Formation and Reactivity of heavy Group 14-15 bonds.

A series of low-valent Group 14-15 compounds were obtained starting from [(Dipp2 NacNac)MCl] (M=Ge-Pb) (I-III) (Dipp2 NacNac=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 [(Dipp2 NacNac)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 [(Dipp2 NacNac)SnAs(SiMe3 )2 ] (2As ), the reaction with red selenium yields [(Dipp2 NacNac)Sn-Se-As(SiMe3 )2 ] (4) which exhibits a Sn-Se-As chain.

f-Element Zintl Chemistry: Actinide-Mediated Dehydrocoupling of H2Sb1- Affords the Trithorium and Triuranium Undeca-Antimontriide Zintl Clusters [{An(TrenTIPS)}3(µ3-Sb11)] (An = Th, U; TrenTIPS = {N(CH2CH2NSiiPr3)3}3-).

Reaction of the cesium antimonide complex [Cs(18C6)2][SbH2] (1, 18C6 = 18-crown-6 ether) with the triamidoamine actinide separated ion pairs [An(TrenTIPS)(L)][BPh4] (TrenTIPS = {N(CH2CH2NSiiPr3)3}3-; An/L = Th/DME (2Th); U/THF (2U)) affords the triactinide undeca-antimontriide Zintl clusters [{An(TrenTIPS)}3(µ3-Sb11)] (An = Th (3Th), U (3U)) by dehydrocoupling. Clusters 3Th and 3U provide two new examples of the Sb113- Zintl trianion and are unprecedented examples of molecular Sb113- being coordinated to anything since all previous reports featured isolated Sb113- Zintl trianions in separated ion quadruple formulations with noncoordinating cations. Quantum chemical calculations describe dominant ionic An-Sb interactions in 3Th and 3U, though the data suggest that the latter exhibits slightly more covalent An-Sb linkages than the former. Complexes 3Th and 3U have been characterized by single crystal X-ray diffraction, NMR, IR, and UV/vis/NIR spectroscopies, elemental analysis, and quantum chemical calculations.

Beryllium-Mediated Halide and Aryl Transfer onto Silicon.

The reactivity of hexamethylcyclotrisiloxane (D3 ) towards BeCl2 , BeBr2 , BeI2 and [Be3 Ph6 ]3 was investigated. While BeCl2 only showed unselective reactivity, BeBr2 , BeI2 and [Be3 Ph6 ] cleanly react to the trinuclear complexes [Be3 Br2 (OSiMe2 Br)4 ], [Be3 I2 (OSiMe2 I)4 ] and [Be3 Ph2 (OSiMe2 Ph)4 ]. These unprecedented bromide, iodide and phenyl transfer reactions from a group II metal onto silicon offer a versatile access to previously unknown diorgano bromo and iodo silanolates.

Bismuth Cations: Fluoride Ion Abstraction, Isocyanide Coordination, and Impact of Steric Bulk on Lewis Acidity.

The molecular compound [BiDipp2 (SbF6 )], containing the bulky, donor-free bismuth cation [BiDipp2 ]+ has been synthesized and fully characterized (Dipp=2,6-iPr2 -C6 H3 ). Using its methyl analog [BiMe2 (SbF6 )] as a second reference point, the impact of steric bulk on bismuth-based Lewis acidity was investigated in a combined experimental (Gutmann-Beckett and modified Gutmann-Beckett methods) and theoretical approach (DFT calculations). Reactivity studies of the bismuth cations towards [PF6 ]- and neutral Lewis bases such as isocyanides C≡NR' revealed facile fluoride ion abstraction and straightforward Lewis pair formation, respectively. The first examples of compounds featuring bismuth-bound isocyanides have been isolated and fully characterized.

Bismuth Cations: Fluoride Ion Abstraction, Isocyanide Coordination, and Impact of Steric Bulk on Lewis Acidity.

Invited for the cover of this issue are the groups of Carsten von Hänisch and Crispin Lichtenberg at the Philipps University of Marburg. The image depicts a bismuth kraken, eagerly grabbing Lewis basic substrates, thereby solving scientific puzzles about bismuth-based Lewis acidity. Read the full text of the article at 10.1002/chem.202204012.

