Preparation of a high-coordinated-silicon-centered spiro-cyclic compound.

Silicon compounds containing silicon-silicon bond with a variety of unusual oxidation states are quite important, because their high reactivity leads to the formation of a variety of silicon compounds. The isolation of such compounds with unusual oxidation states requires a resilient synthetic strategy. Herein, we report the synthesis of a silicon based spirocyclic compound containing a hyper-valent silicon atom and a silicon-silicon bond. The computational calculations employing natural bond orbital (NBO) analysis and energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV) reveal that the nature of bonding between the silicon atoms is of an electron sharing nature.

En Route to a Molecular Terminal Tin Oxide.

In the pursuit of terminal tin chalcogenides, heteroleptic stannylenes bearing terphenyl- and hexamethyldisilazide ligands were reacted with carbodiimides to yield the respective guanidinato complexes. Further supported by quantum chemical calculations, this revealed that the iso-propyl-substituted derivative provides the maximum steric protection achievable. Oxidation with elemental selenium produced monomeric terminal tin selenides with four-coordinate tin centers. In reactions with N2O as oxygen transfer reagent, silyl migration toward putative terminal tin oxide intermediates gave rise to tin complexes with terminal ─OSiMe3 functionality. To prevent silyl migration, the silyl groups were substituted with cyclohexyl moieties. This analogue exhibited distinctively different reactivities toward selenium and N2O, yielding a 1,2,3,4,5-tetraselenastannolane and chalcogenide-bridged dimeric compounds, respectively.

Boron bis-(4-methylbenzoxazol-2-yl)-methanide complexes.

Boron compounds have attracted the attention of chemists because of their unique catalytic properties and potential wider material applications. Although group 13 metal compounds, which are based on the bis-(benzoxazol-2-yl)-methane system (Box, ({NCOC6H4}2CH2)), have been reported in the last several years, boron containing Box compounds were still missing. Now we report their successful syntheses and spectroscopic characterisation in this work. The borane compound [({NCOC6H3}2CH)BH2] (1) and haloboranes [({NCOC6H3}2CH)BF2] (2), [({NCOC6H3}2CH)BCl2] (3) and [({NCOC6H3}2CH)BBr2] (4) were characterised in the solid state by single crystal X-ray diffraction and in solution by NMR techniques. In addition, the fluorescence properties of compounds 1-4 are communicated.

Correspondence to "Structure of Violet Phosphorus and Its Phosphorene Exfoliation".

The structure described in the publication "Structure of Violet Phosphorus and Its Phosphorene Exfoliation" (Angew. Chem. Int. Ed. 2020, 59, 1074-1080) is identical to the structure by Thurn and Krebs determined already in 1969 and therefore by no means a new modification.

Synthesis, Reactivity, and Complexation with Fe(0) of a Tight-bite Bis(N-heterocyclic silylene).

The synthesis, reactivity, and complexation with Fe(0) precursor of a tight-bite bis(N-heterocyclic silylene) (bis(NHSi)) ligand 1 are reported. The reaction of 1 with p-toluidine led to the activation of both N-H bonds across Si(II) atoms to afford a four-membered heterocyclic cyclodisilazane 2, with hydride substituents attached to five-coordinate Si atoms. A 1 : 2 reaction of 1 with Fe(CO)5 led to an intriguing dinuclear complex 3 featuring a five-membered (N-Si-Fe-Fe-Si) ring with a Fe-Fe bond distance of 2.6892(13) Å. All compounds (1-3) were thoroughly characterized by various spectroscopic methods and X-ray diffraction studies conclusively established their molecular structures. DFT calculations were carried out to shed light on bonding and energetic aspects in 1-3.

Preparation of a Compound with a SiII -SiIV -SiII Bonding Arrangement.

Herein, we report the synthesis of a rare bis-silylene, 1, in which two SiII atoms are bridged by a SiIV atom. Compound 1 contains an unusual SiII -SiIV -SiII bonding arrangement with SiII -SiIV bond distances of 2.4212(8) and 2.4157(7) Å. Treatment of 1 with Fe(CO)5 afforded a dinuclear Fe0 complex 2 with two unusually long Si-Si bonds (2.4515(8) and 2.4488(10) Å). We have also carried out a detailed computational study to understand the nature of the Si-Si bonds in these compounds. Natural bond orbital (NBO) and energy decomposition analysis-natural orbital for chemical valence (EDA-NOCV) analyses reveal that the Si-Si bonds in 1 and 2 are of an electron-sharing nature.

