Diverse Reactivity of bis(Silylene) and bis(Germylene) [LE−EL (E=Si and Ge: L=PhC(NtBu)2)] in the Oxidative Activation of C−F Bond: Si−Si Bond is Retained While the Ge−Ge Bond Is Cleaved

Herein we report the reactions of 3,4,5,6-tetrafluoroterephthalonitrile ( 1 ) with bis(silylene) and bis(germylene) LE−EL [E=Si ( 2 ) and Ge( 3 ): L=PhC(N^tBu)₂)]. The reaction of LSi−SiL (L=PhC(N^tBu)₂) ( 2 ) with two equivalents of 1 resulted in an unprecedented oxidative addition of a C−F bond of 1 leading to disilicon(III) fluoride {L(4-C₈F₃N)FSi−SiF(4-C₈F₃N)L}( 4 ), wherein the Si−Si single bond was retained. In contrast, the reaction of LGe−GeL (L=PhC(N^tBu)₂) ( 3 ) with one equivalent of 1 resulted in the oxidative cleavage of Ge−Ge bond leading to L(4-C₈F₃N₂)Ge ( 5 ) and LGeF ( 6 ). All three compounds ( 4 – 6 ) were characterized by NMR spectroscopy, EI-MS spectrometry, and elemental analysis. X-ray single-crystal structure determination of compound 4 unequivocally established that the Si^III−Si^III bond remains uncleaved.     

Cyanidosilicates—Synthesis and Structure

Starting from fluoridosilicate precursors in neat cyanotrimethylsilane, Me₃Si?CN, a series of different ammonium salts [R₃NMe]⁺ (R=Et, ⁿPr, ⁿBu) with the novel [SiF(CN)₅]^2? and [Si(CN)₆]^2? dianions was synthesized in facile, temperature controlled F^?/CN^? exchange reactions. Utilizing decomposable, non‐innocent cations, such as [R₃NH]⁺, it was possible to generate metal salts of the type M₂[Si(CN)₆] (M⁺=Li⁺, K⁺) via neutralization reactions with the corresponding metal hydroxides. The ionic liquid [BMIm]₂[Si(CN)₆] (m.p.=72 °C, BMIm=1‐butyl‐3‐methylimidazolium) was obtained by a salt metathesis reaction. All the synthesized salts could be isolated in good yields and were fully characterized.     

Ab initio Study on Formation Mechanism of Spiro-Si-Heterocyclic Ring Compound Involving Ge from H2Ge=Si: and Formaldehyde

H₂Ge=Si: and its derivatives (X₂Ge=Si:, X=H, Me, F, Cl, Br, Ph, Ar,…) are new species. Its cycloaddition reactions are new area for the study of silylene chemistry. The cycloaddition reaction mechanism of singlet H₂Ge=Si: and formaldehyde has been investigated with the MP2/aug-cc-pVDZ method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rule is that two reactants firstly form a four-membered Ge-heterocyclic ring silylene through the [2+2] cycloaddition reaction. Because of the 3p unoccupied orbital of Si: atom in the four-membered Ge-heterocyclic ring silylene and the π orbital of formaldehyde forming a π→p donor-acceptor bond, the four-membered Ge-heterocyclic ring silylene further combines with formaldehyde to form an intermediate. Because the Si: atom in the intermediate undergoes sp³ hybridization after transition state, then the intermediate isomerizes to a spiro-Si-heterocyclic ring compound involving Ge via a transition state. The result indicates the laws of cycloaddition reaction between H₂Ge=Si: or its derivatives (X₂Ge=Si:, X=H, Me, F, Cl, Br, Ph, Ar,…) and asymmetric π-bonded compounds are significant for the synthesis of small-ring involving Si and Ge and spiro-Si-heterocyclic ring compounds involving Ge.     

Organogermane homopolymers and copolymers with organosilane

The first high molecular weight soluble, formable organogermane homopolymer (n-Bu₂Ge)_n was synthesized by the sodium coupling of n-Bu₂GeCl₂ in toluene. Soluble organogermane/organosilane copolymers [(X₂Ge)_x(YZSi)_y]_n were prepared by sodium coupling of X₂GeCl₂ and YZSiCl₂ in different molar ratios (X = n-bu, Ph; Y = n-hexyl, cyclohexyl; Z = Me). Germanium-containing polymers and copolymers with organosilanes are highly absorbing between 300–360 nm, with the absorption maxima dependent on the nature of the substituent and the ratio of X₂Ge:YZSi in the polymer. These polymers are photoactive and display bleaching behavior with photoscission.     