Heavy Chains: Synthesis, Reactivity and Decomposition of Interpnictogen Chains with Terminal Diaryl Bismuth Fragments.

In this work, we report the preparation of multiple interpnictogen chain compounds with three consecutive pnictogen atoms and terminal Ar2 Bi fragments (Ar=Ph, Mes). Symmetrical compounds of the form Ar2 Bi-E(tBu)-Bi2 Ar (1: Ar=Ph, E=P; 2: Ar=Ph, Mes, E=As) as well as ternary interpnictogen compounds of the form Ar2 Bi-E1 (tBu)-E2 tBu2 (Ar=Ph, Mes; 4: E1 =P, E2 =As; 5: E1 =P, E2 =Sb; 6: E1 =As, E2 =P) were prepared. The decomposition in solution at room temperature and under the influence of light was studied for compounds 1-6. The reactivity of 1Ph and 2Ph with the small N-heterocyclic carbene 1,3,4,5-tetramethylimidazol-2-ylidene (Me2 IMe) was also studied. In the case of 1Ph , the formation and consecutive decomposition of Me2 IMe=PtBu (8) was observed in solution. Hence, it was shown that 1Ph can react as a "masked phosphinidene". In the case of 2Ph , no reaction with Me2 IMe was observed. All isolated compounds were analysed by NMR and IR spectroscopy, mass spectrometry, elemental analysis and single-crystal X-ray diffraction.

Heavy Chains: Synthesis, Reactivity and Decomposition of Interpnictogen Chains with Terminal Diaryl Bismuth Fragments.

Invited for the cover of this issue is the group of Carsten von Hänisch at the Philipps-University Marburg. The image depicts a bismuth crystal, a chain formed from it and the molecular structures of different chain molecules with diaryl-bismuth groups. Read the full text of the article at 10.1002/chem.202202932.

Synthesis and Application of Alkali Metal Antimonide-A New Approach to Antimony Chemistry.

Alkali metal dihydrogen-antimonides [M(L)x SbH2 ], short: alkali metal antimonides (M=Li, Na, K, Rb, Cs; 1: L=pmdta; 2: L=crown-ether), were prepared from stibine and n-Butyllithium, M(hmds) (hmds=hexamethyldisilazane) or MOtBu, respectively. We developed a generally applicable synthesis route for these compounds and the obtained compounds were examined on their stability depending on the alkali metal and stabilizing additives used, whereby the use of appropriate crown-ethers allowed their isolation and characterization at room temperature. Moreover, the 1,4-dioxane adduct [Na(dioxane)x SbH2 ] was the appropriate starting compound for the synthesis of the first primary silylstibane (Me3 Si)3 SiSbH2 (3) which was characterized by NMR and IR spectroscopy. Reaction of 3 with (Dipp2 NacNac)Ga (Dipp2 NacNac=HC{C(Me)N(Dipp)}2 ; Dipp=2,6-iPr2 C6 H3 ) resulted in the formation of (Dipp2 NacNac)GaH(SbHSi(SiMe3 )3 ) (4) which was furthermore characterized by single crystal x-ray diffraction.

Construction of Inorganic Crown Ethers by s-Block-Metal-Templated Si-O Bond Activation.

We herein report the synthesis, structures, coordination ability, and mechanism of formation of silicon analogs of crown ethers. An oligomerization of 2 D2 (I) (2 Dn ,=(Me4 Si2 O)n ) was achieved by the reaction with GaI3 and MIx (M=Li, Na, Mg, Ca, Sr). In these reactions the metal cations serve as template and the anions (I- /[GaI4 ]- ) are required as nucleophiles. In case of MIx =LiI, [Li(2 D3 )GaI4 ] (1) is formed. In case of MIx =NaI, MgI2 , CaI2 , and SrI2 the compounds [M(2 D4 )(GaI4 )x ] (M=Mg2+ (3), Ca2+ (4), Sr2+ (5) are obtained. Furthermore the proton complex [H(2 D3 )][Ga2 I7 ] (6) was isolated and structurally characterized. All complexes were characterized by means of multinuclear NMR spectroscopy, DOSY experiments and, except for compound 3, also by single crystal X-ray diffraction. Quantum chemical calculations were carried out to compare the affinity of M+ to 2 Dn and other ligands and to shed light on the formation of larger rings from smaller ones.

