Siliconoid Expansion by a Single Germanium Atom through Isolated Intermediates.

The growth of (semi-)metal clusters is pivotal for nucleation processes in gaseous and condensed phases. We now report the isolation of intermediates during the expansion of a stable unsaturated silicon cluster (siliconoid) by a single germanium atom through a sequence of substitution, rearrangement and reduction. The reaction of ligato-lithiated hexasilabenzpolarene LiSi6 Tip5 (1Li⋅(thf)2 , Tip=2,4,6-triisopropylphenyl) with GeCl2 ⋅NHC (NHC=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) initially yields the product with exohedral germanium(II) functionality, which then inserts into an Si-Si bond of the Si6 scaffold. The concomitant transfer of the chloro functionality from germanium to an adjacent silicon preserves the electron-precise nature of the formed endohedral germylene. Full incorporation of the germanium heteroatom to the Si6 Ge cluster core is finally achieved either by reduction under loss of the coordinating NHC or directly by reaction of 1Li⋅(thf)2 with GeCl2 ⋅1,4-dioxane.

Diarylpnictogenyldialkylalanes─Synthesis, Structures, Bonding Analysis, and CO2 Capture.

Several new diphenylamino- and diphenylphosphanyldialkylalanes are reported, which were characterized in solution and in the solid state, assisted by in-depth bonding analysis within the DFT framework. In the case of bulky alkyl substituents on the aluminum atom, the species are stable in their monomeric form and were structurally characterized by single crystal X-ray diffraction, expanding the relatively small field of monomeric pnictogenylalanes. In the case of oligomeric diphenylpnictogenyldimethylalanes, their reactivity toward different σ-donor ligands was studied, and several examples of monomeric adducts could be structurally characterized, including the first cyclic(alkyl)(amino)carbene complexes. The reactivity of these CAAC complexes, their oligomeric precursors, and an unstabilized monomeric aminoalane toward CO2 was probed, leading to different insertion products that could be characterized. Additionally, the mechanism was elucidated by DFT calculations.

Synthesis and Hydrogen-Bond Patterns of Aryl-Group Substituted Silanediols and -triols from Alkoxy- and Chlorosilanes.

Organosilanols typically show a high condensation tendency and only exist as stable isolable molecules under very specific steric and electronic conditions at the silicon atom. In the present work, various novel representatives of this class of compounds were synthesized by hydrolysis of alkoxy- or chlorosilanes. Phenyl, 1-naphthyl, and 9-phenanthrenyl substituents at the silicon atom were applied to systematically study the influence of the aromatic substituents on the structure and reactivity of the compounds. Chemical shifts in 29 Si NMR spectroscopy in solution, correlated well with the expected electronic situation induced by the substitution pattern on the Si atom. 1 H NMR studies allowed the detection of strong intermolecular hydrogen bonds. Single-crystal X-ray structures of the alkoxides and the chlorosilanes are dominated by π-π interactions of the aromatic systems, which are substituted by strong hydrogen bonding interactions representing various structural motifs in the respective silanol structures.

Transition Metal Complexes of Heavier Vinylidenes: Allylic Coordination vs Vinylidene-Alkyne Rearrangement at Nickel.

Transition metal π-allyl complexes are key reagents/intermediates of various catalytic and stoichiometric allylation reactions. We now report the first transition metal complex of a heavier allylic π-system. The η3-Si2Ge allyl nickel complex is formally obtained by the oxidative addition of the Si-Cl bond of the heavier vinylidene [R2(Cl)Si-(R)Si═(NHC)Ge:] to [Ni(COD)2] (R = 2,4,6-triisopropylphenyl; NHC = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene; COD = 1,5-cyclooctadiene). Due to geometric constraints, the coordination to the Ni(II) center occurs through the formal Si═Ge double bond instead of the residual lone pair of electrons at germanium. In contrast, the Si-N bond of the analogous vinylidene [R2(Me2N)Si-(R)Si═(NHC)Ge:] (obtained by nucleophilic substitution of Cl by NMe2) does not oxidatively add to Ni(0), and a hydridosilagermene-η2-nickel complex is obtained instead. The formation of this complex necessarily implies the isomerization of the heavier vinylidene to the corresponding heteroalkyne with the Si≡Ge triple bond in the coordination sphere of nickel followed by the activation of a C-H bond of one of the isopropyl groups of an N-heterocyclic carbene (NHC) ligand.