Group 14 structural variations: perhalo derivatives of the “dimetallenes”: dicarbenes, disilenes, digermenes, distannenes, and diplumbenes

Trends in the structural variations of all perhalo derivatives of dicarbenes and their Group 14 analogues have been studied. This included all M₂X₄ molecules, where M = C, Si, Ge, Sn, or Pb, and X = F, Cl, Br, or I. Mapping the potential energy surface of all molecules has uncovered several isomers. The stability of these isomers depends on both the Group 14 atoms and the halogen ligands. Several isomers were found stable; the ones that are global minima include (with their symmetries and an example in parenthesis): the typical ethene structure X₂M=MX₂ (D _2h, F₂C=CF₂), an X₃M–MX structure (C _S, F₃Si–SiF, a trifluorosilyl–silylene), another X₃M–MX structure (C ₁, Cl₃Si–SiCl), one more X₃M–MX structure with a single halogen bridge (C ₁, I₂Si–μI–SiI), a trans double halogen bridged structure (D _2h, FSn–μF₂–SnF), and another trans double-bridged structure with puckered ring (C _S, IPb–μI₂–PbI). Some of the other structures that are stable but are not the global minima include: a trans-bent structure X₂M–MX₂ (C _2h, all X₂Si–SiX₂), cis double-bridged structure (C _2v with planar ring, FPb–μF₂–PbF, or with puckered ring, C _2v, IGe–μI₂–GeI), and even a square bipyramidal structure (D _4h, Sn–μF₄–Sn). The energy differences between some of the structures are small and the application of another computational method and using a different basis set might alter their relative stabilities. Reasons for the difference in the stabilities of isomers have been discussed.     

Halogen Bonding to Amplify Luminescence: A Case Study Using a Platinum Cyclometalated Complex

The cocrystallization of a weakly luminescent platinum complex [Pt(btpy)(PPh₃)Cl] ( 1 ) (Hbtpy=2‐(2benzothienyl)pyridine; emission quantum yield Φ_em=0.03) with fluorinated bromo‐ and iodoarenes C₆F_6‐nX_n (X=Br, I; n=1, 2) results in the formation of efficient halogen‐bonding (XB) interactions Pt? Cl???X? R. An up to 22‐fold enhancement (Φ_em=0.65) in the luminescence intensity of the cocrystallized compound is detected, without a substantial change of the emission energy. Based on crystallographic, photophysical, and theoretical investigations, the contribution of the XB donors C₆F_6‐nX_n to the amplification of luminescence intensity is attributed to the enhancement of spin–orbit coupling through the heavy‐atom effect, and simultaneously to the suppression of the nonradiative relaxation pathways by increasing the rigidity of the chromophore center.     

Three Roles for the Fluoride Ion in Palladium‐Catalyzed Hiyama Reactions: Transmetalation of [ArPdFL2] by Ar′Si(OR)3

From the kinetic data on the transmetalation/reductive elimination in fluoride‐promoted Hiyama reactions, obtained using electrochemical techniques, it has been established that fluoride ions play three roles. F^? reacts with trans‐[ArPdBrL₂] (L=PPh₃) to form trans‐[ArPdFL₂], which reacts with Ar′Si(OMe)₃ in the rate‐determining transmetalation, whereas trans‐[ArPdBrL₂] does not react with Ar′Si(OMe)₃. F^? reacts with Ar′Si(OMe)₃ to deliver the unreactive silicate Ar′SiF(OMe)₃^?, thus leading to two antagonistic kinetic effects. In addition, F^? catalyzes the reductive elimination from intermediate trans‐[ArPdAr′L₂].     

First-principle studies of Ca-X (X=Si,Ge,Sn,Pb) intermetallic compounds

The structural properties, elastic properties, heats of formation, electronic structures, and densities of states of 20 intermetallic compounds in the Ca-X (X=Si, Ge, Sn, Pb) systems have been systematically investigated by using first-principle calculations. Our computational results indicated that with increasing atomic weight of X, the bulk modulus of Ca-X intermetallic compounds decreases gradually. It was also found that Ca₃₆Sn₂₃ and CaPb are mechanically unstable phases. Results on the electronic energy band and densities of states also indicated that Ca₃Si₄ is an indirect band gap semiconductor with a band gap of 0.598 eV, and Ca₂Si, Ca₂Ge, Ca₂Sn, and Ca₂Pb are direct band gap semiconductors with band gaps of 0.324, 0.265, 0.06, and 0.07 eV, respectively. In addition, it is found that the absolute values of heats of formation for all Ca-X intermetallics are larger than 30 kJ/mol atom.     