Synthesis of a Molecule with Five Different Adjacent Pnictogens.

The first molecular compound with all five pnictogens was obtained by a multi-step reaction. Lithiation of the (bisamido)diazadiarsetidine (tBuNAs)2 (tBuNH)2 in aliphatic solvents leads to the dimeric metallated species [(tBuNAs)2 (tBuNLi)2 ]2 (12 ). Upon reactions with AsCl3 , SbCl3 and BiCl3 the polycyclic compounds [(tBuNAs)2 (tBuN)2 ]PnCl (Pn=As (2), Sb (3), Bi (4)) can be obtained. Conversion of 2-4 with [tBu2 SbP(tBu)Li(OEt2 )]2 leads to the remarkable interpnictogens [(tBuNAs)2 (tBuN)2 ]PnP(tBu)SbtBu2 (Pn=As (5), Sb (6), Bi (7)), whereby 7 is the first example of a molecule containing all five Group 15 elements. The compound with adjacent AsNBiPSb-chains is surprisingly stable and does not show high sensibility against light as the labile Bi-P bond might suggest.

Low-Valent Group†14 Phosphinidenide Complexes [({SIDipp}P)2 M] Exhibit P-M pπ-pπ Interaction (M=Ge, Sn, Pb).

Herein, the synthesis of new low-valent Group 14 phosphinidenide complexes [({SIDipp}P)2 M] exhibiting P-M pπ-pπ interactions (SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolidin-2-ylidene, M=Ge, Sn, Pb), is presented. These compounds were investigated by means of structural, spectroscopic, and quantum-chemical methods. Furthermore, the monosubstituted compounds [(SIDippP)MX]2 (M=Sn, X=Cl; M=Pb, X=Br) are presented, which show dimeric structures instead of multiple bonding interaction.

A Second Modification of Beryllium Bromide: ß-BeBr2.

The synthesis of a second beryllium bromide modification, ß-BeBr2, was accomplished through recrystallization of α-BeBr2 from benzene in the presence of cyclo-decamethylpentasiloxane. This phase was analyzed via single-crystal X-ray diffraction and IR and Raman spectroscopy as well as density functional theory calculations. This enabled a comparison to α-BeBr2 and the α and ß phases of beryllium chloride and iodide.

Low-Valent Group†14 NHC-Stabilized Phosphinidenide ate Complexes and NHC-Stabilized K/P-Clusters.

The N-heterocyclic carbene (NHC)-stabilized phosphinidenide, SIMesPK [SIMes=1,3-bis(2,4,6-trimethylphenyl)imidazolidine-2-ylidene], was used as an (NHC)P-transfer reagent for the synthesis of the low-valent Group 14 ate complexes K[(SIMesP)3 E] (E=Ge: 2, Sn: 3, Pb: 4), which were characterized by 1 H NMR, 31 P NMR, IR spectroscopy as well as elemental and X-ray analysis. Furthermore, SIMesPK was used in reactions with potassium amides and alkoxides to form the molecular phosphorus-potassium clusters [K4 (SIMesP)2 (hmds)2 ] [5, hmds=N(SiMe3 )2 ] and [K6 (SIMesP)2 (OtBu)4 ] (6). Finally, the reaction of SIMesPK with Li[Al(OC4 F9 )4 ] led to the potassium-rich ionic compound [(SIMesP)4 K5 ][Al(OC4 F9 )4 ] (7).

Alkaline Earth Metal Template (Cross-)Coupling Reactions with Hybrid Disila-Crown Ether Analogues.