Metathesis of Ge=Ge double bonds.

The metathesis of carbon-carbon double bonds-the 'reshuffling' of their constituting carbene fragments-is a tremendously important preparative tool in industry and academia. Metathesis of heavier alkene homologues is restricted to occasional unproductive examples in phosphorus chemistry and cross-metathesis to mixed heavier alkynes. We now report the thermally induced, transition-metal-free metathesis of purpose-built unsymmetrically substituted digermenes. The A2Ge=GeAB starting materials are thus converted to symmetrically substituted derivatives of the A2Ge=GeA2 and ABGe=GeAB types. The use of tethered auxiliary donors (dimethylaniline groups) in substituents B ensures intramolecular donor-acceptor stabilization of the transient germylene fragments, the intermediacy of which is proven by trapping experiments. Density functional theory calculations shed light on the thermodynamic driving force of the metathesis and validate the crucial role of the tethered donor. With an analogously equipped bridged tetragermadiene precursor (A2Ge=GeB-X-BGe=GeA2), heavier acyclic diene metathesis polymerization occurs, in analogy to the widespread acyclic diene metathesis (ADMET) polymerization in the carbon case, yielding a polydigermene.

Diphosphanylmetallocenes of Main-Group Elements.

Several 1,1'-diphosphanyl-substituted metallocenes of magnesium (magnesocenes) were synthesized, structurally characterized, and their reactivity and coordination chemistry were investigated. Transmetalation of these magnesocenes gives access to group 14 metallocenes (tetrelocenes), as well as to group 15 stibonocenes. These s- and p-block metallocenes represent a novel class of bis(phosphanyl) ligands, exhibiting Lewis-amphiphilic character. Their coordination chemistry towards different transition-metal and main-group fragments was investigated and different complexes are presented.

A Mixed Heavier Si=Ge Analogue of a Vinyl Anion.

The versatile reactivities of disilenides and digermenide, heavier analogues of vinyl anions, have significantly expanded the pool of silicon and germanium compounds with various unexpected structural motifs in the past two decades. We now report the synthesis and isolation of a cyclic heteronuclear vinyl anion analogue with a Si=Ge bond, potassium silagermenide as stable thf-solvate and 18-c-6 solvate by the KC8 reduction of germylene or digermene precursors. Its suitability as synthon for the synthesis of functional silagermenes is proven by the reactions with chlorosilane and chlorophospane to yield the corresponding silyl- and phosphanyl-silagermenes. X-ray crystallographic analysis, UV/Vis spectroscopy and DFT calculations revealed a significant degree of π-conjugation between N=C and Si=Ge double bonds in the title compound.

Five new complexes with deferiprone and N,N-donor ligands: evaluation of cytotoxicity against breast cancer MCF-7 cell line and HSA-binding determination.

In this study, five new complexes containing deferiprone (dfp) and N,N-donor ligands [bipyridine (bpy), 1,10-phenanthroline (phen) and ethylenediamine (en)] were synthesized: [Fe(dfp)2(bpy)](PF6) (1), [Fe(dfp)2(phen)](PF6) (2), [Cu2(dfp)2(bpy)2](PF6)2 (3), [Ga(dfp)2(bpy)](PF6) (4), and [Fe(dfp)2(en)](PF6) (5). Characterization of these complexes was carried out through elemental analysis and FT-IR, and single-crystal X-ray crystallography was used to determine their structures. Whilst the polyhedron has a distorted octahedral geometry in 1, 2, 4, and 5, it adopts a distorted square-pyramidal geometry in 3. Interaction of these compounds with human serum albumin (HSA) has been investigated through electronic absorption and fluorescence titration techniques. Emission quenching was performed separately for each complex at three different temperatures and thermodynamic parameters were calculated using binding constants to better understand the power of different binding forces with the HSA. Results demonstrated that compounds interact strongly with the HSA with a static quenching mechanism. Our evaluation of the cytotoxicity of complexes against the breast cancer MCF-7 cell line showed that complex 2 presents a better cytotoxicity than the standard cis-Pt. Finally, using the AutoDock 4.2 program, simulations to analyze the mechanism of complex-HSA interactions and their binding mode were carried out. Results showed that the best binding mode is located in subdomain IB for 1, 2, and 4, in I/II for 3, and in IA/IIA for 5. Communicated by Ramaswamy H. Sarma.