Atomic interactions in the hydrides and alkyls of C,Si, Ge,and Sn

The spectra of these group IV (M=C, Si, Ge, and Sn) compounds show that induction from M increases in a sequence that qualitatively agrees with the Pauli-Gordy-Mulliken scale; the induction constant o* for (CH₃)₃M is –0.3, –0.72, –0.76, and –0.9 in the four cases. M also acts as an electron acceptor, the effect increasing from Si via Ge to Sn; this and the induction determine the electron-density distribution in adjacent bonds. These concepts explain the anomalous behavior of the optical parameters and chemical shifts in the methyl derivatives of M. The analogy with the magnetic parameters indicates that the Olred-Rakhov electronegativity scale (X _C=2.6; X _Sl=1.9; X _Ge=2.0; X _Sn=1.93) does not reflect the induction effects of M in pure form but provides a good measure of the sum of the electronic effects. The present results do not confirm the view that silicon transmits induction less readily than carbon.     

Die Ammonolyse von (NH4)2GeF6. Darstellung und Struktur von NH4[Ge(NH3)F5]

Ammonolysis Reaction of (NH₄)₂GeF₆. Synthesis and Structure of NH₄[Ge(NH₃)F₅] (NH₄)₂GeF₆ reacts with ammonia to yield NH₄[Ge(NH₃)F₅] at 280°C. The reaction path was elucidated by in situ time and temperature resolved X-ray powder diffraction. NH₄[Ge(NH₃)F₅] crystallizes isostructurally to NH₄[Si(NH₃)F₅] in the tetragonal space group P4/n (No. 85) with lattice constants a = 619.41(1) pm and c = 724.70(1) pm. The germanium atom is coordinated by five fluorine atoms and the nitrogen atom of the ammonia molecule. The ammonium cation is located on the Wyckoff position (2 a) in P4/n. The crystal structure is stabilized by extensive hydrogen bonding.     

Two‐, One‐, and Zero‐Dimensional Elemental Nanostructures Based on Ge9‐Clusters

We investigated the structural principles of novel germanium modifications derived by oxidative coupling of Zintl‐type [Ge₉]^4?clusters in various ways. The structures, stabilities, and electronic properties of the predicted {²_∞[Ge₉]_n} sheet, {¹_∞[Ge₉]_n} nanotubes, and fullerene‐like {Ge₉}_n cages were studied by using quantum chemical methods. The polyhedral {Ge₉}_n cages are energetically comparable with bulk‐like nanostructures of the same size, in good agreement with previous experimental findings. Three‐dimensional structures derived from the structures of lower dimensionality are expected to shed light on the structural characteristics of the existing mesoporous Ge materials that possess promising optoelectronic properties. Furthermore, 3D networks derived from the polyhedral {Ge₉}_n cages lead to structures that are closely related to the well‐known LTA zeolite framework, suggesting further possibilities for deriving novel mesoporous modifications of germanium. Raman and IR spectra and simulated X‐ray diffraction patterns of the predicted materials are given to facilitate comparisons with experimental results. The studied novel germanium modifications are semiconducting, and several structure types possess noticeably larger band gaps than bulk α‐Ge.     

Geometries,vibrational frequencies,and electron affinities of X2Cl (X=C,Si,Ge) clusters

Ab initio quantum chemical calculations have been performed on X₂Cl^? and X₂Cl (X = C, Si, Ge) clusters. The geometrical structures, vibrational frequencies, electronic properties and dissociation energies are investigated at the Hartree–Fock (HF), Møller–Plesset second‐ and fourth‐order (MP2, MP4), CCSD(T) level with the 6‐311+G(d) basis set. The X₂Cl (X = C, Si, Ge) and X₂Cl^? (X = Si, Ge) take a bent shape obtained at the ground state, while C₂Cl^? has a linear structure. The impact on internal electron transfer between the X₂Cl and the corresponding anional clusters is studied. The three different types of electron affinities (EAs) at the CCSD(T) are reported. The most reliable adiabatic electronic affinities, obtained at the CCSD(T)/cc‐pvqz level of theory, are predicted to be 3.30, 2.62, and 1.98 eV for C₂Cl, Si₂Cl, and Ge₂Cl, respectively. The calculated EAs of C₂Cl and Ge₂Cl are in good agreement with theoretical results reported. The correlation effects and basis sets effects on the geometrical structures and dissociation energies are discussed. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

