Different Reactivity of As4 towards Disilenes and Silylenes

The activation of yellow arsenic is possible with the silylene [PhC(NtBu)₂SiN(SiMe₃)₂] ( 1 ) and the disilene [(Me₃Si)₂N(η¹-Me₅C₅)Si=Si(η¹-Me₅C₅)N(SiMe₃)₂] ( 3 ). The reaction of As₄ with 1 leads to the unprecedented As₁₀ cage compound [(LSiN(SiMe₃)₂)₃As₁₀] ( 2 ; L=PhC(NtBu)₂) with an As₇ nortricyclane core stabilized by arsasilene moieties containing silicon(II)bis(trimethylsilyl)amide substituents. In contrast, the compound [Cp*{(SiMe₃)₂N}SiAs]₂ ( 4 ) containing a butterfly-like diarsadisilabicyclo[1.1.0]butane unit is formed by the reaction of As₄ with the disilene 3 . Both compounds were characterized by single-crystal X-ray diffraction analysis, NMR spectroscopy, and mass spectrometry. The reaction outcomes demonstrate the different reaction behavior of yellow arsenic (As₄) compared to white phosphorus (P₄) in the reactions with the corresponding silylenes and disilenes.     

Rational Development of a Metal-Free Bifunctional System for the C−H Activation of Methane: A Density Functional Theory Investigation

The activation or heterolytic splitting of methane, a challenging substrate usually restricted to transition metals, has so far proven elusive in experimental frustrated Lewis pair (FLP) chemistry. In this article, we demonstrate, using density functional theory (DFT), that 1-aza-9-boratriptycene is a conceptually simple intramolecular FLP for the activation of methane. Systematic comparison with other FLP systems allows to gain insight into their reactivity with methane. The thermodynamics and kinetics of methane activation are interpreted by referring to the analysis of the natural charges and by employing the distortion-interaction/activation strain (DIAS) model. These showed that the nature of the Lewis base influences the selectivity over the reaction pathway, with N Lewis bases favoring the deprotonation mechanism and P bases the hydride abstraction one. The lower barrier of activation for 1-aza-9-boratriptycene and the higher products stability are due to a better interaction energy than its counterparts, itself due to electrostatic interactions with the methane moiety, favorable orbital overlaps allowed by the side-attack, and space proximity between the B and N atoms.     

The solution structure of (Me3Si)3CSiBr--an ab initio/NMR study

The first halosilylene stable in solution was investigated by ab initio/NMR calculations (IGLO SOS-DFPT PW91/B2//B3LYP/6-31+G(d)). The delta (29)Si(calc) of (Me(3)Si)(3)CSiBr (446 ppm) does not agree with the measured NMR signal at 106 ppm assigned to the free halosilylene. From the possible silylene complexes in the reaction solution, two structures agree with the observed NMR signal: the (Me(3)Si)(3)CSiBr(2) anion (delta (29)Si(calc)=124 ppm) and the unsolvated and solvated complex of the anion with two Li(+) (delta (29)Si(calc)=117 and estimated 134 ppm). Additionally the delta (29)Si(calc) of alkylsilylenes, R-Si-X, ranging from 200 to 900 ppm are presented to guide NMR identification in future silylene synthesis.     

A Stable Homoleptic Divinyl Tetrelene Series

The synthesis of the new bulky vinyllithium reagent (^MeIPr=CH)Li, (^MeIPr=[(MeCNDipp)₂C]; Dipp=2,6-iPr₂C₆H₃) is reported. This vinyllithium precursor was found to act as a general source of the anionic 2σ, 2π-electron donor ligand [^MeIPr=CH]⁻. Furthermore, a high-yielding route to the degradation-resistant Si^II precursor ^MeIPr⋅SiBr₂ is presented. The efficacy of (^MeIPr=CH)Li in synthesis was demonstrated by the generation of a complete inorganic divinyltetrelene series (^MeIPrCH)₂E: (E=Si to Pb). (^MeIPrCH)₂Si: represents the first two-coordinate acyclic silylene not bound by heteroatom donors, with dual electrophilic and nucleophilic character at the Si^II center noted. Cyclic voltammetry shows this electron-rich silylene to be a potent reducing agent, rivalling the reducing power of the 19-electron complex cobaltocene (Cp₂Co).     

