An N‐Heterocyclic Silylene‐Stabilized Digermanium(0) Complex

The synthesis of an N‐heterocyclic silylene‐stabilized digermanium(0) complex is described. The reaction of the amidinate‐stabilized silicon(II) amide [LSiN(SiMe₃)₂] ( 1 ; L=PhC(NtBu)₂) with GeCl₂?dioxane in toluene afforded the Si^II–Ge^II adduct [L{(Me₃Si)₂N}Si→GeCl₂] ( 2 ). Reaction of the adduct with two equivalents of KC₈ in toluene at room temperature afforded the N‐heterocyclic carbene silylene‐stabilized digermanium(0) complex [L{(Me₃Si)₂N}Si→ Ge?Ge←Si{N(SiMe₃)₂}L] ( 3 ). X‐ray crystallography and theoretical studies show conclusively that the N‐heterocyclic silylenes stabilize the singlet digermanium(0) moiety by a weak synergic donor–acceptor interaction.     

Halometallate Complexes of Germanium(II) and (IV): Probing the Role of Cation,Oxidation State and Halide on the Structural and Electrochemical Properties

The Ge^IV chlorometallate complexes, [EMIM]₂[GeCl₆], [EDMIM]₂[GeCl₆] and [PYRR]₂[GeCl₆] (EMIM=1‐ethyl‐3‐methylimidazolium; EDMIM=2,3‐dimethyl‐1‐ethylimidazolium; PYRR=N‐butyl‐N‐methylpyrrolidinium) have been synthesised and fully characterised; the first two also by single‐crystal X‐ray diffraction. The imidazolium chlorometallates exhibited significant C?H???Cl hydrogen bonds, resulting in extended supramolecular assemblies in the solid state. Solution ¹H NMR data also showed cation–anion association. The synthesis and characterisation of Ge^II halometallate salts [EMIM][GeX₃] (X=Cl, Br, I) and [PYRR][GeCl₃], including single‐crystal X‐ray analyses for the homologous series of imidazolium salts, are reported. In these complexes, the intermolecular interactions are much weaker in the solid state and they appear not to be significantly associated in solution. Cyclic‐voltammetry experiments on the Ge^IV species in CH₂Cl₂ solution showed two distinct, irreversible reduction waves attributed to Ge^IV–Ge^II and Ge^II–Ge⁰, whereas the Ge^II species exhibited one irreversible reduction wave. The potential for the Ge^II–Ge⁰ reduction was unaffected by changing the cation, although altering the oxidation state of the precursor from Ge^IV to Ge^II does have an effect; for a given cation, reduction from the [GeCl₃]^? salts occurred at a less cathodic potential. The nature of the halide co‐ligand also has a marked influence on the reduction potential for the Ge^II–Ge⁰ couple, such that the reduction potentials for the [GeX₃]^? salts become significantly less cathodic when the halide (X) is changed Cl→Br→I.     

Concerning the silicon-germanium bond: mass spectral fragmentations of isomeric SiGe compounds R3EE′R3 (E  Si,E′  Ge,R  Ph,Me,(η5-C5H4)Fe (C5H5), (η5-C5H5)Fe(CO)2 and (η5-C9H7) Fe(CO)2)

Isomeric pairs of silicon-germanium compounds containing a SiGe bond (Me₃SiGePh₃ (I) and Ph₃SiGeMe₃ (II); FpSiMe₂GeMe₃ (III) and FpGeMe₂SiMe₃ (IV) (Fp = (η⁵-C₅H₅)Fe(CO)₂); IFpSiMe₂GeMe₃ (V) and IFpGeMe₂SiMe₃ (VI) (IFp = (η⁵-C₉H₇)Fe(CO)₂); IFpSiMe₂GePh₃ (VII) and IFpGeMe₂SiPh₃ (VIII) and the complex FcSiMe₂GeMe₂Fc (IX) (Fc = ferrocenyl) have been synthesized and examined by mass spectrometry.The R₃SiGeR′₃ compounds I and II exhibit considerable exchange of R groups to produce [R_3-nR′_nSi]⁺ and [R′_3-nR_nGe]⁺ ion in progressively lesser amounts as n = 1 → 2 → 3. For the metal-substituted complexes containing the grouping FeSiGe fragmentation occurs predominantly via SiGe bond cleavage with formation of ions containing the silylene ligand [FeSiR₂]⁺. Complexes with the FeGeSi backbone undergo preferential scission of the FeGe bond, illustrating the general bond strength trend FeSi > SiGe. Upon direct cleavage of the SiGe bond in R₃SiGeR₃ compounds, the percentage of the charge carried by [R₃Si]⁺ ions significantly exceeds that carried by [R₃Ge]⁺ ions, reflecting the greater electronegativity of Ge polarizing the SiGe bond.     

