Ab Initio energetics of Si?O bond cleavage

A multilevel approach that combines high‐level ab initio quantum chemical methods applied to a molecular model of a single, strain‐free Si O Si bridge has been used to derive accurate energetics for Si O bond cleavage. The calculated Si O bond dissociation energy and the activation energy for water‐assisted Si O bond cleavage of 624 and 163 kJ mol⁻¹, respectively, are in excellent agreement with values derived recently from experimental data. In addition, the activation energy for H₂O‐assisted Si O bond cleavage is found virtually independent of the amount of water molecules in the vicinity of the reaction site. The estimated reaction energy for this process including zero‐point vibrational contribution is in the range of −5 to 19 kJ mol⁻¹. © 2017 Wiley Periodicals, Inc.     

Synthesis and properties of new Si?H-containing polymers

Poly[(methylsilylene)ethynylene] ( 1 ) and poly[2,5-thiophenediyl(methylsilylene)] ( 2 ) are prepared in good yields. Thermogravimetric analysis and differential scanning calorimetry indicate the Si H group to increase the pyrolysis residue yields. Gelation was achieved from polymer 1 to get improved preceramic materials. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2275–2282, 1998     

Heterocyclizations of hydroxyketones with two‐coordinated (trimethylsilylamino)phosphines, (Me3Si)2N?PE?SiMe3

The reaction of two‐coordinated (trimethylsilylamino)phosphines (Me₃Si)₂N PE SiMe₃ 1 (E = N) and 2 (E = CH) with hydroxycarbonyl compounds proceeded with four‐ or five‐member heterocyclization to yield derivatives of oxaphosphetane, oxaphospholanes, and oxaphospholes. The reaction rate depends on the structure of hydroxyketones as well as on the type of the two‐coordinated phosphorus compound in accordance with the polarity of the P=N and P=C bonds. Thus, reaction was completed in 30 min in the case of the ortho carbonyl phenoxy derivatives with the phosphine 1 , but required 2 h in the case of the alkyl hydroxy carbonyls. All reactions with the phosphine 2 took about 24 h. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:413–417, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20033     

Nitridsulfidchloride der Lanthanide: II. Der Formeltyp M6N3S4Cl (M = La?Nd)

Nitride Sulfide Chlorides of the Lanthanides. II. The Composition M₆N₃S₄Cl (M = La? Nd) The oxidation of the “light” lanthanides (M = La? Nd) with sulfur and NaN₃ in the presence of the chlorides MCl₃ yields chlorine-poor nitride sulfide chlorides with the composition M₆N₃S₄Cl when appropriate molar ratios of the reactants are used. Additional NaCl as a flux secures complete and fast reactions (7 d) at 850°C in evacuated silica vessels as well as single-crystalline products (red-brown needles). The crystal structure was determined from X-ray single crystal data for the limiting representatives La₆N₃S₄Cl (orthorhombic, Pnma (no. 62), Z = 4, a = 1159.7(4), b = 410.95(7), c = 2756.8(9)pm, R = 0.030, R_w = 0.027) and Nd₆N₃S₄Cl (a = 1137.1(3), b = 399.34(6), c = 2687.6(9)pm, R = 0.034, R_w = 0.033). Guinier powder data revealed the cerium and praseodymium analogues to be isotypic. The crystal structure exhibits two different chains of connected [NM₄] tetrahedra which are commensurate in translation. Six crystallographically different M³⁺ are present, two of them (M1 and M2) build up the chain [(N1)(M1) · (M2)]³⁺ together with (N1)^3? by cis-edge connection of tetrahedra. The four remainders (M3? M6) arrange as pairs [N₂M₆] of edge-shared [NM₄] tetrahedra with (N2)^3? and (N3)^3? which are further connected via four vertices to form the [(M5)(N-2){(M3)_(1+1)/(1+1)(M4)_(1+1)/(1+1))}^e(N3)(M6)]⁶⁺ double chain. Bundled along [010] like a closest packing of rods, both types of chains are held together by five crystallographically different but by X-ray diffraction indistinguishable anions S^2? (S1? S4) and Cl^? adjusting the charge balance in a molar ratio of 4:1.     

