqueous media. The R-MA and S-MA enantiomers can be easily discriminated in the presence of small (1.2-6.2 mol %) amounts of MC 1 by the 1H NMR signals of multiple protons exhibiting an enantiomeric shift difference (ΔΔδ) of 0.06 ppm up to 0.31 ppm. Additionally, a possibility of coordination of MA to the metallacrown was investigated by the ESI-MS technique and a Density Functional Theory modeling of the molecular electrostatic potential and noncovalent interactions.

The reactivity of antimony and bismuth N,C,N-pincer compounds toward K[BEt3H] - the formation of heterocyclic compounds vs. element-element bonds vs. stable terminal Sb-H bonds.

The oxidative addition of CF3SO3CH2Si(CH3)3 (NpSiOTf) toward organopnictogen(I) N,C,N-pincer compounds, i.e. [2,6-(DippNCH)2C6H3]E (1-E, where E = Sb, Bi; Dipp = 2,6-iPr2C6H3) produced compounds [2,6-(DippNCH)2C6H3]E(NpSi)(OTf) (2-E, where E = Sb, Bi). By analogy, the in situ reduction of [2,6-(Me2NCH2)2C6H3]ECl2 (3-E, where E = Sb, Bi) followed by treatment with NpSiOTf or MeI gave compounds [2,6-(Me2NCH2)2C6H3]E(R)(X) (R/X = NpSi/OTf 4-E, where E = Sb, Bi; R/X = Me/I 5-Sb). The reactivity of these compounds toward 1 eq. of K[BEt3H] was examined showing remarkable differences depending both on the ligand backbone and the pnictogen used. Thus in the case of 2-E, the addition of the hydride across the imino-function was achieved thereby yielding azapnicta-heterocyclic compounds [2-(DippNCH2)-6-(DippNCH)C6H3]E(NpSi) (6-E, where E = Sb, Bi). The same reaction of 4-Bi produced dibismuthine {[2,6-(Me2NCH2)2C6H3]Bi(NpSi)}2 (7-Bi), but in the case of 4/5-Sb the analogous distibines {[2,6-(Me2NCH2)2C6H3]Sb(R)}2 (R = NpSi7-Sb, Me 8-Sb) were not formed directly and hydrides [2,6-(Me2NCH2)2C6H3]Sb(R)H (R = NpSi9-Sb, Me 10-Sb) could be isolated instead. Nevertheless, heating of both 9-Sb and 10-Sb led to an activation of a labile Sb-H bond and the formation of distibines 7/8-Sb.

Ionization of Decamethylmanganocene: Insights from the DFT-Assisted Laser Spectroscopy.

Metallocenes represent one of the most important classes of organometallics with wide prospects for practical use in various fields of chemistry, materials science, molecular electronics, and biomedicine. Many applications of these metal complexes are based on their ability to form molecular ions. We report the first results concerning the changes in the molecular and electronic structure of decamethylmanganocene, Cp*2Mn, upon ionization provided by the high-resolution mass-analyzed threshold ionization (MATI) spectroscopy supported by DFT calculations. The precise ionization energy of Cp*2Mn is determined as 5.349 ± 0.001 eV. The DFT modeling of the MATI spectrum shows that the main structural deformations accompanying the detachment of an electron consist in the elongation of the Mn-C bonds and a change in the Me out-of-plane bending angles. Surprisingly, the DFT calculations predict that most of the reduction in electron density (ED) upon ionization is associated with the hydrogen atoms of the substituents, despite the metal character of the ionized orbital. However, the ED difference isosurfaces reveal a complex mechanism of the charge redistribution involving also the carbon atoms of the molecule.

Beyond simple hetero Diels-Alder cycloadditions. A new type of element-ligand cooperativity at N,C,N-coordinated arsinidene and stibinidene centres in the reaction with an electron-deficient alkyne.

