The nature of structure and bonding between transition metal and mixed Si‐Ge tetramers: A 20‐electron superatom system

A novel superatom species with 20‐electron system, Si_xGe_yM⁺ (x + y = 4; M = Nb, Ta), was properly proposed. The trigonal bipyramid structures for the studied systems were identified as the putative global minimum by means of the density functional theory calculations. The high chemical stability can be explained by the strong p‐d hybridization between transition metal and mixed Si‐Ge tetramers, and closed‐shell valence electron configuration [1S²1P⁶2S²1D¹⁰]. Meanwhile, the chemical bondings between metal atom and the tetramers can be recognized by three localized two‐center two‐electron (2c‐2e) and delocalized 3c‐2e σ‐bonds. For all the doped structures studied here, it was found that the π‐ and σ‐electrons satisfy the 2(N + 1)² counting rule, and thus these clusters possess spherically double (π and σ) aromaticity, which is also confirmed by the negative nucleus‐independent chemical shifts values. Consequently, all the calculated results provide a further understanding for structural stabilities and electronic properties of transition metal‐doped semiconductor clusters. © 2016 Wiley Periodicals, Inc.     

Structural Changes in 2‐Diarylthiophene‐Substituted Starburst Compounds upon Charging: A Theoretical and Spectroelectrochemical Study

The role of charging in structural changes of 2‐diarylaminothiophene‐substituted starburst compounds is clarified by combining theoretical and spectroelectrochemical studies. A systematic and comparative theoretical calculation based on density functional theory and semiempirical Austin Model 1 (AM1) calculations is performed on the neutral and charged states of four model tris(5‐diarylamino‐5‐thienyl)‐terminated starburst compounds with a central triphenylamine and 1,3,5‐triphenylbenzene moiety. Our results indicate that the charging of molecules leads to structural changes by quinoid‐type components mostly on the dendrimers terminated by phenothiazinyl fragments. Based on the optimal geometries, the spectroscopic properties were calculated using the semiempirical Zerner’s intermediate neglect overlap method. The presented theoretical results and the spin electron distributions of charged states and their spectra are supported by the spectroelectrochemical observations caused by the different electron localization within the studied molecules after charging. The satisfactory agreement between theoretical electronic transitions and experimental values indicates that a rational design of tunable molecular layers in organic devices based on the starburst compounds described is possible.     

Palladium‐Catalyzed Cyclopropanation of Alkenyl Silanes by Diazoalkanes: Evidence for a Pd0 Mechanism

Pd ⁰ does the trick! Alkenyl silanes are efficiently cyclopropanated by diazoalkanes at low Pd loadings (see scheme). Clear evidence for the involvement of a Pd⁰ resting state for this reaction is given.

     

The Geometric Structure of Silver‐Doped Silicon Clusters

Cationic silver‐doped silicon clusters, Si_nAg⁺ (n=6–15), are studied using infrared multiple photon dissociation in combination with density functional theory computations. Candidate structures are identified using a basin‐hopping global optimizations method. Based on the comparison of experimental and calculated IR spectra for the identified low‐energy isomers, structures are assigned. It is found that all investigated clusters have exohedral structures, that is, the Ag atom is located at the surface. This is a surprising result because many transition‐metal dopant atoms have been shown to induce the formation of endohedral silicon clusters. The silicon framework of Si_nAg⁺ (n=7–9) has a pentagonal bipyramidal building block, whereas the larger Si_nAg⁺ (n=10–12, 14, 15) clusters have trigonal prism‐based structures. On comparing the structures of Si_nAg⁺ with those of Si_nCu⁺ (for n=6–11) it is found that both Cu and Ag adsorb on a surface site of bare Si_n⁺ clusters. However, the Ag dopant atom takes a lower coordinated site and is more weakly bound to the Si_n⁺ framework than the Cu dopant atom.     

Hydroxo‐Bridged Dimers of Oxo‐Centered Ruthenium(III) Triangle: Synthesis and Spectroscopic and Theoretical Investigations