Synthesis and characterization of an amidinate-stabilized cis-1,2-disilylenylethene [cis-LSi{C(Ph)=C(H)}SiL] and a singlet delocalized biradicaloid [LSi(μ(2)-C(2)Ph(2))(2)SiL

The synthesis and characterization of novel cis-1,2-disilylenylethene [cis-LSi{C(Ph)=C(H)}SiL] (2; L=PhC(NtBu)(2)) and a singlet delocalized biradicaloid [LSi(μ(2)-C(2)Ph(2))(2)SiL] (3) are described. Compound 2 was prepared by the reaction of [{PhC(NtBu)(2)}Si:](2) (1) with one equivalent of PhC[triple chemical bond]CH in toluene. Compound 3 was synthesized by the reaction of 1 with two equivalents of PhC[triple chemical bond]CPh in toluene. The results suggest that the reaction proceeds through an [LSi{C(Ph)==C(Ph)}SiL] intermediate, which then reacts with another molecule of PhC[triple chemical bond]CPh to form 3. Compounds 2 and 3 have been characterized by X-ray crystallography and NMR spectroscopy. X-ray crystallography and DFT calculations of 3 show that the singlet biradicals are stabilized by the amidinate ligand and the delocalization within the "Si(μ(2)-C(2)Ph(2))(2)Si" six-membered ring.     

A Triatomic Silicon(0) Cluster Stabilized by a Cyclic Alkyl(amino) Carbene

Reduction of the neutral carbene tetrachlorosilane adduct (cAAC)SiCl₄ (cAAC=cyclic alkyl(amino) carbene :C(CMe₂)₂(CH₂)N(2,6‐iPr₂C₆H₃) with potassium graphite produces stable (cAAC)₃Si₃, a carbene‐stabilized triatomic silicon(0) molecule. The Si?Si bond lengths in (cAAC)₃Si₃ are 2.399(8), 2.369(8) and 2.398(8) Å, which are in the range of Si?Si single bonds. Each trigonal pyramidal silicon atom of the triangular molecule (cAAC)₃Si₃ possesses a lone pair of electrons. Its bonding, stability, and electron density distributions were studied by quantum chemical calculations.     

Stereoselective Activation of Small Molecules by a Stable Chiral Silene

The reaction of the dilithium salt of the enantiopure (S)-BINOL (1,1’-bi-2-naphthol) with two equivalents of the amidinate-stabilized chlorosilylene [L^PhSiCl] (L^Ph=PhC(NtBu)₂) led to the formation of the first example of a chiral cyclic silene species comprising an (S)-BINOL ligand. The reactivity of the Si=C bond was investigated by reaction with elemental sulfur, CO₂ and HCl. The reaction with S₈ led to a Si=C bond cleavage and concomitantly to a ring-opened product with imine and silanethione functional groups. The reaction with CO₂ resulted in the cleavage of the CO₂ molecule into a carbonyl group and an isolated O atom, while a new stereocenter is formed in a highly selective manner. According to DFT calculations, the [2+2] cycloaddition product is the key intermediate. Further reactivity studies of the chiral cyclic silene with HCl resulted in a stereoselective addition to the Si=C bond, while the fully selective formation of two stereocenters was achieved. The quantitative stereoselective addition of CO₂ and HCl to a Si=C bond is unprecedented.     

Activation of SO2 and CO2 by Trivalent Uranium Leading to Sulfite/Dithionite and Carbonate/Oxalate Complexes

The first sulfite [{((^nP,MeArO)₃tacn)U^IV}₂(μ‐κ¹:κ²‐SO₃)] (tacn=triazacyclononane) and dithionite [{((^nP,MeArO)₃tacn)U^IV}₂(μ‐κ²:κ²‐S₂O₄)] complexes of uranium from reaction with gaseous SO₂ have been prepared. Additionally, the reductive activation of CO₂ was investigated with respect to the rare oxalate [{((^nP,MeArO)₃tacn)U^IV}₂(μ‐κ²:κ²‐C₂O₄)] formation. This ultimately provides the unique S₂O₄^2?/C₂O₄^2? and SO₃^2?/CO₃^2? complex pairs. All new complexes were characterized by a combination of single‐crystal X‐ray diffraction, elemental analysis, UV/Vis/NIR electronic absorption, IR vibrational, and ¹H NMR spectroscopy, as well as magnetization (VT SQUID) studies. Moreover, density functional theory (DFT) calculations were carried out to gain further insight into the reaction mechanisms. All observations, together with DFT, support the assumption that SO₂ and CO₂ show similar (dithionite/oxalate) to analogous (sulfite/carbonate) activation behavior with uranium complexes.     