Single-Source Precursors for the Chemical Vapor Deposition of Iron Germanides

Binary iron-germanium phases are promising materials in magnetoelectric, spintronic or data storage applications due to their unique magnetic properties. Previous protocols for preparation of Fe_xGe_y thin films and nanostructures typically involve harsh conditions and are challenging in terms of phase composition and homogeneity. Herein, we report the first example of single source chemical vapor deposition (CVD) of Fe_xGe_y films. The appreciable volatility of [Ge[Fe₂(CO)₈]₂], [Cl₂GeFe(CO)₄]₂ and ^Me₂iPr₂NHC ⋅ GeCl₂ ⋅ Fe(CO)₄ allowed for their application as precursors under standard CVD conditions (^Me₂iPr₂NHC=1,3-diisopropoyl-4,5-dimethylimidazol-2-ylidene). The thermal decomposition products of the precursors were characterized by TGA and powder XRD. Deposition experiments in a cold-wall CVD reactor resulted in dense films of Fe_xGe_y. During the optimization of synthetic conditions for precursor preparation the new iron-germanium cluster Cl₂Ge[Fe₂(CO)₈]Ge[Fe₂(CO)₈] was obtained in experiments with a higher stoichiometric ratio of GeCl₂ ⋅ 1,4-dioxane vs. Fe₂(CO)₉.     

Zintl Clusters as Wet‐Chemical Precursors for Germanium Nanomorphologies with Tunable Composition

[Ge₉]^4? Zintl clusters are used as soluble germanium source for a bottom–up fabrication of Ge nanomorphologies such as inverse opal structures with tunable composition. The method is based on the assembly and oxidation of [Ge₉]^4? clusters in a template mold using SiCl₄, GeCl₄, and PCl₃ leading to Si and P‐containing Ge phases as shown by X‐ray diffraction, Raman spectroscopy, and energy‐dispersive X‐ray analysis. [Ge₉]^4? clusters are retained using ethylenediamine (en) as a transfer medium to a mold after removal of the solvent if water is thoroughly excluded, but are oxidized to amorphous Ge in presence of water traces. ¹H NMR spectroscopy reveals the oxidative deprotonation of en by [Ge₉]^4?. Subsequent annealing leads to crystalline Ge. As an example for wet‐chemical synthesis of complex Ge nanomorphologies, we describe the fabrication of undoped and P‐doped inverse opal‐structured Ge films with a rather low oxygen contents. The morphology of the films with regular volume porosity is characterized by SEM, TEM, and grazing incidence small‐angle X‐ray scattering.     

Isolation of an Imino‐N‐heterocyclic Carbene/Germanium(0) Adduct: A Mesoionic Germylene Equivalent

An autoionization of germanium dichloride/dioxane complex with an imino‐N‐heterocyclic carbene ligand ( L ) afforded a novel germyliumylidene ion, [( L )GeCl]⁺[GeCl₃]^?, which was fully characterized. Reduction of the germyliumylidene ion with potassium graphite produced a cyclic species [( L )Ge], which can be viewed as both a Ge⁰ species and a mesoionic germylene. X‐ray diffraction analysis and computational studies revealed one of the lone pairs on the Ge atom is involved in the π system on the GeC₂N₂ five‐membered ring. It was also confirmed that the nucleophilic behavior of [( L )Ge] as a two lone‐pair donor.     

