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We present complexes of alkali metal ions and the ammonium ion with the large cyclodimethylsiloxanes D7 and D8 (D=Me2SiO). The formation of such complexes is accompanied by rearrangements of the ligands to form complexes with a suitable ring size for the metal used. These rearrangements could be suppressed by suitable reaction conditions and rapid work‐up of the reaction mixtures. This enabled the isolation of [Li(D7)][GaI4] (1), [Li(D8)][GaI4] (2), [Na(D8)][GaI4] (3), [K(D8)][GaI4] (4) and [NH4(D8)][GaI4] (5). All of the prepared compounds were analysed using single‐crystal X‐ray diffraction as well as multinuclear NMR spectroscopy. This reveals very different coordination modes in the compounds obtained. [ABSTRACT FROM AUTHOR]

A series of transition metal‐pnictogenide compounds were prepared starting from [(Dipp2NacNac)MCl] (M=Cr, Mn, Fe, Zn) (Dipp2NacNac=HC{C(Me)N(Dipp)}2) and [M'E(SiMe3)2] (M'=Li, K; E=P, As, Sb) as well as [Li(Et2O)nPH2] and [Li(tmeda)AsH2]. In the course of these investigations we were able to characterize all permutations for compounds of the composition [(Dipp2NacNac)ZnE(SiMe3)2] (E=P, As, Sb) and [(Dipp2NacNac)ZnEH2] (E=P, As). Moreover, the synthesis of selected compounds of type [(Dipp2NacNac)ME(SiMe3)2] for M=Cr, Mn, Fe and E=P−Sb are described. As part of our efforts, we established a number of bonding motifs that are underexplored in the literature to date. All isolated compounds, were examined by NMR spectroscopy, IR spectroscopy, Elemental analysis and X‐Ray structure analysis. DFT calculations on the chromium compounds were performed to investigate the binding situation between chromium and the group 15 element in more detail. [ABSTRACT FROM AUTHOR]

A series of low‐valent Group 14–15 compounds were obtained starting from [(Dipp2NacNac)MCl] (M=Ge‐Pb) (I–III) (Dipp2NacNac=HC{C(Me)N(Dipp)}2) and M'E(SiMe3)2 (M'=Li, E=As; M'=K, E=Sb, Bi) (IV–VI). In the course of this investigations we were able to fully characterize all permutations except Pb−Bi for compounds of the composition [(Dipp2NacNac)ME(SiMe3)2] (1E: M=Ge, 2E: M=Sn, 3E: M=Pb). Thus, we report the first low valent tetrelene with Sn−Bi bond. All isolated compounds, were examined by NMR spectroscopy, IR spectroscopy and except compound 1As by X‐ray structure analysis. Moreover, were examined UV‐Vis spectroscopy and investigated the reactivity of these compounds towards different substrates in more detail. Starting with the compound [(Dipp2NacNac)SnAs(SiMe3)2] (2As), the reaction with red selenium yields [(Dipp2NacNac)Sn−Se‐As(SiMe3)2] (4) which exhibits a Sn−Se−As chain. [ABSTRACT FROM AUTHOR]

Antimony, stibane, inorganic chemistry, gas induction, vacuum synthesis [28] Since the chemistry of SbH SB 3 sb in inorganic synthesis is almost unexplored, we focused on an easy-to-use preparation and further processing of this compound, building on the aforementioned preliminary work. Taming SbH3: A Simple and Safe Approach to Using Stibane in Synthesis on a Laboratory Scale Keywords: antimony; stibane; inorganic chemistry; vacuum synthesis; gas induction EN antimony stibane inorganic chemistry vacuum synthesis gas induction 1777 1780 4 08/29/23 20230915 NES 230915 Graph The hydrogen compounds (EH SB 3 sb ) of the pnictogens nitrogen, phosphorus, and arsenic have been known for several centuries and are well established in inorganic synthesis. [Extracted from the article]

Herein, we report about the preparation of several new 2,6‐diisopropylphenyl (Dipp) substituted (halido‐) bismuthanes, namely, Dipp3Bi (1) and compounds of the form DippBiX2 (X=Cl, Br, I; 2–4). The compounds 2–4 show a variety of structural motifs in their solid state structures. Reactivity of 2 towards the nucleophiles LiNMe2 and MeLi was examined, where mostly scrambling reactions with a preference for two Dipp substituents at bismuth were observed. Therefore, the compounds Dipp2BiNMe2 (5) and Dipp2BiMe (6) are the main products of these reactions. Moreover, new interpnictogen compounds with Bi−N, ‐P, and ‐Sb single bonds were prepared. Compound 5 was successfully used as precursor for the preparation of Dipp2BiNHtBu (7) and Dipp2BiSbMes2 (8), one of very few isolated compounds with a Bi‐Sb single bond. Moreover, bismuthanyl phosphanes bearing functional groups (Dipp2BiPtBu(SiMe3) (9), Dipp2BiPHtBu (10)) have been prepared. Compound 10 is the first isolated secondary phosphane with a bismuthanyl substituent. All isolated compounds were analyzed via IR and NMR spectroscopy, mass spectrometry, elemental analysis and single crystal X ray diffraction. [ABSTRACT FROM AUTHOR]