The homometallic hexameric ruthenium cluster of the formula [Ru^III₆(μ₃‐O)₂(μ‐OH)₂((CH₃)₃CCO₂)₁₂(py)₂] ( 1 ) (py=pyridine) is solved by single‐crystal X‐ray diffraction. Magnetic susceptibility measurements performed on 1 suggest that the antiferromagnetic interaction between the Ru^III centers is dominant, and this is supported by theoretical studies. Theoretical calculations based on density functional methods yield eight different exchange interaction values for 1 : J₁=?737.6, J₂=+63.4, J₃=?187.6, J₄=+124.4, J₅=?376.4, J₆=?601.2, J₇=?657.0, and J₈=?800.6 cm^?1. Among all the computed J values, six are found to be antiferromagnetic. Four exchange values (J₁, J₆, J₇ and J₈) are computed to be extremely strong, with J₈, mediated through one μ‐hydroxo and a carboxylate bridge, being by far the largest exchange obtained for any transition‐metal cluster. The origin of these strong interactions is the orientation of the magnetic orbitals in the Ru^III centers, and the computed J values are rationalized by using molecular orbital and natural bond order analysis. Detailed NMR studies (¹H, ¹³C, HSQC, NOESY, and TOCSY) of 1 (in CDCl₃) confirm the existence of the solid‐state structure in solution. The observation of sharp NMR peaks and spin‐lattice time relaxation (T1 relaxation) experiments support the existence of strong intramolecular antiferromagnetic exchange interactions between the metal centers. A broad absorption peak around 600–1000 nm in the visible to near‐IR region is a characteristic signature of an intracluster charge‐transfer transition. Cyclic voltammetry experiments show that there are three reversible one‐electron redox couples at ?0.865, +0.186, and +1.159 V with respect to the Ag/AgCl reference electrode, which corresponds to two metal‐based one‐electron oxidations and one reduction process.     

A Theoretical DFT‐Based and Experimental Study of the Transmetalation Step in Au/Pd‐Mediated Cross‐Coupling Reactions

In this work a combined theoretical and experimental investigation of the cross‐coupling reaction involving two metallic reaction centers, namely gold and palladium, is described. One metal center (Au) hereby is rather inert towards change in its oxidation state, whereas Pd undergoes oxidative insertion and reductive elimination steps. Detailed mechanistic and energetic studies of each individual step, with the focus on the key transmetalation step are presented and compared for different substrates and ligands on the catalytic Pd center. Different aryl halides (Cl, Br, I) and aryl triflates were investigated. Hereby the nature of the counteranion X turned out to be crucial. In the case of X=Cl and L=PMe₃ the oxidative addition is rate‐determining, whereas in the case of X=I the transmetalation step becomes rate‐determining in the Au/Pd‐cross‐coupling mechanism. A variety of Au–Pd transmetalation reaction scenarios are discussed in detail, favoring a transition state with short intermetallic Au–Pd contacts. Furthermore, without a halide counteranion the transmetalation from gold(I) to palladium(II) is highly endothermic, which confirms our experimental findings that the coupling does not occur with aryl triflates and similar weakly coordinating counteranions—a conclusion that is essential in designing new Au–Pd catalytic cycles. In combination with experimental work, this corrects a previous report in the literature claiming a successful coupling potentially catalytic in both metals with weakly coordinating counteranions.     

The Quest for Photoswitches Activated by Near‐Infrared Light: A Theoretical Study of the Photochemistry of BF2‐Coordinated Azo Derivatives

Recently synthesized BF₂‐coordinated azo derivatives have been proposed as photoswitches that operate in the optical window (λ=600–1200 nm) for use in bioimaging applications. Herein, we have theoretically analyzed these compounds and modified some substituents to analyze which properties of the molecule govern its photochemistry. Our results compare rather well with the available experimental data, so our methodology, based on density functional theory (DFT) calculations for the ground electronic state and time‐dependent‐DFT for the first excited electronic state, is validated. Through systematic modification of different substituents of the parent system, we designed compounds that are predicted to operate fully within the optical window. We also analyzed several molecules for which the cis isomer is the more stable isomer, a quite unusual result for azobenzene derivatives that is a much coveted property for some applications of these photoactive molecules in pharmacology. Our results also provide insight into other properties relevant for photoswitches, such as the thermal stability of the less stable isomer and the magnitude of the gap between the wavelengths of the radiation that activates each isomerization process, which must be as large as possible to improve the yield of each photoisomerization. From a more general perspective, our results may provide a step towards the rational design of new photoswitches that fulfill a set of desired characteristics.     

Syntheses,Optical Properties,and Theoretical Investigation of Silafluorenes and Spirobisilafluorenes Bearing Electron‐Donating Aminostyryl Arms around a Silafluorene Core

π‐Extended silafluorenes and spirobisilafluorenes bearing electron‐donating aminostyryl substituents at the 2,7‐ or 3,6‐positions were synthesized by a Horner–Wadsworth–Emmons reaction. The electronic influence of spirocyclic structure and substitution mode of the aminostyryl substituents was investigated by UV/Vis spectroscopy, which indicated the existence of a spiroconjugation effect in the 3,6‐substituted spirobisilafluorene. They exhibited moderate to strong fluorescence emission, and the fluorescence properties were compatible with the UV/Vis absorption characteristics, except for the 3,6‐substituted spirobisilafluorene, which showed relatively large enhancement of fluorescence quantum yield and Stokes shift. The influence of the spirocyclic structure and substitution mode on the photophysical properties of the silicon compounds was investigated by DFT calculations.     