Direct Evidence for Intermolecular Oxidative Addition of σ(Si?Si) Bonds to Gold

Oxidative addition plays a major role in transition‐metal catalysis, but this elementary step remains very elusive in gold chemistry. It is now revealed that in the presence of GaCl₃, phosphine gold chlorides promote the oxidative addition of disilanes at low temperature. The ensuing bis(silyl) gold(III) complexes were characterized by quantitative ³¹P and ²⁹Si NMR spectroscopy. Their structures (distorted Y shape) and the reaction profile of σ(Si Si) bond activation were analyzed by DFT calculations. These results provide evidence for the intermolecular oxidative addition of σ(Si Si) bonds to gold and open promising perspectives for the development of new gold‐catalyzed redox transformations.     

Homolytic S?S Bond Dissociation of 11 Bis(thiocarbonyl)disulfides R‐C(S)?S?S?C(S)R and Prediction of A Novel Rubber Vulcanization Accelerator

The structures and energetics of eight substituted bis(thiocarbonyl)disulfides (RCS₂)₂, their associated radicals RCS₂^., and their coordination compounds with a lithium cation have been studied at the G3X(MP2) level of theory for R=H, Me, F, Cl, OMe, SMe, NMe₂, and PMe₂. The effects of substituents on the dissociation of (RCS₂)₂ to RCS₂^. were analyzed using isodesmic stabilization reactions. Electron‐donating groups with an unshared pair of electrons have a pronounced stabilization effect on both (RCS₂)₂ and RCS₂^.. The S? S bond dissociation enthalpy of tetramethylthiuram disulfide (TMTD, R=NMe₂) is the lowest in the above series (155 kJ mol^?1), attributed to the particular stability of the formed Me₂NCS₂^. radical. Both (RCS₂)₂ and the fragmented radicals RCS₂^. form stable chelate complexes with a Li⁺ cation. The S? S homolytic bond cleavage in (RCS₂)₂ is facilitated by the reaction [Li(RCS₂)₂]⁺+Li⁺→2 [Li(RCS₂)]^.+. Three other substituted bis(thiocarbonyl) disulfides with the unconventional substituents R=OSF₅, Gu¹, and Gu² have been explored to find suitable alternative rubber vulcanization accelerators. Bis(thiocarbonyl)disulfide with a guanidine‐type substituent, (Gu¹CS₂)₂, is predicted to be an effective accelerator in sulfur vulcanization of rubber. Compared to TMTD, (Gu¹CS₂)₂ is calculated to have a lower bond dissociation enthalpy and smaller associated barrier for the S? S homolysis.     

M4(CH2)4 Cubane‐Type Rare‐Earth Methylidene Complexes: Unique Reactivity toward Unsaturated C?O,C?N,and C?S Bonds

The reactivity of the cubane‐type rare‐earth methylidene complex [Cp′Lu(μ₃‐CH₂)]₄ ( 1 , Cp′=C₅Me₄SiMe₃) with various unsaturated electrophiles was investigated. The reaction of 1 with CO (1 atm) at room temperature gave the bis(ketene dianion)/dimethylidene complex [Cp′₄Lu₄(μ₃‐CH₂)₂(μ₃,η²‐O‐C?CH₂)₂] ( 2 ) in 86 % yield through the insertion of two molecules of CO into two of the four lutetium–methylidene units. In the reaction with the sterically demanding N,N‐diisopropylcarbodiimide at 60 °C, only one of the four methylidene units in 1 reacted with one molecule of the carbodiimide substrate to give the mono(ethylene diamido)/trimethylidene complex [Cp′₄Lu₄(μ₃‐CH₂)₃{iPrNC(=CH₂)NiPr}] ( 3 ) in 83 % yield. Similarly, the reaction of 1 with phenyl isothiocyanate gave the ethylene amido thiolate/trimethylidene complex [Cp′₄Lu₄(μ₃‐CH₂)₃{PhNC(S)=CH₂}] ( 4 ). In the case of phenyl isocyanate, two of the four methylidene units in 1 reacted with four molecules of the substrate at ambient temperature to give the malonodiimidate/dimethylidene complex [Cp′₄Lu₄(μ₃‐CH₂)₂{PhN=C(O)CH₂(O)C?NPh}₂] ( 5 ) in 87 % yield. In this reaction, each of the two lutetium–methylidene bonds per methylidene unit inserted one molecule of phenyl isocyanate. All the products have been fully characterized by NMR spectroscopy, X‐ray diffraction, and microelemental analyses.     