Herein, the characterization and reactivity of the metalated arsinidenyl (SIDipp)AsK (1 a) is described. This compound was obtained via deprotonation of the saturated "parent arsinidene" (SIDipp)AsH (1) with the strong base benzyl potassium and appears as pyrophoric, insoluble, red solid. The ability of crown ethers to improve the solubility of metal compounds through complex formation has been used to obtain crystals of (SIDipp)AsK. Thus, the crown ether complex [K(18‐crown‐6)(SIDipp)As] (1 b) was characterized as the first of its kind by single crystal x‐ray diffraction. Furthermore, (SIDipp)AsK was treated with di‐tert‐butylchloropnictogens (tBu2ECl, E=P, As, Sb, Bi) to give the interpnictogen compounds of the type (SIDipp)AsEtBu2 (2–5) with low valent arsenic substituents. [ABSTRACT FROM AUTHOR]

The Mg and Ca complexes of the tert‐butyl substituted bis(amido)diazadiarsetidinides [{(tBuNAs)2(tBuN)2}M(thf)2] (M=Mg (1), Ca (6)) were prepared by addition of nBu‐secBuMg or [{(p‐tBu)(C6H4)CH2}2Ca] to [(tBuNAs)2(tBuNH)2] (Ia). Upon evaporation of coordinating THF, 1 is selectively converted to the amido(imino)arsenide complex [Mg{As(NtBu)2}2] (2) whereas 6 decomposes to several products under these conditions. Hydrolysis of 2 with H2O yields the hitherto unknown compound As(NHtBu)3 (3) whereas hydrolysis of Ia leads to the formation of the oxygen bridged bis(amidodiazadiarsetidine) [O{(tBuNH)(tBuNAs)2}2] (4). Reaction of 2 with 3 yields the heteroleptic Mg complex with an amido(imino)arsenide and a bis(amido)diazadiarsetidinide ligand [{(tBuNAs)2(NHtBu)(NtBu)}Mg{As(NtBu)2}] (5). The homologous Ca compound (7) was obtained by conversion of Ia with Ca(hmds)2 (hmds=N(SiMe3)2). Finally, the tetrylene complexes [E{(tBuNAs)2(tBuN)2}] (E=Ge (8), Sn (9), Pb (10)) were prepared by either conversion of Ia with E(hmds)2 for E=Sn, Pb or by addition of the dichlorides of Ge and Sn to [(tBuNAs)2(tBuNLi)2] (Ib). All compounds were characterised by NMR and IR spectroscopy, mass spectrometry and single crystal x‐ray diffraction for 1, 2, 4, 5, 6 and 10. [ABSTRACT FROM AUTHOR]

Oxidative addition reactions of (Dipp2NacNac)Ga with the primary silylphosphanes R2R'Si‐PH2 in toluene led to the phospha‐gallanes (Dipp2NacNac)GaH(PHSiR2R'); R=R'=Me (1), R=Me, R'=Thex (2), R=R'=iPr (3) and R=Ph, R'=tBu (4). The same reaction starting from the diphosphane iPr2Si(PH2)2 yields the digallane {(Dipp2NacNac)GaH(PH)}2(SiiPr2) (5 a). In contrast, reaction with the hypersilylphosphane resulted in the elimination of (Me3Si)3SiH and formation of the diphospha‐gallane (Dipp2NacNac)Ga(PH2)(PHSi(SiMe3)3) (6). The primary organo‐phosphane tBuPH2 shows a similar reaction behavior in toluene though both the di‐ and monophospha‐gallanes (Dipp2NacNac)GaX(PHtBu) (7 a: X=PH2, 7 b: X=H) occur. In a row of used solvents, only pyridine led selective to the formation of 7 b thus we tested the influence of this solvent on the reaction of iPr2Si(PH2)2 with only one equivalent (Dipp2NacNac)Ga which yields the compound (Dipp2NacNac)GaH(PHSiiPr2PH2) (5 b). Additionally, a derivative of compound 3, (Dipp2NacNac)GaCl(PHSiiPr3) (8), with an Cl atom bond to gallium instead of a hydrogen was obtained by the reaction of (Dipp2NacNac)GaCl2 with iPr3SiPHLi. [ABSTRACT FROM AUTHOR]