Reactivity of a N-Coordinated Germylene-Borane Complex: From Ge→B to Ge→Ga Coordination

Reactivity studies of the Ge^II→B complex L(Cl)Ge⋅BH₃ ( 1 ; L=2-Et₂NCH₂-4,6-tBu₂-C₆H₂) were performed to determine the effect on the Ge^II→B donation. N-coordinated compounds L(OtBu)Ge⋅BH₃ ( 2 ) and [LGe⋅BH₃]₂ ( 3 ) were prepared. The possible tuning of the Ge^II→B interaction was proved experimentally, yielding compounds 1-PPh₂-8-(LGe)-C₁₀H₆ ( 4 ) and L(Cl)Ge⋅GaCl₃ ( 5 ) without a Ge^II→B interaction. In 5 , an unprecedented Ge^II→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the Ge^II→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed.     

Synthesis,Structures, and Light‐Induced Transformation of Keto‐Functionalized Selenidogermanate Complexes

A double‐decker (DD) type selenidogermanate complex with C=O functionalized organic decoration, [(R¹Ge₄)Se₆] ( 1 , R¹ = CMe₂CH₂COMe), was synthesized by reaction of R¹GeCl₃ with Na₂Se, and subsequently underwent a light‐induced transformation reaction to yield [Na(thf)₂][(RGe^IV)₂(RGe^III)(Ge^IIISe)Se₅] ( 2 ). Similar to the observations reported previously for the Sn/S homologue of 1 , the product comprises a mixed‐valence complex with a newly formed Ge–Ge bond. However, different from the transformation of the tin sulfide complex, the selenidogermanate precursor did not produce a paddle‐wheel‐like dimer of the DD type structure, but led to the formation of a noradamantane (NA) type architecture, which has so far been restricted to the Si/Se and Ge/Te elemental combination.     

A bis(silylene)pyridine pincer ligand can stabilize mononuclear manganese(0) complexes: facile access to isolable analogues of the elusive d7-Mn(CO)5 radical

Using the potentially tridentate N,N′-bis(N-heterocyclic silylene)pyridine [SiNSi] pincer-type ligand, 2,6-N,N′-diethyl-bis[N,N′-di-tert-butyl(phenylamidinato)silylene] diaminopyridine, led to the first isolable bis(silylene)pyridine-stabilized manganese(0) complex, {κ³-[SiNSi]Mn(dmpe)} 4 (dmpe = (Me₂P)₂C₂H₄), which represents an isolobal 17 VE analogue of the elusive Mn(CO)₅ radical. The compound is accessible through the reductive dehalogenation of the corresponding dihalido (SiNSi)Mn(ii) complexes 1 (Cl) and 2 (Br) with potassium graphite. Exposing 4 towards the stronger π-acceptor ligands CO and 2,6-dimethylphenyl isocyanide afforded the related Mn(0) complexes κ²-[SiNSi]Mn(CO)₃ (5) and κ³-[SiNSi]Mn(CNXylyl)₂(κ¹-dmpe) (6), respectively. Remarkably, the stabilization of Mn(0) in the coordination sphere of the [SiNSi] ligand favors the d⁷ low-spin electronic configuration, as suggested by EPR spectroscopy, SQUID measurements and DFT calculations. The suitability of 4 acting as a superior pre-catalyst in regioselective hydroboration of quinolines has also been demonstrated.

An isolable bis(silylene)pyridine stabilized manganese(0) complex {κ³-[SiNSi]Mn(dmpe)}, isolobal to elusive Mn(CO)₅ radical has been synthesized and fully characterised.     