Bridging M?Cl Bonds with Ambiphilic Phosphine–Borane Ligands

Bridging or pendant? Palladium and rhodium complexes deriving from an ambiphilic phosphine–borane ligand are shown to adopt a bridging P→M? Cl→B coordination mode in the solid state. DFT calculations provide more insight into the Cl→B interaction and suggest the possible interconversion of the bridging and B‐pendant forms in solution.

     

Luminescent Cyanoruthenate(II)?Diimine and Cyanoruthenium(II)?Diimine Complexes

To improve the emission and excited‐state properties of luminescent cyanometalates, new classes of highly solvatochromic luminescent cyanoruthenium(II) and cyanoruthenate(II) complexes of the general formulae [Ru(PR₃)₂(CN)₂($\widehat{NN}$ )] and K[Ru(PR₃)(CN)₃($\widehat{NN}$ )], respectively, were developed. These complexes could be readily synthesized through the ligand‐substitution reaction of K₂[Ru(CN)₄(PR₃)₂] with a diimine ligand. The geometrical isomerism of these complexes was characterized by using various spectroscopic techniques. Their photophysical properties, solvatochromism, and electrochemistry have also been investigated. Our detailed study showed that many of these complexes exhibited extremely environmentally sensitive emissions and significantly improved emission quantum efficiencies and lifetimes compared with the well‐studied tetracyanoruthenate systems.     

Infrared Spectrum of the Si3H8+ Cation: Evidence for a Bridged Isomer with an Asymmetric Three‐Center Two‐Electron Si?H?Si Bond

The IR spectrum of Si₃H₈⁺ ions produced in a supersonic plasma molecular beam expansion of SiH₄, He, and Ar is inferred from photodissociation of cold Si₃H₈⁺–Ar complexes. Vibrational analysis of the spectrum is consistent with a Si₃H₈⁺ structure ( 2⁺ ) obtained by a barrierless addition reaction of SiH₄ to the disilene ion (H₂Si?SiH₂⁺) in the silane plasma. In this structure, one of the electronegative H atoms of SiH₄ donates electron density into the partially filled electrophilic π orbital of the disilene cation. The resulting asymmetric Si? H? Si bridge of the 2⁺ isomer with a bond energy of approximately 60 kJ mol^?1 is characteristic for a weak three‐center two‐electron bond, which is identified by its strongly IR active asymmetric Si? H? Si stretching fundamental at about 1765 cm^?1. The observed 2⁺ isomer is calculated to be only a few kJ mol^?1 less stable than the global minimum structure of Si₃H₈⁺ ( 1⁺ ), which is derived from vertical ionization of trisilane. Although more stable, 1⁺ is not detected in the measured IR spectrum of Si₃H₈⁺–Ar, and its lower abundance in the supersonic plasma is rationalized by the production mechanism of Si₃H₈⁺ in the silane plasma, in which a high barrier between 2⁺ and 1⁺ prevents the efficient formation of 1⁺ . The potential energy surface of Si₃H₈⁺ is characterized in some detail by quantum chemical calculations. The structural, vibrational, electronic and energetic properties as well as the chemical bonding mechanism are investigated for a variety of low‐energy Si₃H₈⁺ isomers and their fragments. The weak intermolecular bonds of the Ar ligands in the Si₃H₈⁺–Ar isomers arise from dispersion and induction forces and induce only a minor perturbation of the bare Si₃H₈⁺ ions. Comparison with the potential energy surface of C₃H₈⁺ reveals the differences between the silicon and carbon species.     

Ethylenedithio?Tetrathiafulvalene?Helicenes: Electroactive Helical Precursors with Switchable Chiroptical Properties

Electroactive fused ethylenedithio? tetrathiafulvalene? [4]helicene and ‐[6]helicenes have been synthesized through a strategy that involved the preparation of 2,3‐dibromo‐helicene derivatives as intermediates. The dihedral angles between the terminal helicenes, as determined by single‐crystal X‐ray analysis, are 22.7° and 50.7° for the [4]helicene and [6]helicene, respectively. Their solid‐state architectures show interplay between S???S and π???π intermolecular interactions. The chiroptical properties of the enantiopure EDT? TTF? [6]helicene derivatives have been investigated and supported by TDDFT calculations. Remarkable redox switching of the circular dichroism (CD) signal between the neutral and radical‐cation species has been achieved.     