The reactivity of two types of organopnictogen(I) N,C,N-pincer ligand coordinated compound, i.e. [2,6-(DippNCH)2C6H3]E (1-E, where E = As, Sb, Bi; Dipp = 2,6-iPrC6H3) and [2-(DippNCH)-6-(DippNHCH2)C6H3]E (6-E, where E = As or Sb), toward an electron-deficient alkyne, i.e. dimethyl acetylenedicarboxylate (DMAD), is reported. All reactions represent remarkable examples of element-ligand cooperation (ELC). In the first step, all compounds react via dearomatization of a latent heteropnictole ring producing rare examples of hetero Diels-Alder (DA) adducts. These compounds then smoothly convert to 1-arsanaphthalenes via hydrogen migration, thereby recovering the aromatic 10π-electron system. Furthermore, in the case of bis(imino) derivatives of 1-E, heating of DA adducts in pyridine led to a hydrogenation of the triple bond of DMAD with the concomitant recovery of the univalent pnictinidene centre, which is in turn able to activate the second molecule of DMAD. In contrast, the non-symmetric derivative of 6-As upon heating in pyridine produced bicyclic trivalent arsenic compounds as a result of an attack of the pendant secondary NH group into the arsa-heterocyclic system. For 6-Sb, a remarkable stoichiometric hydrogenation of the DMAD molecule was observed by NMR spectroscopy involving the reductive elimination of dimethylfumarate in the final step of the reaction sequence. The whole study is accompanied by a theoretical survey that describes the main thermodynamic parameters of the reported reactions and explains the reaction pathways observed in the experiments.

Magnetically induced ring currents in metallocenothiaporphyrins.

The magnetically induced current-density susceptibility tensor (CDT) of the lowest singlet and triplet states of the metallocenothiaporphyrins, where the metal is V, Cr, Mn, Fe, Co, Ni, Mo, Tc, Ru, or Rh, have been studied with the gauge-including magnetically induced currents (GIMIC) method. The compounds containing V, Mn, Co, Tc or Rh were studied as cations because the neutral molecules have an odd number of electrons. The calculations show that the aromatic nature of most of the studied molecules follows the Hückel and Baird rules of aromaticity. CDT calculations on the high-spin states of the neutral metallocenothiaporphyrins with V, Mn, Co, Tc or Rh also shows that these molecules follow a unified extended Hückel and Baird aromaticity orbital-count rule stating that molecules with an odd number of occupied conjugated valence orbitals are aromatic, whereas molecules with an even number of occupied conjugated orbitals are antiaromatic.

Perfluorinated Trialkoxysilanol with Dramatically Increased Brønsted Acidity.

The Brønsted acidity of the perfluorinated trialkoxysilanol {(F3 C)3 CO}3 SiOH is more than 13 orders of magnitude higher than that of orthosilicic acid, Si(OH)4 , and even more for most previously known silanols. It is easily deprotonated by simple amines and pyridines to give the conjugate silanolates [OSi{OC(CF3 )3 }3 ]- , which possess extremely short Si-O bonds, comparable to those of silanones.

Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties.

A new monoiminoacenaphthenone 3,5-(CF3)2C6H3-mian (complex 2) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl2(dpp-mian)(CH3CN)] (3) and [VOCl(3,5-(CF3)2C6H3-bian)(H2O)][VOCl3(3,5-(CF3)2C6H3-bian)]·2.85DME (4) from [VOCl2(CH3CN)2(H2O)] (1) or [VCl3(THF)3]. The structure of all compounds was determined using X-ray structural analysis. The vanadium atom in these structures has an octahedral coordination environment. Complex 4 has an unexpected structure. Firstly, it contains 3,5-(CF3)2C6H3-bian instead of 3,5-(CF3)2C6H3-mian. Secondly, it has a binuclear structure, in contrast to 3, in which two oxovanadium parts are linked to each other through V=O···V interaction. This interaction is non-covalent in origin, according to DFT calculations. In structures 2 and 3, non-covalent π-π staking interactions between acenaphthene moieties of the neighboring molecules (distances are 3.36-3.40 Å) with an estimated energy of 3 kcal/mol were also found. The redox properties of the obtained compounds were studied using cyclic voltammetry in solution. In all cases, the reduction processes initiated by the redox-active nature of the mian or bian ligand were identified. The paramagnetic nature of complexes 3 and 4 has been proven by EPR spectroscopy. Complexes 3 and 4 exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The yields of products of cyclohexane oxidation were 43% (complex 3) and 27% (complex 4). Based on the data regarding the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play the most crucial role in the reaction. The initial products in the reactions with alkanes are alkyl hydroperoxides, which are easily reduced to their corresponding alcohols by the action of triphenylphosphine (PPh3). According to the DFT calculations, the difference in the catalytic activity of 3 and 4 is most likely associated with a different mechanism for the generation of ●OH radicals. For complex 4 with electron-withdrawing CF3 substituents at the diimine ligand, an alternative mechanism, different from Fenton's and involving a redox-active ligand, is assumed.

Lewis Superacidic Tellurenyl Cation-Induced Electrophilic Activation of an Inert Carborane.