Stabilization of NH- Group Adjacent to Naked Silicon(II) Atom in Base Stabilized Aminosilylenes.

Aminosilylene, comprising reactive NH- and Si(II) sites next to each other, is an intriguing class of compounds due to its ability to show diverse reactivity. However, stabilizing the reactive NH- group next to the free Si(II) atom is challenging and has not yet been achieved. Herein, we report the first examples of base stabilized free aminosilylenes Ar*NHSi(PhC(Nt Bu)2 ) (1 a) and Mes*NHSi(PhC(Nt Bu)2 ) (1 b) (Ar*=2,6-dibenzhydryl-4-methylphenyl and Mes*=2,4,6-tri-tert-butylphenyl), tolerating a NH- group next to the naked Si(II) atom. Remarkably, 1 a and 1 b exhibited interesting differences in their reactivity upon heating. With 1 a, an intramolecular C(sp3 )-H activation of one of the benzhydryl methine hydrogen atoms to the Si(II) atom produced the five-membered cyclic silazane 2. However, with 1 b, a rare 1,2-hydrogen shift to the Si(II) atom afforded a silanimine 3, with a hydride ligand attached to an unsaturated silicon atom. Further, the coordination capabilities of 1 a were also tested with Ru(II) and Fe(0) precursors. Treatments of 1 a with [Ru(η6 -p-cymene)Cl2 ]2 led to the isolation of a η6 -arene tethered complex [RuCl2 {Ar*NHSi(PhC(t BuN)2 )-κ1 -Si-η6 -arene}] (4), whereas with the Fe(CO)5 precursor a Fe(0) complex [Fe(CO)4 {Ar*NHSi(PhC(t BuN)2 )-κ1 -Si}] (5) was obtained. Density functional theory (DFT) calculations were conducted to shed light on the structural, bonding, and energetic aspects in 1-5.

A Neutral Planar Four-Membered Si2B2 2π-Aromatic Ring.

The synthesis of the first inorganic four-membered neutral 2π-aromatic compound 2 is reported. This unique ring has been synthesized from a simple and straightforward reaction of amidinato-silylene with dichlorophenylborane, followed by the reduction with KC8 in THF. Compound 2 has been fully characterized by single-crystal X-ray diffraction (SC-XRD), NMR spectroscopy, and mass spectrometry. The computational calculations reveal that the Si2B2 ring is a π-delocalized system resulting from the interaction of pπ orbital of B and Si-N σ* orbitals having pseudo π symmetry. Compound 2 is the first known example of a neutral planar inorganic analogue of cyclobutenyl dication.

A new polymorph of white phosphorus at ambient conditions.

Phosphorus exists in several different allotropes: white, red, violet and black. For industrial and academic applications, white phosphorus is the most important. So far, three polymorphs of white phosphorus, all consisting of P4 tetrahedra, have been described. Among these, ß-P4 crystallizes in the space group P1 and γ-P4 in the space group C2/m. α-P4 forms soft plastic crystals with a proposed structure in the cubic space group I43m with the lattice constant a = 18.51 (3) Å, consisting of 58 rotationally disordered tetrahedra and thus is similar to the structure of α-Mn. Here we present a new polymorph, δ-P4. It crystallizes as a sixfold twin with the cell dimensions a = 18.302 (2), b = 18.302 (2), c = 36.441 (3) Šin the space group P212121 with 29 P4 tetrahedra in the asymmetric unit. The arrangement resembles the structure of α-Mn, but δ-P4 differs from α-P4. DFT calculations show δ-P4 to be metastable at a similar energy level to that of γ-P4.

Indium Kα radiation from a MetalJet X-ray source: comparison of the Eiger2 CdTe and Photon III detectors.

The MetalJet source makes available new Kα radiation wavelengths for use in X-ray diffraction experiments. The purpose of this paper is to demonstrate the application of indium Kα radiation in independent-atom model refinement, as well as approaches using aspherical atomic form factors. The results vary greatly depending on the detector employed, as the energy cut-off of the Eiger2 CdTe provides a solution to a unique energy contamination problem of the MetalJet In radiation, which the Photon III detector cannot provide.