Alkaline earth metal iodides were used as templates for the synthesis of novel silicon-based ligands. Siloxane moieties were (cross-)coupled and ion-specific, silicon-rich crown ether analogues were obtained. The reaction of 1,2,7,8-tetrasila[12]crown-4 (I) and 1,2-disila[9]crown-3 (II) with MgI2 yielded exclusively [Mg(1,2,7,8-tetrasila[12]crown-4)I2 ] (1). The larger Ca2+ ion was then employed for cross-coupling of I and II and yielded the complex [Ca(1,2,7,8-tetrasila[15]crown-5)I2 ] (2). Cross-coupling of I and 1,2,4,5-tetrasila[9]crown-3 (III) with SrI2 enables the synthesis of the silicon-dominant 1,2,4,5,10,11-hexasila[15]crown-5 ether complex of SrI2 (3). Further, the compounds [Sr(1,2,10,11-tetrasila[18]crown-6)I2 ] (4), [Sr(1,2,13,14-tetrasila[24]crown-8)I2 ] (5), and [Sr(1,2,13,14-tetrasila-dibenzo[24]crown-8)I2 ] (6) were obtained by coupling I, 1,2-disila[12]crown-4 (IV) or 1,2-disila-benzo[12]crown-4 (V), respectively. Using various anions, the (cross-)coupled ligands were also observed in an X-ray structure within the mentioned complexes. These template-assisted (cross-)couplings of various ligands are the first of their kind and a novel method to obtain macrocycles and/or their metal complexes to be established. Further, the Si-O bond activations presented herein might be of importance for silane or even organic functionalization.

Insights into the Coordination Ability of Siloxanes Employing Partially Silicon Based Crown Ethers: A Comparative Analysis of s-Block Metal Complexes.

Herein we present the synthesis and coordination chemistry of the partially silicon based crown ether analogues 1,2,4,5-tetrasila-benzo[15]crown-5 (1) and 1,2,4,5-tetrasila[18]crown-6 (7). Stable complexes of alkali and alkaline earth metal iodides could be obtained showing the good coordination ability of these ligands. The complexes [M A(1,2,4,5-tetrasila-benzo[15]crown-5)I] (M A = Li+ (2), Na+ (4)) and [M EA(1,2,4,5-tetrasila-benzo[15]crown-5)I2] (M EA = Mg2+ (3), Ca2+ (5), Sr2+ (6)) were obtained by equimolar reaction of 1 with the respective alkali or alkaline earth metal iodide. Depending on the ionic radii of the respective cations, the coordination modes of the siloxane backbone are significantly different and could be well-represented by means of 29Si NMR spectroscopy. In addition, we were able to generate the unusual dinuclear complex [Ba2(1,2,4,5-tetrasila[18]crown-6)2I4] (8) by reaction of 7 with BaI2. All compounds were characterized via single crystal X-ray diffraction (XRD) analysis.

Not Non-Coordinating at All: Coordination Compounds of the Cyclodimethylsiloxanes Dn (D = Me2SiO; n = 6, 7) and Group 2 Metal Cations.

We present the coordination chemistry of the cyclodimethylsiloxanes D6 and D7 toward alkaline earth metal salts. The coordination chemistry of these macrocycles toward alkaline earth metals has been unprecedented to date, and we could show that these ligands coordinate better than previously thought. Direct reaction of alkaline earth metal salts with these ligands yields stable complexes even with a relatively strongly coordinating iodide anion. A handful of counterintuitive coordination compounds could be characterized by single-crystal X-ray diffraction analysis. Quantum chemical calculations of suited Born-Haber cycles showed that these complexes are indeed stable, for Mg2+ and Ca2+ even with iodide employed as the anion and for Sr2+ and Ba2+ in the presence of GaI3.

Alkali and Alkaline Earth Metal Derivatives of Disila-Bridged Podands: Coordination Chemistry and Structural Diversity.