A Theoretical Study of the Interaction of Hydrogen and Oxygen with Palladium or Gold Adsorbed on Pyridine‐Like Nitrogen‐Doped Graphene

The interaction of H₂ and O₂ molecules in the presence of nitrogen‐doped graphene decorated with either a palladium or gold atom was investigated by using density functional theory. It was found that two hydrogen molecules were adsorbed on the palladium atom. The interaction of these adsorbed hydrogen molecules with two oxygen molecules generates two hydrogen peroxide molecules first through a Eley–Rideal mechanism and then through a Langmuir–Hinshelwood mechanism. The barrier energies for this reaction were small; therefore, we expect that this process may occur spontaneously at room temperature. In the case of gold, a single hydrogen molecule is adsorbed and dissociated on the metal atom. The interaction of the dissociated hydrogen molecule on the surface with one oxygen molecule generates a water molecule. The competitive adsorption between oxygen and hydrogen molecules slightly favors oxygen adsorption.     

Regioselectivity Control in the Metal‐Catalyzed Functionalization of γ‐Allenols,Part 2: Theoretical Study

Calculating cyclization : Theoretical work directed towards the elucidation of the mechanisms of the gold‐, palladium‐, and lanthanum‐catalyzed oxycyclizations (5‐exo versus 6‐endo versus 7‐endo) of γ‐allenols has been pursued in close relationship with the experimental study (Part 1, accompanying paper) and has corroborated the bench results to provide a complete study of the reactivity of γ‐allenols under different metal‐catalyzed conditions.

     

Unexpected reaction of the unsaturated cluster host and catalyst [Pd3(mu3-CO)(dppm)3]2+ with the hydroxide ion: spectroscopic and kinetic evidence of an inner-sphere mechanism

The title cluster, [Pd(3)(mu(3)-CO)(dppm)(3)](2+) (dppm=bis(diphenylphosphino)methane), reacts with one equivalent of hydroxide anions (OH(-)), from tetrabutylammonium hydroxide (Bu(4)NOH), to give the paramagnetic [Pd(3)(mu(3)-CO)(dppm)(3)](+) species. Reaction with another equivalent of OH(-) leads to the zero-valent compound [Pd(3)(mu(3)-CO)(dppm)(3)](0). From electron paramagnetic resonance analysis of the reaction medium using the spin-trap agent 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), the 2-tetrahydrofuryl or methyl radicals, deriving from the tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO) solvent, respectively, were detected. For both [Pd(3)(mu(3)-CO)(dppm)(3)](2+) and [Pd(3)(mu(3)-CO)(dppm)(3)](+), the mechanism involves, in a first equilibrated step, the formation of a hydroxide adduct, [Pd(3)(mu(3)-CO)(dppm)(3)(OH)]((n-1)+) (n=1, 2), which reacts irreversibly with the solvent. The kinetics were resolved by means of stopped-flow experiments and are consistent with the proposed mechanism. In the presence of an excess of Bu(4)NOH, an electrocatalytic process was observed with modest turnover numbers (7-8). The hydroxide adducts [Pd(3)(mu(3)-CO)(dppm)(3)(OH)]((n-1)+) (n=1, 2), which bear important similarities to the well-known corresponding halide adducts [Pd(3)(mu(3)-CO)(dppm)(3)(mu(3)-X)](n) (X=Cl, Br, I), have been studied by using density functional theory (DFT). Although the optimised geometry for the cluster in its +2 and 0 oxidation states (i.e., cation and anion clusters, respectively) is the anticipated mu(3)-OH form, the paramagnetic species, [Pd(3)(mu(3)-CO)(dppm)(3)(OH)](0), shows a mu(2)-OH form; this suggests an important difference in electronic structure between these three species.     