The aryltellurenyl cation [2-(tBuNCH)C6 H4 Te]+ , a Lewis super acid, and the weakly coordinating carborane anion [CB11 H12 ]- , an extremely weak Brønsted acid (pKa =131.0 in MeCN), form an isolable ion pair complex [2-(tBuNCH)C6 H4 Te][CB11 H12 ], in which the Brønsted acidity (pKa 7.4 in MeCN) of the formally hydridic B-H bonds is dramatically increased by more than 120 orders of magnitude. The electrophilic activation of B-H bonds in the carborane moiety gives rise to a proton transfer from boron to nitrogen at slightly elevated temperatures, as rationalized by the isolation of a mixture of the zwitterionic isomers 12- and 7-[2-(tBuN{H}CH)C6 H4 Te(CB11 H11 )] in ratios ranging from 62 : 38 to 80 : 20.

Laser spectroscopic and computational insights into unexpected structural behaviours of sandwich complexes upon ionization.

Transition-metal sandwich complexes play key roles in various fields such as fundamental and applied chemistry; many of their unique properties arise from their ability to form stable or reactive ions. The first mass-analyzed threshold ionization (MATI) spectra of mixed sandwich compounds, (Ch)(Cp)Cr and (Cot)(Cp)Ti (Ch = η7-C7H7, Cp = η5-C5H5, Cot = η8-C8H8), presented in this work provide an extremely accurate description of the electron detachment. The ionization energies of the neutrals and stabilization energies of the metal-ligand interactions upon ionization are derived from the MATI data with an accuracy of 0.0006 eV. In combination with DFT calculations, laser threshold ionization spectroscopy reveals surprisingly different structural variations accompanying the detachment of the non-bonding dz2 electron from the sandwich molecules. The geometry of (Ch)(Cp)Cr remains practically unchanged while the ionization of (Cot)(Cp)Ti causes a noticeable shortening of the inter-ring distance, similar to that resulting from the ionization of a typical antibonding orbital. Electron density analysis throws light on the nature of these amazing effects.

Reversible Addition of Carbon Dioxide to Main Group Metal Complexes at Temperatures about 0 °C.

The reaction of dialane [LAl-AlL] (1; L=dianion of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene, dpp-bian) with carbon dioxide results in two different products depending on solvent. In toluene at temperatures of about 0 °C, the reaction gives cycloadduct [L(CO2 )Al-Al(O2 C)L] (2), whereas in diethyl ether, the reaction affords oxo-bridged carbamato derivative [L(CO2 )(Et2 O)Al(µ-O)AlL] (3). The DFT and QTAIM calculations provide reasonable explanations for the reversible formation of complex 2 in the course of two subsequent (2+4) cycloaddition reactions. Consecutive transition states with low activation barriers were revealed. Also, the DFT study demonstrated a crucial effect of diethyl ether coordination to aluminium on the reaction of dialane 1 with CO2 . The optimized structures of key intermediates were obtained for the reactions in the presence of Et2 O; calculated thermodynamic parameters unambiguously testify the irreversible formation of the product 3.

Metal-Organic Frameworks Derived from Calcium and Strontium Complexes of a Redox-Active Ligand.

The reactions of monomeric [(dpp-Bian)M(thf)4] (M = Ca (1a), Sr (1b); dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with 4,4'-bipyridyl (4,4'-bipy) proceed with electron transfer from dpp-Bian2- to 4,4'-bipy0 to afford calcium and strontium complexes containing simultaneously radical-anionic dpp-Bian- and 4,4'-bipy- ligands. In tetrahydrofuran (thf) the reactions result in 1D coordination polymers [{(dpp-Bian)M(4,4'-bipy)(thf)2}·4thf]n (M = Ca (2a), Sr (2b)), while in a thf/benzene mixture the reaction between 1a and 4,4'-bipy affords the 2D metal-organic framework [{(dpp-Bian)Ca(4,4'-bipy)2}·2thf·2C6H6]n (3). The structures of compounds 2a,b and 3 have been determined by single-crystal X-ray analyses. The presence of the ligand-localized unpaired electrons allows the use of ESR spectroscopy for characterization of the compounds 2a,b and 3. DFT calculations of model calcium complexes with the dpp-Bian, 4,4'-bipy, and thf ligands confirm the energetically favorable open-shell configurations of the molecules bearing the 4,4'-bipy fragments. The magnetic susceptibility measurements confirm the presence of two unpaired electrons per monomeric unit in 2a,b and 3. The thermal stability of compounds 2a,b and 3 was studied by thermogravimetric analysis (TGA). To the best of our knowledge, 3 is the first MOF simultaneously containing two different paramagnetic bridging ligands inside the framework.