Reactions of GeCl2 with the Thiolate LiSC(SiMe3)3: From thf Activation to Insertion of GeCl2 Molecules into C−S Bonds

The reaction system GeCl₂ ⋅ dioxane/LiSTsi (Tsi=C(SiMe₃)₃) opens a fruitful area in germanium chemistry, depending on the stoichiometry and solvent used during the reaction. For example, the reaction of GeCl₂ ⋅ dioxane in toluene with two equivalents of the thiolate gives the expected germylene Ge(STsi)₂ in excellent yield. This germylene readily reacts with hydrogen and acetylene, however, in a non-selective way. By using an excess amount of the thiolate and toluene as the solvent, the germanide [Ge(STsi)₃][Li(thf)] is obtained. Performing the same reaction in thf leads to a C−H activation of thf to give (H₇C₄O)Ge[STsi](μ²-S)₂Ge[STsi]₂, in which the thf molecule is still intact. Using a sub-stoichiometric amount of the thiolate leads to the heteroleptic compound [ClGe(STsi)]₂ and to the insertion product (thf)Ge[S-GeCl₂-Tsi]₂, in which additional GeCl₂ molecules insert into the C−S bonds of Ge(STsi)₂. The synthesis and the experimentally determined structures of all compounds are presented together with first reactivity studies of Ge(STsi)₂.     

Two Different Products Observed in the Reaction of a Bis(germylene) with Molybdenum Hydride [Mo(H)Cp(CO)3]

The reaction of the dimeric bis(germylene) [Ge{3,5‐(CF₃)₂pz}₂]₂ ( 2 ) with protic molybdenum hydride [Mo(H)Cp(CO)₃] yielded two different products. In diethyl ether the divalent germylene readily inserts into the Mo–H σ‐bond and the product of the oxidative addition, [Ge(H){Mo}(pz)₂] ( 4 ) (with pz = 3,5‐disubstituted pyrazole, 3,5‐(CF₃)₂pz; {Mo} = [MoCp(CO)₃]), was isolated featuring a germanium(IV) hydride moiety. In toluene an interesting “cascade” reaction takes place furnishing a bis‐metal substituted digermane [{Mo}(H)(pz)Ge–Ge(pz)₂{Mo}]. Although the detailed mechanism of the reaction remains the subject of speculation it seems likely that a germylene, [Ge^II(pz){Mo}], inserts into the germanium(IV) hydrogen bond of [Ge(H){Mo}(pz)₂] under formation of a germanium‐germanium bond, which is a rare reaction behaviour.     

A Coordination Compound of Ge0 Stabilized by a Diiminopyridine Ligand

Reduction of the cationic Ge^II complex [dimpyrGeCl][GeCl₃] (dimpyr=2,6‐(ArN=CMe)₂NC₅H_3, Ar=2,6‐iPr₂C₆H₃) with potassium graphite in benzene affords an air sensitive, dark green compound of Ge⁰, [dimpyrGe], which is stabilized by a bis(imino)pyridine platform. This compound is the first example of a complex of a zero‐valent Group 14 element that does not contain a carbene or carbenoid ligand. This species has a singlet ground state. DFT studies revealed partial delocalization of one of the Ge lone pairs over the π*(C?N) orbitals of the imines. This delocalization results in a partial multiple‐bond character between the Ge atom and imine nitrogen atoms, a fact supported by the X‐ray crystallography and IR spectroscopy data.     

Trigonal-bipyramidale Heterometallatomcluster vom Typ closo-Fe3(CO)9-[μ3- MRe(CO)5]2 (M = Ge,Sn)

Trigonal Bipyramidic Heteronuclear Metal Atom Clusters of the Type closo-Fe₃(CO)₉-[μ₃- MRe(CO)₅]₂ (M = Ge, Sn) The diamagnetic title compounds were prepared by the reaction of SnCl₂ (or Ge/GeCl₄), MnRe(CO)₁₀, and Fe(CO)₅ at 220°C in a glass tube. The result of the single crystal X-ray analysis of Fe₃(CO)₉[μ₃-SnRe(CO)₅]₂ showed that the triangular molecular fragment of Fe₃(CO)₉ with a fac-CO ligand arrangement at each Fe atom was capped by two μ₃-SnRe(CO)₅ groups forming a trigonal bipyramidic metal atom polyhedron. The characterization of its Sn? Re bond length [av. 272,6(2) pm] was undertaken by comparison with that of Cl₂Sn[Re(CO)₅]₂ [277.9(4) pm] obtained from a further structural determination. This type of polyhedron with Ge^IV and transition metal atoms bonds was before unknown. The ν(CO) i.r. absorption bands of both heteronuclear metal atom clusters and their electron absorption bands above λ = 350 nm were measured.     