Unprecedented Electron‐Poor Octahedral Ta6 Clusters in a Solid‐State Compound: Synthesis,Characterisations and Theoretical Investigations of Cs2BaTa6Br15O3

The crystal structure of Cs₂BaTa₆Br₁₅O₃ has been elucidated by using synchrotron X‐ray powder diffraction and absorption experiments. It is built from edge‐bridged octahedral [(Ta₆${{\rm Br}{{{\rm i}\hfill \atop 9\hfill}}}$ ${{\rm O}{{{\rm i}\hfill \atop 3\hfill}}}$ )${{\rm Br}{{{\rm a}\hfill \atop 6\hfill}}}$ ]^4? cluster units with a singular poor metallic electron (ME) count equal to thirteen. This leads to a paramagnetic behaviour related to one unpaired electron. The arrangement of the Ta₆ clusters is similar to that of Cs₂LaTa₆Br₁₅O₃ exhibiting 14‐MEs per [(Ta₆${{\rm Br}{{{\rm i}\hfill \atop 9\hfill}}}$ ${{\rm O}{{{\rm i}\hfill \atop 3\hfill}}}$ )${{\rm Br}{{{\rm a}\hfill \atop 6\hfill}}}$ ]^5? motif. The poorer electron‐count cluster presents longer metal–metal distances as foreseen according to the electronic structure of edge‐bridged hexanuclear cluster. Density functional theory (DFT) calculations on molecular models were used to rationalise the structural properties of 13‐ and 14‐ME clusters. Periodic DFT calculations demonstrate that the electronic structure of these solid‐state compounds is related to those of the discrete octahedral units. Oxygen–barium interactions seem to prevent the geometry of the octahedral cluster to strongly distort, allowing stabilisation of this unprecedented electron‐poor Ta₆ cluster in the solid state.     

Control over the Chemoselectivity of Pd‐Catalyzed Cyclization Reactions of (2‐Iodoanilino)carbonyl Compounds

The factors that control the chemoselectivity of palladium‐catalyzed cyclization reactions of (2‐iodoanilino)carbonyl compounds have been explored by an extensive experimental computational (DFT) study. It was found that the selectivity of the process, that is, the formation of fused six‐ versus five‐membered rings, can be controlled by the proper selection of the initial reactant, reaction conditions, and additives. Thus, esters or amides produce ketones by a nucleophilic addition process, whereas the addition of PhO^? ions leads to the formation of indolines by an α‐arylation reaction. In contrast, the corresponding ketone reactants yield a mixture of both reaction products, the ratio of which depends on the base used, in the presence of phenol. The outcome of the processes can be explained by the formation of a common four‐membered palladacycle intermediate from which the competitive nucleophilic addition and α‐arylation reactions occur. The remarkable effect of phenol in the process, which makes the α‐arylation reaction easier, favored the formation of enol complexes, which are stabilized by an intramolecular hydrogen bond between the hydroxy group of the enol moiety and the oxygen atom of the phenoxy ligand. Moreover, the chemoselectivy of the process can be also controlled by the addition of bidendate ligands that lead to the almost exclusive formation of indoles at expenses of the corresponding alcohols.     

Ionic‐Radius‐Driven Selection of the Main‐Group‐Metal Cage for Intermetalloid Clusters [Ln@PbxBi14−x]q− and [Ln@PbyBi13−y]q− (x/q=7/4, 6/3; y/q=4/4, 3/3)

Reactions of the binary, pseudo‐homoatomic Zintl anion (Pb₂Bi₂)^2? with Ln(C₅Me₄H)₃ (Ln=La, Ce, Nd, Gd, Sm, Tb) in the presence of [2.2.2]crypt in ethane‐1,2‐diamine/toluene yielded ten [K([2.2.2]crypt)]⁺ salts of lanthanide‐doped semimetal clusters with 13 or 14 surface atoms. Single‐crystal X‐ray diffraction and energy‐dispersive X‐ray spectroscopy indicated the presence of the anions [Ln@Pb₆Bi₈]^3?, [Ln@Pb₃Bi₁₀]^3?, [Ln@Pb₇Bi₇]^4?, or [Ln@Pb₄Bi₉]^4? in single or double salts; the latter showed various ratios of the components in the solid state. The anions are the first ternary intermetalloid clusters comprising only elements of the sixth period of the periodic table, namely, Pb, Bi and lanthanides. This study, which was complemented by ESI mass spectrometry and ¹³⁹La NMR spectroscopy in solution, rationalizes a continuous development of the ratio of 13:14‐atom cages with the ionic radius of the embedded Ln³⁺ ion, which seems to select the most suitable cage type. Quantum chemical investigations helped to analyze this situation in more detail and to explain the observed subtle influence of the atomic radii. Magnetic measurements confirmed that the embedded Ln³⁺ ions keep their expected paramagnetic or diamagnetic nature.