Stable N‐Heterocyclic Carbene Adducts of Arylchlorosilylenes and Their Germanium Homologues

The first N‐heterocyclic carbene adducts of arylchlorosilylenes are reported and compared with the homologous germanium compounds. The arylsilicon(II) chlorides SiArCl(Im‐Me₄) [Ar=C₆H₃‐2,6‐Mes₂ (Mes=C₆H₂‐2,4,6‐Me₃), C₆H₃‐2,6‐Trip₂ (Trip=C₆H₂‐2,4,6‐iPr₃)] were obtained selectively on dehydrochlorination of the arylchlorosilanes SiArHCl₂ with 1,3,4,5‐tetramethylimidazol‐2‐ylidene (Im‐Me₄). The analogous arylgermanium(II) chlorides GeArCl(Im‐Me₄) were prepared by metathetical exchange of GeCl₂(Im‐Me₄) with LiC₆H₃‐2,6‐Mes₂ or addition of Im‐Me₄ to GeCl(C₆H₃‐2,6‐Trip₂). All compounds were fully characterized. Density functional calculations on ECl(C₆H₃‐2,6‐Trip₂)(Im‐Me₄), where E=Si, Ge, at different levels of theory show very good agreement between calculated and experimental bonding parameters, and NBO analyses reveal similar electronic structures of the two aryltetrel(II) chlorides. The low gas‐phase Gibbs free energy of bond dissociation of SiCl(C₆H₃‐2,6‐Trip₂)(Im‐Me₄) (Δ${G{{{\circ}\hfill \atop {\rm calcd}\hfill}}}$ =28.1 kJ mol^?1) suggests that the carbene adducts SiArCl(Im‐Me₄) may be valuable transfer reagents of the arylsilicon(II) chlorides SiArCl.     

Fixation and Release of Intact E4 Tetrahedra (E=P,As)

By the reaction of [NacnacCuCH₃CN] with white phosphorus (P₄) and yellow arsenic (As₄), the stabilization and enclosure of the intact E₄ tetrahedra are realized and the disubstituted complexes [(NacnacCu)₂(μ,η^2:2‐E₄)] ( 1 a : E=P, 1 b : E=As) are formed. The mono‐substituted complex [NacnacCu(η²‐P₄)] ( 2 ), was detected by the exchange reaction of 1 a with P₄ and was only isolated using low‐temperature work‐up. All products were comprehensively spectroscopically and crystallographically characterized. The bonding situation in the products as intact E₄ units (E=P, As) was confirmed by theory and was experimentally proven by the pyridine promoted release of the bridging E₄ tetrahedra in 1 .     

Functionalization of a cyclo‐P5 Ligand by Main‐Group Element Nucleophiles

Unprecedented functionalized products with an η⁴‐P₅ ring are obtained by the reaction of [Cp*Fe(η⁵‐P₅)] ( 1 ; Cp*=η⁵‐C₅Me₅) with different nucleophiles. With LiCH₂SiMe₃ and LiNMe₂, the monoanionic products [Cp*Fe(η⁴‐P₅CH₂SiMe₃)]^? and [Cp*Fe(η⁴‐P₅NMe₂)]^?, respectively, are formed. The reaction of 1 with NaNH₂ leads to the formation of the trianionic compound [{Cp*Fe(η⁴‐P₅)}₂N]^3?, whereas the reaction with LiPH₂ yields [Cp*Fe(η⁴‐P₅PH₂)]^? as the main product, with {[Cp*Fe(η⁴‐P₅)]₂PH}^2? as a byproduct. The calculated energy profile of the reactions provides a rationale for the formation of the different products.     

Unveiling the Noncovalent Interaction of Thiazol-2-ylidene and Its Derivatives as N-heterocyclic Carbene with Different Proton Donor Molecules

The importance of noncovalent interaction has gained attention in various domains covering drug and novel catalyst design. The present study mainly characterizes the role of hydrogen bond (H-bond) and other intermolecular interactions in different (1 : 1) complex analogues formed between the N-aryl-thiazol-2-ylidene (YR) and five proton donor (HX) molecules. The analysis of the singlet-triplet energy gap ( ) confirmed the stability of the singlet state for this class of N-aryl-thiazol-2-ylidenes than the triplet state. The interaction energy values of the YR-HX complexes follow the order: YR-NH₃<YR-HCN<YR-H₂O<YR-MeOH<YR-HF. In addition, substituting the H-atom of the N−H bond with bulky groups (−R) leads to an increase in the interaction energy of the YR-HX complexes. Hence, it was found that the replacement of N-atom in N-heterocyclic carbene (NHC) by S-atom forming N-aryl-thiazol-2-ylidene results in comparable intermolecular interactions with proton donor molecules similar to imidazole-2-ylidene (NHC). The current study enlightened the role of noncovalent interactions in carbene complexes with proton donor molecules. We hope that our work on carbene chemistry will pave the way for its application in the designing and synthesis of efficient catalysts.