Indium Kα radiation from a MetalJet X-ray source: the long way to a successful charge-density investigation.

The MetalJet X-ray source provides indium Kα radiation with a wavelength even shorter than Ag radiation. This paper reports on problematic spectral impurities and presents possible countermeasures so that collection of data with excellent quality up to a high resolution is possible. It is demonstrated that these data can be used in the refinement of a multipole model, the results of which are used for a topological analysis to assess the bonding situation in a sulfur ylide compound.

In data we trust: X-ray diffraction experiments for charge density investigations.

A short commentary is given on the paper by Vosegaard et al. [Acta Cryst. (2023), 79, 380-391], which compares charge density models derived from four datasets measured on conventional diffractometers with the results of a high-quality dataset from SPring-8.

Synthesis and Characterization of Substituted Phosphasilenes and its Rare Homologue Stibasilene >Si=Sb.

Herein we report the reduction of R-EX2 (E=P, Sb) with two equivalents of KC8 in the presence of silylene (LSiR; L=PhC(NtBu)2 ) to give Trip-P=SiL(C6 H4 PPh2 ) (1), Ter Ph-P=(tBu)SiL (2) and Ter Ph-Sb=(tBu)SiL (3). The last (3) belongs to a new class of heavier analogues of Schiff bases (>C=N-), containing a formal >Si=Sb- double bond. The theoretical calculations suggest that lone pairs on the dicoordinated group-15 centers are stabilized by hyperconjugative interactions resulting in pseudo-Si-P/Si-Sb multiple bonds which are highly reactive as indicated by the high first and second proton affinities.

A Neutral Borylene and its Conversion to a Radical by Selective Hydrogen Transfer.

A successful selective reduction of X2B-Tip (Tip = 1,3,5-iPr3-C6H2, X = I, Br) with KC8 and Mg metal, respectively, in the presence of a hybrid ligand (C6H4(PPh2)LSi) leads to a stable low-valent five-membered ring as a boryl radical [C6H4(PPh2)LSiBTip][Br] (1) and neutral borylene [C6H4(PPh2)LSiBTip] (2). Compound 2 reacts with 1,4-cyclohexadiene, resulting in hydrogen abstraction to afford the radical [C6H4(PPh2)LSiB(H)Tip] (3). Quantum chemical studies reveal that compound 1 is a B-centered radical, and compound 2 is a phosphane and silylene stabilized neutral borylene in a trigonal planar environment, whereas compound 3 is an amidinate-centered radical. Although compounds 1 and 2 are stabilized by hyperconjugation and π-conjugation, they display high H-abstraction energy and basicity, respectively.

[2+4] Cycloaddition Product of an Amidinate Substituted Dialumene with Toluene.

Reduction of LAlI2 (L=PhC(Ni Pr2 C6 H3 )2 ) with two equivalents of KC8 in toluene affords the [2+4]cycloaddition product of a dialumene with toluene. The mechanism for the formation of product complex was investigated using density functional theory (DFT) methods.

One silicon atom of bis(silylene) functions as a selective Lewis base under adduct formation with a Lewis acid.

Herein, we describe the facile and selective one-pot synthetic route to silylene-aluminum and silylene-gallium adducts. Reduction of silylene LSiCl (L = PhC(NtBu)2) with KC8 in the presence of bulky and sterically hindered cyclopentadienyl aluminum Cp'''AlCl2 (Cp''' = 1,2,4-tBu3C5H2) and gallium [η1-Cp'''Ga(µ-Cl)Cl]2 to afford the Lewis acid-base adducts η1-Cp'''M(Cl2) ← Si(L)-SiL (M = Al, 1; M = Ga, 3). To confirm the formation of the Lewis acid-base adduct, the bis(silylene) LSi(I)-Si(I)L reacts with Cp'''AlI2 to form η1-Cp'''Al(I2) ← Si(L)-SiL (2). These are the first examples where one Si atom in the bis(silylene) is a Lewis base and coordinates with aluminum or gallium to form a Lewis acid-base adduct, while the other Si atom in the bis(silylene) still maintains the characteristics of silylene. Compound 3 was heated to 70 °C in toluene for 4 hours and decomposed into the silylene LSiCl and Cp'''GaI. Compounds 1-3 are well characterized with NMR spectroscopic methods and single-crystal X-ray structural analysis.