Asymmetric C(sp2)?H Activation

A “niche” topic in the past decade, the asymmetric C? H bond activation has been attracting growing interest over the last few years. Particularly significant advances have been achieved in the field of direct, stereoselective transformations of C(sp²)? H bonds. This Concept article intends to showcase different types of asymmetric C(sp²)? H bond activation reactions, emphasising both the nature of the stereo‐discriminating step and the variability of valuable scaffolds that could be rapidly constructed by means of such strategies.     

Intramolecular Pnicogen Interactions in PHF?(CH2)n?PHF (n=2–6) Systems

A computational study of the intramolecular pnicogen bond in PHF? (CH₂)_n? PHF (n=2–6) systems was carried out. For each compound, two different conformations, (R,R) and (R,S), were considered on the basis of the chirality of the phosphine groups. The characteristics of the closed conformers, in which the pnicogen interaction occurs, were compared with those of the extended conformer. In several cases, the closed conformations are more stable than the extended conformations. The calculated interaction energies of the pnicogen contact, by means of isodesmic reactions, provide values between ?3.4 and ?26.0 kJ mol^?1. Atoms in molecules and electron localization function analysis of the electron density showed that the systems in the closed conformations with short P ??? P distances have a partial covalent character in this interaction. The calculated absolute chemical shieldings of the P atoms showed an exponential relationship with the P ??? P distance. In addition, a search in the Cambridge crystallographic database was carried out to detect those compounds with a potential intramolecular pnicogen bond in the solid phase.     

N-Silylierung und Si?O-Bindungsspaltung bei der Reaktion lithiierter Siloxy-silylamino-silane mit Chlortrimethylsilan

N-Silylation and Si? O Bond Splitting at the Reaction of Lithiated Siloxy-silylamino-silanes with Chlorotrimethylsilane Lithiated Siloxy-silylamino-silanes were allowed to react in tetrahydrofurane (THF) and in n-octane (favoured) and n-hexane, resp., with chlorotrimethylsilane. The monoamide (Me₃SiO)Me₂Si(NLiSiMe₃) gives in THF and in n-octane the N-substitution product (Me₃SiO)Me₂Si · [N(SiMe₃)₂] 1 , the diamide (Me₃SiO)MeSi(NLiSiMe₃)₂ only in THF the N-substitution products (Me₃SiO)MeSi[N(SiMe₃)₂]₂ 2 (main product) and (Me₃SiO)MeSi[N(SiMe₃)₂](NHSiMe₃) 3 . In n-octane the diamide reacts mainly under Si? O bond splitting. The cyclodisilazane [(Me₃SiNH)MeSi? NSiMe₃]₂ 6 is obtained as the main product. Byproducts are 2, 3 and the tris(trimethylsilylamino) substituted disilazane (Me₃SiO)(Me₃SiNH)MeSi? N · (SiMe₃)? SiMe(NHSiMe₃)₂ 7 . The triamide (Me₃SiO)Si · (NLiSiMe₃)₃ reacts under Si? O and Si? N bond splitting in n-octane as well as in THF. The cyclodisilazanes [(Me₃SiNH)₂ · Si? NSiMe₃]₂ 10 and ( 11 : R = Me₃SiNH, 12 : R = (Me₃Si)₂N) are formed. in THF furthermore the N-substitution products (Me₃SiO)Si[N(SiMe₃)₂] · (NHSiMe₃)₂ 4 and (Me₃SiO)Si[N(SiMe₃)₂]₂(NHSiMe₃) 5 . The Si? O bond splitting occurs in boiling n-octane also in absence of the chlorotrimethylsilane. An amide solution of (Me₃SiO)MeSi(NHSiMe₃)₂ with n-butyllithium in the molar ratio 1 : 1 leads in n-octane and n-hexane to 6 and 7 , in THF to 3 . The amide solutions of (Me₃SiO)Si · (NHSiMe₃)₃ with n-butyllithium the molar ratio 1 : 1 and 1 : 2 give in THF 4 and 5 , respectively.     