Low-coordinate Sm(II) and Yb(II) complexes derived from sterically-hindered 1,2-bis(imino)acenaphthene (ArBIG-bian).

Reduction of ArBIG-bian (1, 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene) with an excess of samarium in tetrahydrofuran (thf) and crystallization of the crude product from a thf/toluene mixture affords [(ArBIG-bian)Sm]·C7H8 (2a), which is free of the coordinating solvent. The use of 1,2-dimethoxyethane (dme) as the reaction medium resulted in the same product, [(ArBIG-bian)Sm]·C4H10O2 (2b), which differs from 2a only in the crystal lattice solvent. Reduction of 1 with an excess of ytterbium in dme gives compound [(ArBIG-bian)Yb(dme)]·2.5C7H8 (3), containing a coordinated dme molecule. All three products consist of dianionic ArBIG-bian ligands whose bulky 2,6-(Ph2CH)2-4-Me-C6H2 groups shield effectively the metal atoms. The newly prepared compounds 2a, 2b and 3 were characterized by 1H NMR and IR spectroscopy. The molecular structures of complexes 2a, 2b and 3 have been established by single crystal X-ray analysis. The intramolecular interactions were analysed on the basis of DFT calculations. The temperature dependence of the magnetic susceptibility of 2b and 3 in the region of 2-300 K was studied. The magnetic moments of complex 2b correspond to divalent samarium.

Water-Soluble Bismuth(III) Polynuclear Tyrosinehydroximate Metallamacrocyclic Complex: Structural Parallels to Lanthanide Metallacrowns.

Recently there has been a great deal of interest and associated research into aspects of the coordination chemistry of lanthanides and bismuth-elements that show intriguing common features. This work focuses on the synthesis and characterization of a novel bismuth(III) polynuclear metallamacrocyclic complex derived from aminohydroxamic acid, in order to compare the coordination ability of Bi3+ with the similarly sized La3+ ions. A polynuclear tyrosinehydroximate Bi(OH)[15-MCCu(II)Tyrha-5](NO3)2 (1) was obtained according to the synthetic routes previously described for water-soluble Ln(III)-Cu(II) 15-MC-5 metallacrowns. Correlations between structural parameters of Bi(III) and Ln(III) complexes were analyzed. DFT calculations confirmed the similarity between molecular structures of the model bismuth(III) and lanthanum(III) tyrosinehydroximate 15-metallacrowns-5. Analysis of the electronic structures revealed, however, stronger donor-acceptor interactions between the central ion and the metallamacrocycle in the case of the lanthanum analogue. Thermochromic properties of 1 were studied.

Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays.

OLED technology beyond small or expensive devices requires light-emitters, luminophores, based on earth-abundant elements. Understanding and experimental verification of charge transfer in luminophores are needed for this development. An organometallic multicore Cu complex comprising Cu-C and Cu-P bonds represents an underexplored type of luminophore. To investigate the charge transfer and structural rearrangements in this material, we apply complementary pump-probe X-ray techniques: absorption, emission, and scattering including pump-probe measurements at the X-ray free-electron laser SwissFEL. We find that the excitation leads to charge movement from C- and P- coordinated Cu sites and from the phosphorus atoms to phenyl rings; the Cu core slightly rearranges with 0.05 Å increase of the shortest Cu-Cu distance. The use of a Cu cluster bonded to the ligands through C and P atoms is an efficient way to keep structural rigidity of luminophores. Obtained data can be used to verify computational methods for the development of luminophores.

A planar binuclear cobalt(ii) phthalocyanine as a highly efficient catalyst for the oxidation of a mercaptan.

This paper reports on a binuclear Co(ii)Pc which exhibits a previously unknown extremely high catalytic activity for the oxidation of a thiol to the corresponding disulfide. The high activity is explained by an electronic contact between the two Co centres in the complex.

Substituent effects on the electronic structures of sandwich compounds: new understandings provided by DFT-assisted laser ionization spectroscopy of bisarene complexes.

Recent advances on substituent effects in transition metal bisarene complexes studied with high-resolution threshold ionization spectroscopy are reviewed to demonstrate new aspects of the ligand influence on electronic structures of sandwich molecules. Unprecedented accuracy in the determination of ionization energies provided by the laser techniques makes it possible to reveal and describe quantitatively such fine phenomena as isotope effects, the mutual substituent influence or variations of substituent effects on replacing the central metal atom with its Group analogues. In combination with DFT calculations, laser ionization spectroscopy unveils mechanisms of the ligand influence on unique redox properties of sandwich complexes which are of key importance for their practical use.