Donor-Stabilized Monocarba-Bridged Bis(cyclopentadienyl)alanes.

Five monocarba-bridged bis(cyclopentadienyl)aluminum halide NHC and thione complexes and one monocarba-bridged bis(cyclopentadienyl)phosphanylalane NHC complex are reported. The former were synthesized by transmetalation of a C[1]magnesocenophane with the corresponding aluminum(III) chloride and aluminum(III) bromide donor adducts. The phosphanylalane complex was obtained by a subsequent functionalization of the corresponding bromoalane with lithium diphenylphosphide. All complexes were characterized in solution by multinuclear NMR spectroscopy and in the solid state by single crystal X-ray diffraction. Bonding energies of the NHC and thione ligands to the aluminum centres were estimated by DFT calculations.

Nickel-assisted complete cleavage of CO by a silylene/siliconoid hybrid under formation of an Si[double bond, length as m-dash]C enol ether bridge.

Reaction of a silylene-functionalized Si6 siliconoid with CO in the presence of catalytic quantities of a nickel(0) complex results in the complete cleavage of the CO triple bond, but preserves the Si6 scaffold with an exohedrally incorporated Si[double bond, length as m-dash]C enol ether bridge. The uncompromised cluster core emphasizes the role of the so-called benzpolarene motif as the energetic silicon pendants of benzene in carbon chemistry.

Pentamethylcyclopentadienyl-substituted hypersilylsilylene: reversible and irreversible activation of C[double bond, length as m-dash]C double bonds and dihydrogen.

Recent studies of low-valent main group species underscore their resemblance to transition metal complexes with regards to the ability to activate small molecules. Here, we report synthesis and full characterisation of the persistent (hypersilyl)(pentamethylcyclopentadienyl)silylene Cp*[(Me3Si)3Si]Si: as well as its unique reactivity. Silylene Cp*[(Me3Si)3Si]Si: activates dihydrogen to give the corresponding dihydrosilane Cp*[(Me3Si)3Si]SiH2 at particularly mild conditions as well as ethylene to afford the three-membered cyclic silirane c-Cp*[(Me3Si)3Si]Si(H2CCH2). The addition of N-heterocyclic carbene NHC (NHC = 1,3,4,5-tetramethyl-imidazol-2-ylidene) to dihydrosilane Cp*[(Me3Si)3Si]SiH2 induces the reductive elimination of Cp*H, which according to DFT calculations is thermodynamically preferred over H2 elimination. With NHC, Cp*[(Me3Si)3Si]Si: forms a typical donor-acceptor complex with concomitant change in hapticity of the Cp* ligand from η2 to η1 (σ). In contrast, the reaction with the N-heterocyclic silylene c-[(CH[double bond, length as m-dash]CH(tBuN)2]Si: leads to an unusual "masked" disilene with the former Cp* ligand bridging the two silicon centres. The heterodimer is stable in the solid state, but dissociates reversibly to the constituting silylene fragments in solution.

Chalcogen-Expanded Unsaturated Silicon Clusters: Thia-, Selena-, and Tellurasiliconoids.

Reactions of silylenes with heavier chalcogens (E) typically result in Si=E double bonds or their π-addition products. In contrast, the oxidation of a silylene-functionalized unsaturated silicon cluster (siliconoid) with Group 16 elements selectively yields cluster expanded siliconoids Si7 E (E=S, Se, Te) fully preserving the unsaturated nature of the cluster scaffold as evident from the NMR signatures of the products. Mechanistic considerations by DFT calculations suggest the intermediacy of a Si6 siliconoid with exohedral Si=E functionality. The reaction thus may serve as model system for the oxidation of surface-bonded silylenes at Si(100) by chalcogens and their diffusion into the silicon bulk.

Free Radical Chemistry of Phosphasilenes.