Within this study, the synthesis and coordination chemistry of open-chain ligands bearing disila-units is presented. Instead of basic 1:1 complexes, structural diversity was discovered in the variety of ligand and salt. Stable complexes of alkali and alkaline earth metal complexes were obtained by equimolar reactions of different salts with the disila-bridged podands 8,9-disila-EO5 (1) and 11,12-disila-EO7 (2) (EO5 = pentaethylene glycol; EO7 = heptaethylene glycol). The respective alkaline earth metal complexes of the type [Ca(8,9-disila-EO5)(OTf)2] (3), [Sr(8,9-disila-EO5)I2] (5), [Sr(11,12-disila-EO7)I]I (6), and [Ba(11,12-disila-EO7)OTf2] (7) (OTf = CF3SO3-) were characterized via single-crystal X-ray diffraction analyses. Within the reaction of the alkali metal salt NaPF6 with 1, the sodium ion acts as a template during the complexation process. Under elimination of one molecule of diethylene glycol, the dinuclear species [Na2(8,9,17,18-tetrasila-EO8)(PF6)2]·EO2 (4) (EO8 = octaethylen glycol, EO2 = diethylene glycol) is obtained, in which the sodium cations are 7-fold coordinated within a disilane-bearing framework. The reaction of 2 with CsOTf failed, leading to recrystallization of anhydrous CsOTf. By means of DFT calculations it was shown that the disila-bearing ligands are burdened with negative hyperconjugation interactions between the silicon and the oxygen atoms, but the coordination by sufficiently hard cations can easily overcompensate the competing polarization. In contrast, soft Lewis acids barely share interactions with silicon-bonded oxygen atoms. All findings are consistent with observations made in solution according to 29Si NMR spectroscopical studies.

Crown Ether Complexes of Alkali-Metal Chlorides from SO2.

The structures of alkali-metal chloride SO2 solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO2 Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO2 (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes. As a result, 12-crown-4 reacts exclusively with the heavier alkali-metal chlorides NaCl, KCl and RbCl. Compounds [Na(12-crown-4)2 ]Cl⋅4 SO2 (3) and [M(12-crown-4)2 (SO2 )]Cl⋅4 SO2 (4: M=K; 5: M=Rb) all showed S-coordination to the chloride ions through four SO2 molecules. Compounds 4 and 5 additionally exhibit the first crystallographically confirmed non-bridging O,O'-coordination mode of SO2 . Unexpectedly, the disila-crown ether supports the dissolution of RbCl and CsCl in the solvent and gives the homoleptic SO2 -solvated alkali-metal chlorides [MCl⋅3 SO2 ] (6: M=Rb; 7: M=Cs), which incorporate bridging µ-O,O'-coordinating moieties and the unprecedented side-on O,O'-coordination mode. All compounds were characterised by single-crystal X-ray diffraction. The crown ether complexes were additionally studied by using NMR spectroscopy, and the presence of SO2 at ambient temperature was revealed by IR spectroscopy of the neat compounds.

Stable Alkali-Metal Complexes of Hybrid Disila-Crown Ethers.

The complexation ability of hybrid disilane and ethylene containing crown ether ring systems was analyzed using 1,2-disila[12]crown-4 (1), 1,2-disila[15]crown-5 (2), 1,2-disila[18]crown-6 (3), and 1,2,7,8-tetrasila[12]crown-4 (7). Alkali-metal complexes (Li(+), Na(+), K(+)) were obtained and analyzed via X-ray diffraction. The complex stability of [Li(1,2-disila[12]crown-4)](+) and [Li(1,2,7,8-tetrasila[12]crown-4)](+) was determined, in relation to the lithium complex of [12]crown-4, by density functional theory (DFT) calculations employing the BP86/def2-TZVP level of theory. In solution, the exchange of lithium cations between pure [12]crown-4 and hybrid [12]crown-4 is on even terms, as has been shown from the relative binding affinity of compounds 1 and 7 by means of dynamic proton nuclear magnetic resonance (NMR) spectroscopy.

Easy access to strongly fluorescent higher homologues of BODIPY.

We present the easy and high yield synthesis of several group 13 MesDPM compounds (Al-In) with alkyl substituents at the metal atom. All these compounds were fully characterized using techniques including X-ray diffraction analysis and photoluminescence measurements. It shows that for aluminium and gallium pronounced green fluorescence is observed, which is absent for indium. DFT calculations confirm that the first electronic transition corresponds to a ligand-based π-π* transition.