A series of alkaline metal functionalised tert‐butyl substituted bis(amido)diazadiarsetidinides [(μ‐N(tBu)As)2(N(tBu)M)2] (M=K (1), Rb (2), Cs (3), Na⋅thf (4), Na (5)) were prepared and their solid state structures investigated in detail. Further substitution reactions with tert‐butyl substituted element chlorides of P, As, Sb and Bi were performed. The conversion of two equivalents tBu2AsCl (II) with 1–3 unexpectedly leads to the introduction of only one arsine moiety ([(μ‐N(tBu)As)2(N(tBu)H)(N(tBu)AstBu2] (6)) while the other nitrogen atom gets protonated by ether cleavage. The reaction of one equivalent tBuECl2 (E=As (III), Sb (IV)) with 1, 2 or 3 yielded the intended cage compounds [(μ‐N(tBu)As)2(NtBu)2EtBu] (E=As (7), Sb (8)) in high yields. Reaction of 1–3 with two equivalents of tBu2E'Cl (E'=Sb (V), Bi (VI)) yields the twofold substituted bis(amido)diazadiarsetidines [(μ‐N(tBu)As)2(N(tBu)E'tBu2)2] (E'=Sb (9), Bi (10)), which show weak intramolecular E'–E' interactions. [ABSTRACT FROM AUTHOR]

Siloxanes have evolved into a multi‐million dollar business due to their manifold of commercial and industrial applications. As siloxanes have high hydrophobicity, low basicity, high flexibility and also high chemical inertness in common, their chemistry differs significantly from that of organic ethers. The discovery of organic crown ethers, for instance, is commonly accepted as the birth of synthetic host‐guest chemistry. Regarding the chemical properties of siloxanes, cyclic siloxanes which formally resemble silicon analogues of crown ethers, have received considerably less interest in terms of their host‐guest chemistry. Hence, only little is known about siloxane coordination chemistry in the chemical community and the number of published works in this field has been very low till lately. In the last few years, the field has significantly advanced and elegant methods were established to enable the Si−O−Si unit for coordination. This review therefore summarizes the recent developments in the field, recapitulates the historical aspects of siloxane coordination chemistry and describes the specific Si−O bond character with regard to different siloxane linkages. Implications on Si−O bond activation are included and the limits of siloxane coordination are redefined. [ABSTRACT FROM AUTHOR]

For the first time, room temperature laser emission of an electrically pumped edge emitting laser device based on (Ga,In)(N,As)/Ga(As,Sb)/(Ga,In)(N,As) type‐II W' quantum well heterostructures is shown. The device was grown using metal organic vapour phase epitaxy utilising the alternative nitrogen precursor di‐tert‐butyl‐amino‐arsane and characterised with electroluminescence spectroscopy. At low current densities, the emission wavelength was 1339 nm. It shifted blue with 4.26 meV/(kA/cm2) until the threshold current density was reached. At that point, the peak emission wavelength reached 1270 nm. With a cavity length of 2012 μm, the investigated device reached lasing threshold at 9.5 kA/cm2. [ABSTRACT FROM AUTHOR]

In this contribution we have systematically explored the coordination chemistry of the iodide anion towards SO2. While employing large organocations like s‐block metal complexes of crown‐ethers, we discovered a remarkable structural diversity within the herein characterized compounds together with novel architectures of SO2 solvates. The observed O2S···I– interactions are observed to be strong enough to determine the crystal packing and dimensionality. In the light of chalcogen bonding, the small molecule SO2 is introduced as a supramolecular synthon. In the light of a chemistry in non‐aqueous solutions, the ISO2– anion is revisited. Chalcogen bonding was established to form one‐dimensional networks in the compounds [Li([12]crown‐4)H2O]I·SO2 (1), [Na([15]crown‐5)(SO2)I] (2), [K([18]crown‐6)(SO2)I] (4), [NH4([18]crown‐6)]I·SO2 (5), [Rb([18]crown‐6)I(SO2)]·2SO2 (6) and [Cs([18]crown‐6)(SO2)2I] (7) all of which were obtained by 1:1 complexation of the respective iodide salt and respective crown‐ether in SO2 solution. Two‐dimensional networks were obtained within the alkaline earth metal compounds [Mg([12]crown‐4)2]I2·4SO2 (9) and [Ba2([18]crown‐6)2(SO2I)(SO2)2I3]·SO2 (11). The iodosulfite ion ISO2– was obtained either by shielding Na+ ions with [12]crown‐4, conversion of MgI2 with [15]crown‐5, conversion of CaI2 with [18]crown‐6 or conversion of BaI2 with [18]crown‐6 (11, as aforementioned). [Na([12]crown‐4)2]ISO2 (3), [Mg([15]crown‐5)(ISO2)2] (8) and [Ca2([18]crown‐6)(SO2I)3]I3 (10) were characterized. In these respective compounds the S···I atom distances are considerably shorter than those previously reported. Experimental data around the chemistry of halosulfites is provided. Besides network structures and the iodosulfite formation, an SO2‐rich aggregate could be observed. An SO2 adduct of the composition [I2(SO2)5]2– was found to be present in [Na([12]crown‐4)2]I·2.75SO2 (3a). [ABSTRACT FROM AUTHOR]