Understanding the characteristics of radicals formed from silicon-containing heavy analogues of alkenes is of great importance for their application in radical polymerization. Steric and electronic substituent effects in compounds such as phosphasilenes not only stabilize the Si=P double bond, but also influence the structure and species of the formed radicals. Herein we report our first investigations of radicals derived from phosphasilenes with Mes, Tip, Dur, and NMe2 substituents on the P atom, using muon spin spectroscopy and DFT calculations. Adding muonium (a light isotope of hydrogen) to phosphasilenes reveals that: a) the electron-donor NMe2 and the bulkiest Tip-substituted phosphasilenes form several muoniated radicals with different rotamer conformations; b) bulky Dur-substituted phosphasilene forms two radicals (Si- and P-centred); and c) Mes-substituted phosphasilene mainly forms one species of radical, at the P centre. These significant differences result from intramolecular substituent effects.

Equilibrium Formation of Stable All-Silicon Versions of 1,3-Cyclobutanediyl.

Main group analogues of cyclobutane-1,3-diyls are fascinating due to their unique reactivity and electronic properties. So far only heteronuclear examples have been isolated. Here we report the isolation and characterization of all-silicon 1,3-cyclobutanediyls as stable closed-shell singlet species from the reversible reactions of cyclotrisilene c-Si3 Tip4 (Tip=2,4,6-triisopropylphenyl) with the N-heterocyclic silylenes c-[(CR2 CH2 )(NtBu)2 ]Si: (R=H or methyl) with saturated backbones. At elevated temperatures, tetrasilacyclobutenes are obtained from these equilibrium mixtures. The corresponding reaction with the unsaturated N-heterocyclic silylene c-(CH)2 (NtBu)2 Si: proceeds directly to the corresponding tetrasilacyclobutene without detection of the assumed 1,3-cyclobutanediyl intermediate.

Indirect and Direct Grafting of Transition Metals to Siliconoids.

Unsaturated charge-neutral silicon clusters (siliconoids) are important as gas-phase intermediates between molecules and the elemental bulk. With stable zirconocene- and hafnocene-substituted derivatives, we here report the first examples containing directly bonded transition-metal fragments that are readily accessible from the ligato-lithiated Si6 siliconoid (1Li) and Cp2 MCl2 (M=Zr, Hf). Charge-neutral siliconoid ligands with pending tetrylene functionality were prepared by the reaction of amidinato chloro tetrylenes [PhC(NtBu)2 ]ECl (E=Si, Ge, Sn) with 1Li, thus confirming the principal compatibility of such low-valent functionalities with the unsaturated Si6 cluster scaffold. The pronounced donor properties of the tetrylene/siliconoid hybrids allow for their coordination to the Fe(CO)4 fragment.

Magnesocenophane-Catalyzed Amine Borane Dehydrocoupling.

The Lewis acidities of a series of [n]magnesocenophanes (1 a-d) have been investigated computationally and found to be a function of the tilt of the cyclopentadienyl moieties. Their catalytic abilities in amine borane dehydrogenation/dehydrocoupling reactions have been probed, and C[1]magnesocenophane (1 a) has been shown to effectively catalyze the dehydrogenation/dehydrocoupling of dimethylamine borane (2 a) and diisopropylamine borane (2 b) under ambient conditions. Furthermore, the mechanism of the reaction with 2 a has been investigated experimentally and computationally, and the results imply a ligand-assisted mechanism involving stepwise proton and hydride transfer, with dimethylaminoborane as the key intermediate.

Molecular enneanuclear CuII phosphates containing planar hexanuclear and trinuclear sub-units: syntheses, structures, and magnetism.