Attempted 1,3-trimethylsilyl migration in Me3Si?PSN?R system

A dimer of thioxo-N-t-butylimino(trimethylsiloxy)-phosphorane 5 has been prepared by reaction of tris(trimethylsilyl) phosphine with N-sulfinyl-N-tert-butylamine. The structure of 5 has been confimed by X-ray analysis data. 1-Aza-2-thia-3-phosphaallene 1 , thiaphosphaziridine 3 , iminophosphine P-sulfide 4 are postulated as intermediates of the reaction studied.     

Kinetics and modeling of the H2?O2?NOx system

The addition of NO (0 to 400ppm) to mixtures of H₂ (ca. 1%) and O₂ (0.7 to 22%) has been studied over the temperature range 700 to 825 K, in a flow reactor at atmospheric pressure. The overall effect of NO is to promote the oxidation of H₂ but high concentrations of O₂ actually inhibit the NO-promoted oxidation of H₂. A detailed kinetic mechanism has been constructed and found to describe the experimental observations. The promotion of the oxidation of H₂ arises through the catalytic cycle The ability of R.34 to reactivate chains normally terminated by the formation of HO₂ is a key feature of this system. The predictions are highly sensitive to the rate of the reaction R.5 and the rate constants for this reaction is the only adjustable parameter required in the model. The value of k_5,N2 found to describe all the results has an absolute uncertainty <35%. The uncertainty relative to other important rate constants in the H₂? O₂ system is less than 10%. © 1995 John Wiley & Sons, Inc.     

Revealing Unexpected Mechanisms for Nucleophilic Attack on S?S and Se?Se Bridges

The reactivity of disulfide and diselenide derivatives towards F^? and CN^? nucleophiles has been investigated by means of B3PW91/6‐311+G(2df,p) calculations. This theoretical survey shows that these processes, in contrast with the generally accepted view of disulfide and diselenide linkages, do not always lead to S? S or Se? Se bond cleavage. In fact, S? S or Se? Se bond fission is the most favorable process only when the substituents attached to the S or the Se atoms are not very electronegative. Highly electronegative substituents (X) strongly favor S? X bond fission. This significant difference in the observed reactivity patterns is directly related to the change in the nature of the LUMO orbital of the disulfide or diselenide derivative as the electronegativity of the substituents increases. For weakly electronegative substituents, the LUMO is a σ‐type S? S (or Se? Se) antibonding orbital, but as the electronegativity of the substituents increases the π‐type S? X antibonding orbital stabilizes and becomes the LUMO. The observed reactivity also changes with the nature of the nucleophile and with the S or Se atom that undergoes the nucleophilic attack in asymmetric disulfides and diselenides. The activation strain model provides interesting insights into these processes. There are significant similarities between the reactivity of disulfides and diselenides, although some dissimilarities are also observed, usually related to the different interaction energies between the fragments produced in the fragmentation process.     

Nitridsulfidchloride der Lanthanide: I. Der Formeltyp M4NS3Cl3 (M = La?Nd)

Nitride Sulfide Chlorides of the Lanthanides. I. The Composition M₄NS₃Cl₃ (M = La Nd) The oxidation of the „light”︁ lanthanides (M = La Nd) with sulfur and NaN₃ the presence of the chlorides MCl₃ results in the formation of the first lanthanide nitride sulfide chlorides M₄NS₃Cl₃ when appropriate molar ratios of the reactants are used. The addition of some NaCl (or an excess of MCl₃) as a flux secures complete and fast reaction (7 d) at 850°C in evacuated silica vessels as well as single-crystalline products. Since these nitride sulfide chlorides (fine transparent needles) are not sensitive against hydrolysis, the surplus chloride can be removed easily with water. The crystal structure was determined from X-ray single crystal data for the example of La₄NS₃Cl₃ (hexagonal, P6₃mc (no. 186), Z = 2, a = 941.40(3), c = 700.36(3) pm, R = 0.026, R_w = 0.021) and the nitride sulfide chlorides M₄NS₃Cl₃ with M = Ce Nd proved to be isostructural from Guinier powder data. According to their Ba₃OCl₆-analogue structure, two crystallographically different M³⁺ cations are present (CN(M1) = 10, CN(M2) = 8). „Isolated”︁ tetrahedra [(N³⁻)(M³⁺)₄] build up the Mayn structural feature according to [NM₄]S₃Cl₃. They are hexagonally closest packed and interconnected via the crystallographically different but by X-ray diffraction indistinguishable anions S²⁻ and Cl⁻, which take care for charge neutrality.