The Effect of Ge Incorporation on the Brønsted Acidity of ZSM‐5

The effect of the isomorphous substitution of some of the Si atoms in ZSM‐5 by Ge atoms on the Brønsted acid strength has been investigated by i) DFT calculations on cluster models of the formula ((HO)₃SiO)₃‐Al‐O(H)‐T‐(OSi(OH)₃)₃, with T=Si or Ge, and ((HO)₃SiO)₃‐Al‐O(H)‐Si‐(OGe(OH)₃)(OSi(OH)₃)₂, ii) a ³¹P NMR study of zeolite samples contacted with trimethyl phosphine oxide probe molecules and iii) a X‐ray photoelectron spectroscopy (XPS) study of ZSM‐5 and Ge‐ZSM‐5 samples. The calculations reveal that the effect of Ge incorporation on the framework acidity strongly depends on the degree of substitution and on the exact T‐atom positions that are occupied by Ge. High Ge concentrations allow for enhanced stabilisation of the deprotonated Ge‐ZSM‐5 through structural relaxation, resulting in a slightly higher acidity as compared to ZSM‐5. This structural relaxation is not achievable in Ge‐ZSM‐5 with a low Ge content, which therefore has a slightly lower acidity than ZSM‐5. The NMR study indicates no difference between the Brønsted acidity of ZSM‐5(47) and Ge(0.09)ZSM‐5(36). Instead, evidence for the presence of a substantial amount of Ge? OH groups in the Ge‐containing samples was obtained from the NMR results, which is consistent with earlier FTIR studies. The XPS results do not point to an effect of Ge on the framework acidity of ZSM‐5(47), instead, the results can be best interpreted by assuming the presence of additional Ge? OH and Si? OH groups near the surface of the Ge(0.08)ZSM‐5(47) sample.     

SrNi2Si and BaNi2Si – New Layered Silicides with Fused Nickel Six‐membered Rings in a Boat Conformation

Intermetallic compounds SrNi₂Si and BaNi₂Si were prepared by arc‐melting of stoichiometric mixture of the elements and subsequent annealing in welded niobium ampoules. Both compounds were investigated by X‐ray diffraction on powder as well as single crystal methods. The title compounds both crystallize in the BaNi₂Ge structure type (space group Pmmn, Z = 2), a ternary ordered variant of TiCu₃: a = 4.0296(9) Å, b = 6.5121(14) Å, c = 5.6839(21) Å, R₁ = 0.040 for SrNi₂Si and a = 4.0681(9) Å, b = 6.580(4) Å, c = 5.976(5) Å, R₁ = 0.031 for BaNi₂Si. The structure contains corrugated polyanionic [Ni₂Si]^2– layers, stacked according to the primitive sequence AA along the c axis. Six‐membered Ni rings adopt a boat conformation, silicon atoms are in the plane with nickel, and the alkaline earth cations sit between the layers. These two compounds extend the family AeNi₂X (Ae = Ca, Sr, Ba; X = Si, Ge), where up to date CaNi₂Si, SrNi₂Ge, and BaNi₂Ge are known. LMTO band structure calculations, including DOS, COHP, and ELF were performed to gain more insight into the electronic situation of SrNi₂Si and BaNi₂Si.     

Pentafluoroethylsilicic Acids

Pure anhydrous hexafluorosilicic acid (H₂[SiF₆]) is a still elusive species, although its existence in aqueous solutions is well documented. Desiccation inevitably leads to decomposition to form tetrafluorosilane and hydrogen fluoride. An oxonium hexafluorosilicate turned out to not be stable at room temperature. Partial substitution of the fluorine atoms with strong electron‐withdrawing perfluoroalkyl groups results in substantial stabilization of the corresponding fluorosilicic acids. Mono‐ and bis(pentafluoroethyl)‐substituted fluorosilicic acids were prepared through conversion of the respective halosilanes (Si(C₂F₅)_nX_4?n, with X=Cl, Br) with aqueous HF, and were obtained as colorless solids. They can be stored at room temperature for several months without decomposition, and thus are the first examples of stable fluorosilicic acids.     