An Isolable Bis(Germylene)-Stabilized Plumbylone

We report herein the synthesis of a stable plumbylone ( 3 ) by reduction of a bromodigermylplumbylene ( 2 ) with 2.2 equiv of potassium graphite (KC₈). The molecular structure of 3 was established by a single-crystal X-ray diffraction study and features a two-coordinated Pb center with an acute Ge−Pb−Ge bond angle. Computational studies showed that this complex ( 3 ) possesses a singlet electronic ground state with a Pb⁰ center. Its high thermal stability can be most likely ascribed to the delocalization of π electrons over the Ge−Pb−Ge moiety. A preliminary reactivity study demonstrates that complex 3 can deliver Pb⁰ atoms to an organic azide producing a tetrameric imido complex [(PbNDipp)₄] (Dipp=2,6-ⁱPr-C₆H₃, 4 ) and perform a metathesis reaction with GeCl₂⋅dioxane to produce a bis(germylene)-stabilized germylone ( 5 ), highlighting the synthetic utility of 3 .     

Ge4Cl4[MCp(CO)3]4 (M = Cr,Mo, W): A Series of Transition Metal Substituted Four-membered Cyclogermanes

The reaction of GeCl₂ · dioxane with the sodium salts NaMCp(CO)₃ (M = Cr, Mo, W) leads to new four-membered ring compounds Ge₄Cl₄[MCp(CO)₃]₄, where the remaining chlorine atom cannot be substituted by another MCp(CO)₃ substituent. A large excess of the sodium salts only leads to some minor side-reactions. All Ge₄-compounds exhibit a non-planar four-membered Ge₄ ring, which can be traced back to electrostatic effects as shown by quantum chemical calculations. Furthermore, cluster build-up reactions might be possible due to the halide substituents in the new ring compounds of germanium, showing that GeCl₂ · dioxane is an excellent starting material for the synthesis of cluster compounds of germanium.     

Facile Access to NaOC≡As and Its Use as an Arsenic Source To Form Germylidenylarsinidene Complexes

A facile, one‐pot synthesis of [Na(OC≡As)(dioxane)_x ] (x =2.3–3.3) in 78 % yield is reported through the reaction of arsine gas with dimethylcarbonate in the presence of NaO^t Bu and 1,4‐dioxane. It has been employed for the synthesis of the first arsaketenyl‐functionalized germylene [LGeAsCO] ( 2 , L=CH[CMeN(Dipp)]₂; Dipp=2,6‐ⁱ Pr₂C₆H₃) from the reaction with LGeCl ( 1 ). Upon exposure to ambient light, 2 undergoes CO elimination to form the 1,3‐digerma‐2,4‐diarsacyclobutadiene [L₂Ge₂As₂] ( 3 ), which contains a symmetric Ge₂As₂ ring with ylide‐like Ge=As bonds. Remarkably, the CO ligand located at the arsenic center of 2 can be exchanged with PPh₃ or an N‐heterocyclic carbene ^{i Pr}NHC donor (^{i Pr}NHC=1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) to afford the novel germylidenylarsinidene complexes [LGe‐AsPPh₃] ( 4 ) and [LGe‐As(^{i Pr}NHC)] ( 5 ), respectively, demonstrating transition‐metal‐like ligand substitution at the arsinidene‐like As atom. The formation of 2 – 5 and their electronic structures have been studied by DFT calculations.     

Nickel as a Lewis Base in a T‐Shaped Nickel(0) Germylene Complex Incorporating a Flexible Bis(NHC) Ligand