Linear and Bent Cp*2 Si: Reversible Phase Transition of a Key Molecule.

The solid-state structure of decamethylsilicocene Cp*2 Si with a bent and a linear molecule in the same unit cell was so far considered an exception in relation to the structures of its all-bent heavier analogues Cp*2 E with E=Ge, Sn, Pb. Here, we present the solution to this conundrum by reporting a low-temperature phase, where all three symmetrically independent molecules are present in a bent formation. This reversible enantiotropic phase transition occurs in the temperature range between 80 K and 130 K and provides a rationale for the unexpected linear molecule based in entropy beyond hand-waving explanations such as electronic reasons or packing effects.

Reactivity of Silylene with Gallium- and Boron Trihalide at Reductive Conditions Resulting in Unforeseen Products.

Herein, we report a one-pot reaction of gallium and boron halides with potassium graphite in the presence of benzamidinate stabilized silylene LSi-R, (L=PhC(Nt Bu)2 ). The reaction of LSiCl with an equivalent amount of GaI3 in the presence of KC8 leads to the direct substitution of one chloride group by gallium diiodide simultaneously additional coordination of silylene resulted in L(Cl)Si→GaI2 -Si(L)→GaI3 (1). In compound 1, the structure comprises two differently coordinated gallium atoms where one gallium presents between two silylenes and the other gallium is only coordinated by one silylene. In this Lewis acid-base reaction the oxidation states of the starting materials remain unchanged. The same is valid in the silylene boron adduct formation of L(t Bu)Si-BPhCl2 (2) and L(t Bu)Si-BBr3 (3). This new route provides access to galliumhalosilanes challenging to synthesize by any other method.

Compounds with Alternating Single and Double Bonds of Antimony and Silicon; Isoelectronic to Ethane-1,2-diimine.

We present an approach for preparing chain-type unsaturated molecules with low oxidation state Si(I) and Sb(I) supported by amidinato ligands that exploit to generate heavy analogues of ethane 1,2-diimine. The reduction of antimony dihalide (R-SbCl2) with KC8 in the presence of silylene chloride afforded L─(Cl)Si═Sb─Tip (1) and L(Cl)Si═Sb─TerPh (2), respectively. Compounds 1 and 2 further undergo reduction with KC8 to produce Tip─Sb═LSi─LSi═Sb─Tip (3) and TerPh─Sb═LSi─LSi═Sb─TerPh (4). The solid-state structures and DFT studies show that all compounds have σ-type lone pairs at each Sb atom. It forms a strong pseudo-π-bond with Si. The pseudo-π-bond is formed by the hyperconjugative donation of the π-type lone pair at Sb to the Si-N σ* MO. The quantum mechanical studies indicate that compounds 3 and 4 has delocalized pseudo-π-MOs arising from hyperconjugative interactions. Hence, 1 and 2 can be considered as isoelectronic to imine, while 3 and 4 are isoelectronic to ethane-1,2-diimine. The proton affinity studies indicate that the pseudo-π-bond resulting from the hyperconjugative interaction is more reactive than the σ-type lone pair.

Coordination and Stabilization of a Lithium Ion with a Silylene.

Herein, we report the stabilization of lithium-ion as the source of lithium to use as a trans-metalation reagent [{PhC(Nt Bu)2 Si(t Bu)Li}2 I(t BuN)2 CPh] (1). The reaction of 3 equivalents of the LSit Bu (L=PhC(Nt Bu)2 ) and lithium iodide at low temperature leads to a silylene stabilized lithium-ion with an additional coordination of amidinate ligand. Compound 1 shows two four membered and one six membered ring as confirmed by QTAIM calculations. Whereas the reaction of the LSiCl with 1.5 equivalents of carbodiimide (CyN)2 C at room temperature affords compound [PhC(Nt Bu)2 Si(Cl)(NCy)2 NCy] (2) with the CN2 SiN2 C skeleton containing silicon as a central atom. Both the compounds were fully characterized by NMR, mass spectrometry, X-ray crystallographic analysis, and quantum mechanical calculations.