A Systematic Study of Structure and E−H Bond Activation Chemistry by Sterically Encumbered Germylene Complexes

A series of new germylene compounds has been synthesized offering systematic variation in the σ‐ and π‐capabilities of the α‐substituent and differing levels of reactivity towards E?H bond activation (E=H, B, C, N, Si, Ge). Chloride metathesis utilizing [(terphenyl)GeCl] proves to be an effective synthetic route to complexes of the type [(terphenyl)Ge(ER_n)] ( 1 – 6 : ER_n=NHDipp, CH(SiMe₃)₂, P(SiMe₃)₂, Si(SiMe₃)₃ or B(NDippCH)₂; terphenyl=C₆H₃Mes₂‐2,6=Ar^Mes or C₆H₃Dipp₂‐2,6=Ar^Dipp; Dipp=C₆H₃iPr₂‐2,6, Mes=C₆H₂Me₃‐2,4,6), while the related complex [{(Me₃Si)₂N}Ge{B(NDippCH)₂}] ( 8 ) can be accessed by an amide/boryl exchange route. Metrical parameters have been probed by X‐ray crystallography, and are consistent with widening angles at the metal centre as more bulky and/or more electropositive substituents are employed. Thus, the widest germylene units (θ>110°) are found to be associated with strongly σ‐donating boryl or silyl ancillary donors. HOMO–LUMO gaps for the new germylene complexes have been appraised by DFT calculations. The aryl(boryl)‐germylene system [Ar^MesGe{B(NDippCH)₂}] ( 6 ‐Mes), which features a wide C‐Ge‐B angle (110.4(1)°) and (albeit relatively weak) ancillary π‐acceptor capabilities, has the smallest HOMO–LUMO gap (119 kJ mol^?1). These features result in 6 ‐Mes being remarkably reactive, undergoing facile intramolecular C?H activation involving one of the mesityl ortho‐methyl groups. The related aryl(silyl)‐germylene system, [Ar^MesGe{Si(SiMe₃)₃}] ( 5 ‐Mes) has a marginally wider HOMO–LUMO gap (134 kJ mol^?1), rendering it less labile towards decomposition, yet reactive enough to oxidatively cleave H₂ and NH₃ to give the corresponding dihydride and (amido)hydride. Mixed aryl/alkyl, aryl/amido and aryl/phosphido complexes are unreactive, but amido/boryl complex 8 is competent for the activation of E?H bonds (E=H, B, Si) to give hydrido, boryl and silyl products. The results of these reactivity studies imply that the use of the very strongly σ‐donating boryl or silyl substituents is an effective strategy for rendering metallylene complexes competent for E?H bond activation.     

Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag+/X2 (X=Cl,Br, I) System

The synergistic Ag⁺/X₂ system (X=Cl, Br, I) is a very strong, but ill‐defined oxidant—more powerful than X₂ or Ag⁺ alone. Intermediates for its action may include [Ag_m(X₂)_n]^m+ complexes. Here, we report on an unexpectedly variable coordination chemistry of diiodine towards this direction: ( A )Ag‐I₂‐Ag( A ), [Ag₂(I₂)₄]²⁺( A ^?)₂ and [Ag₂(I₂)₆]²⁺( A ^?)₂?(I₂)_x≈0.65 form by reaction of Ag( A ) ( A =Al(OR^F)₄; R^F=C(CF₃)₃) with diiodine (single crystal/powder XRD, Raman spectra and quantum‐mechanical calculations). The molecular ( A )Ag‐I₂‐Ag( A ) is ideally set up to act as a 2 e^? oxidant with stoichiometric formation of 2 AgI and 2 A ^?. Preliminary reactivity tests proved this ( A )Ag‐I₂‐Ag( A ) starting material to oxidize n‐C₅H₁₂, C₃H₈, CH₂Cl₂, P₄ or S₈ at room temperature. A rough estimate of its electron affinity places it amongst very strong oxidizers like MF₆ (M=4d metals). This suggests that ( A )Ag‐I₂‐Ag( A ) will serve as an easily in bulk accessible, well‐defined, and very potent oxidant with multiple applications.     