Flexible, chelating bis(NHC) ligand 2 , able to accommodate both cis‐ and trans‐coordination modes, was used to synthesize ( 2 )Ni(η²‐cod), 3 . In reaction with GeCl₂, it produced ( 2 )NiGeCl₂, 4 , featuring a T‐shaped Ni⁰ and a pyramidal Ge center. Complex 4 could also be prepared from [( 2 )GeCl]Cl, 5 , and Ni(cod)₂, in a reaction that formally involved Ni–Ge transmetalation, followed by coordination of the extruded GeCl₂ moiety to Ni. A computational analysis showed that 4 possesses considerable multiconfigurational character and the Ni→Ge bond is formed through σ‐donation from the Ni 4s, 4p, and 3d orbitals to Ge. (NHC)₂Ni(cod) complexes 9 and 10 , as well as (NHC)₂GeCl₂ derivative 11 , incorporating ligands that cannot accommodate a wide bite angle, failed to produce isolable Ni–Ge complexes. The isolation of ( 2 )Ni(η²‐Py), 12 , provides further evidence for the reluctance of the ( 2 )Ni⁰ fragment to act as a σ‐Lewis acid.     

Unexpected Photodegradation of a Phosphaketenyl‐Substituted Germyliumylidene Borate Complex

The first zwitterionic borata‐bis(NHC)‐stabilized phosphaketenyl germyliumylidene [(L₂(O=C=P)Ge:] 2 (L₂=(p ‐tolyl)₂B[1‐(1‐adamantyl)‐3‐yl‐2‐ylidene]₂) has been synthesized by salt‐metathesis reaction of [L₂(Cl)Ge:] 1 with sodium phosphaethynolate [(dioxane)_n NaOCP]. Unexpectedly, its exposure to UV light affords, after reductive elimination of the entire PCO group, the unprecedented [L₂Ge‐GeL₂] complex 3 in 54 % yields bearing the Ge₂²⁺ ion with Ge in the oxidation state +1. In addition, the 1,3‐digermylium‐2,4‐diphosphacyclobutadiene [L₂Ge(μ‐P)₂GeL₂] 4 and bis(germyliumylidenyl)‐substituted diphosphene [(L₂Ge‐P=P‐GeL₂)] 5 could also be obtained in moderate yields. The formation of 3 – 5 and their electronic structures have been elucidated with DFT calculations.     

From a Phosphaketenyl‐Functionalized Germylene to 1,3‐Digerma‐2,4‐diphosphacyclobutadiene

The first 4π‐electron resonance‐stabilized 1,3‐digerma‐2,4‐diphosphacyclobutadiene [L^H₂Ge₂P₂] 4 (L^H=CH[CHNDipp]₂ Dipp=2,6‐ⁱPr₂C₆H₃) with four‐coordinate germanium supported by a β‐diketiminate ligand and two‐coordinate phosphorus atoms has been synthesized from the unprecedented phosphaketenyl‐functionalized N‐heterocyclic germylene [L^HGe‐P=C=O] 2 a prepared by salt‐metathesis reaction of sodium phosphaethynolate (P≡C?ONa) with the corresponding chlorogermylene [L^HGeCl] 1 a . Under UV/Vis light irradiation at ambient temperature, release of CO from the P=C=O group of 2 a leads to the elusive germanium–phosphorus triply bonded species [L^HGe≡P] 3 a , which dimerizes spontaneously to yield black crystals of 4 as isolable product in 67 % yield. Notably, release of CO from the bulkier substituted [L^tBuGe‐P=C=O] 2 b (L^tBu=CH[C(^tBu)N‐Dipp]₂) furnishes, under concomitant extrusion of the diimine [Dipp‐NC(^tBu)]₂, the bis‐N,P‐heterocyclic germylene [DippNC(^tBu)C(H)PGe]₂ 5 .     

The Largest Metalloid Group 14 Cluster,Ge18[Si(SiMe3)3]6: An Intermediate on the Way to Elemental Germanium

The oxidation of [Ge₉(Hyp)₃]^? (Hyp=Si(SiMe₃)₃) with an Fe^II salt leads to Ge₁₈(Hyp)₆ ( 1 ), the largest Group 14 metalloid cluster that has been structurally characterized to date. The arrangement of the 18 germanium atoms in 1 shows similarities to that found in the solid‐state structure Ge(cF136). Furthermore, 1 can be described as a macropolyhedral cluster of two Ge₉ units. Quantum‐chemical calculations further hint at a strained arrangement so that 1 can be considered as a first trapped intermediate on the way from Ge₉ units to elemental germanium with the clathrate‐II structure (Ge(cF136)).