Highly symmetric enneanuclear copper(ii) phosphates [Cu9(Pz)6(µ-OH)3(µ3-OH)(ArOPO3)4(DMF)3] (PzH = pyrazole, Ar = 2,6-(CHPh2)2-4-R-C6H2; R = Me, 2MeAr; Et, 2EtAr; iPr, 2iPrAr; and Ar = 2,6-iPr2C6H3, 2Dip) comprising nine copper(ii) centers and pyrazole, hydroxide and DMF as ancillary ligands were synthesized by a reaction involving the arylphosphate monoester, 1, copper(i)chloride, pyrazole, and triethylamine in a 4 : 9 : 6 : 14 ratio. All four complexes were characterized by single crystal structural analysis. The complexes contain two distinct structural motifs within the multinuclear copper scaffold: a hexanuclear unit and a trinuclear unit. In the latter, the three Cu(ii) centres are bridged by a µ3-OH. Each pair of Cu(ii) centers in the trinuclear unit are bridged by a pyrazole ligand. The hexanuclear unit is made up of three dinuclear Cu(ii) motifs where the two Cu(ii) centres are bridged by an -OH and a pyrazole ligand. The three dinuclear units are connected to each other by phosphate ligands. The latter also aid the fusion of the trinuclear and the hexanuclear motifs. Magnetic studies reveal a strong antiferromagnetic exchange between the Cu(ii) centres of the dinuclear units in the hexanuclear part and a strong spin frustration in the trinuclear part leading to a degenerate ground state.

Exohedral functionalization vs. core expansion of siliconoids with Group 9 metals: catalytic activity in alkene isomerization.

Taking advantage of pendant tetrylene side-arms, stable unsaturated Si6 silicon clusters (siliconoids) with the benzpolarene motif (the energetic counterpart of benzene in silicon chemistry) are successfully employed as ligands towards Group 9 metals. The pronounced σ-donating properties of the tetrylene moieties allow for sequential oxidative addition and reductive elimination events without complete dissociation of the ligand at any stage. In this manner, either covalently linked or core-expanded metallasiliconoids are obtained. [Rh(CO)2Cl]2 inserts into an endohedral Si-Si bond of the silylene-functionalized hexasilabenzpolarene leading to an unprecedented coordination sphere of the Rh centre with five silicon atoms in the initial product, which is subsequentially converted to a simpler derivative under reconstruction of the Si6 benzpolarene motif. In the case of [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) a similar Si-Si insertion leads to the contraction of the Si6 cluster core with concomitant transfer of a chlorine atom to a silicon vertex generating an exohedral chlorosilyl group. Metallasiliconoids are employed in the isomerization of terminal alkenes to 2-alkenes as a catalytic benchmark reaction, which proceeds with competitive selectivities and reaction rates in the case of iridium complexes.

Synthesis, Structure, and Reactivity of Disiloxa[3]tetrelocenophanes.

Tetramethyldisiloxa[3]metallocenophanes of the heavy group 14 elements germanium, 2a, tin, 2b, and lead, 2c, (tetrelocenophanes) have been synthesized by the reaction of dilithiated ligand, 1, with the corresponding element(II) chloride. The plumbocenophane, 2c, forms one-dimensional coordination polymers in the solid state, while the germanocenophane, 2a, and the stannocenophane, 2b, are monomeric. Furthermore, the reactivity of the stannocenophane, 2b, and the plumbocenophane, 2c, toward N-heterocyclic carbenes was explored. Although the coordination of carbene is reversible in solution at room temperature, the corresponding carbene complexes, 3a,b, could be structurally characterized, illustrating the Lewis acidity of the central atom in these metallocenophanes.

Boron and Phosphorus Containing Heterosiliconoids: Stable p- and n-Doped Unsaturated Silicon Clusters.

Unsaturated silicon clusters (siliconoids) are short-lived intermediates during the transition from molecules to the elemental bulk; stable representatives reiterate surface features of silicon materials. The incorporation of suitable heteroatoms into the cluster scaffold of stable siliconoids extends this analogy to the technological process of silicon doping. Here, we report boron- and phosphorus-containing heterosiliconoids with BSi5 and PSi5 core based on the global minimum Si6R6 platform (dubbed benzpolarene for its relationship to benzene). The reductive cleavage of an SiR2 moiety (R = 2,4,6-iPr3C6H2) from Si6R6 selectively yields a dianionic Si5R42- cluster as its lithium salt. Treatment with Me3SiCl affords the corresponding trimethylsilyl-substituted (Me3Si)2Si5R4. Reaction of Si5R42- with iPr2NECl2 (E = B, P) yields the unprecedented p- and n-doped heterosiliconoids iPr2NESi5R4. Their peculiar electronic features are compared to those of the hexasilabenzpolarene starting material on grounds of NMR spectroscopy, X-ray diffraction, and DFT calculations.