A theoretical study of electronic effects in alkyne‐linked reactive intermediates: (nitrenoethynyl)methylenes, (nitrenoethynyl)silylenes,and (nitrenoethynyl)germylenes

Acetylene‐linked reactive intermediates of (nitrenoethynyl)‐X‐methylenes, (nitrenoethynyl)‐X‐silylenes, and (nitrenoethynyl)‐X‐germylenes are almost experimentally unreachable (X–M–C≡C–N; X=H ( 1 ), CN ( 2 ), OH ( 3 ), NH₂ ( 4 ), NO₂ ( 5 ), and CHO ( 6 ); M=C, Si, and Ge). The effects of the electron‐donating and electron withdrawing groups were compared and contrasted at seven levels of theory. All singlet species as ground states with one local open‐shell singlet carbene subunit (π¹π¹) and another local open‐shell singlet nitrene subunit (π¹π¹) were found to be more stable than their corresponding triplets including one local open‐shell singlet carbene (δ¹π¹) (or one local closed‐shell singlet carbene [δ²π⁰]) and another local triplet nitrene subunit (π¹π¹) with 45.94–77.996 kcal/mol singlet–triplet energy gap (ΔE_s‐t). Their relative silylenes and germylenes made reduction of ΔE_s‐t, so the triplet ground states were found for species 3 _Si , 4 _Si , 5 _Si , 2 _Ge , 3 _Ge , 4 _{Ge ,} and 5 _Ge . All the singlet silylenes/germylenes formed by one local closed‐shell singlet silylenes/germylenes (δ²π⁰) and one local closed‐shell singlet nitrene subunit (π²π⁰). Also, one local closed‐shell singlet silylene/germylene subunit (δ²π⁰) and one local triplet nitrene subunit (π¹π¹) were observed for triplet silylenes/germylenes. The singlet and triplet species 3 _Si , 4 _Si , 3 _Ge , and 4 _Ge , due to their electrophilic (Si₄/Ge₄) and nucleophilic (X₅) centers, could be identified as intermediates in chemical reactions.     

Amorphous Silicon: New Insights into an Old Material

Amorphous silicon is synthesized by treating the tetrahalosilanes SiX₄ (X=Cl, F) with molten sodium in high boiling polar and non‐polar solvents such as diglyme or nonane to give a brown or a black solid showing different reactivities towards suitable reagents. With regards to their technical relevance, their stability towards oxygen, air, moisture, chlorine‐containing reaction partners RCl (R=H, Cl, Me) and alcohols is investigated. In particular, reactions with methanol are a versatile tool to deliver important products. Besides tetramethoxysilane formation, methanolysis of silicon releases hydrogen gas under ambient conditions and is thus suitable for a decentralized hydrogen production; competitive insertion into the MeO?H versus the Me?OH bond either yields H‐ and/or methyl‐substituted methoxy functional silanes. Moreover, compounds, such as Me_nSi(OMe)_4?n (n=0–3) are simply accessible in more than 75 % yield from thermolysis of, for example, tetramethoxysilane over molten sodium. Based on our systematic investigations we identified reaction conditions to produce the methoxysilanes Me_nSi(OMe)_4?n in excellent (n=0:100 %) to acceptable yields (n=1:51 %; n=2:27 %); the yield of HSi(OMe)₃ is about 85 %. Thus, the methoxysilanes formed might possibly open the door for future routes to silicon‐based products.     

Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag+/X2 (X=Cl,Br, I) System

The synergistic Ag⁺/X₂ system (X=Cl, Br, I) is a very strong, but ill‐defined oxidant—more powerful than X₂ or Ag⁺ alone. Intermediates for its action may include [Ag_m(X₂)_n]^m+ complexes. Here, we report on an unexpectedly variable coordination chemistry of diiodine towards this direction: ( A )Ag‐I₂‐Ag( A ), [Ag₂(I₂)₄]²⁺( A ⁻)₂ and [Ag₂(I₂)₆]²⁺( A ⁻)₂⋅(I₂)_x≈0.65 form by reaction of Ag( A ) ( A =Al(OR^F)₄; R^F=C(CF₃)₃) with diiodine (single crystal/powder XRD, Raman spectra and quantum‐mechanical calculations). The molecular ( A )Ag‐I₂‐Ag( A ) is ideally set up to act as a 2 e⁻ oxidant with stoichiometric formation of 2 AgI and 2 A ⁻. Preliminary reactivity tests proved this ( A )Ag‐I₂‐Ag( A ) starting material to oxidize n‐C₅H₁₂, C₃H₈, CH₂Cl₂, P₄ or S₈ at room temperature. A rough estimate of its electron affinity places it amongst very strong oxidizers like MF₆ (M=4d metals). This suggests that ( A )Ag‐I₂‐Ag( A ) will serve as an easily in bulk accessible, well‐defined, and very potent oxidant with multiple applications.