Imide Ligands Research Articles

A convenient route to prepare mono- and dinuclear 2-benzoylpyridine palladacycles with imidate ligands

New dinuclear cyclometallated palladium complexes of general formula [{Pd(μ-NCO)(CˆN)} 2] (CˆN = 2-benzoylpyridine (bzpy) I; NCO = saccharinate (sacc) a, Phthalimidate (phthal) b or 4,5-dichlorophthalimidate (DiClphthal) c have been synthesized by a simple acid-base reaction involving the di-μ-hydroxo-precursor [{Pd(μ-OH)(bzpy)}2] recently reported. Analogous to Ic, complex IIc with CˆN = 2-phenylpyridine (phpy) II has also been prepared, meaning the first examples reported to date of complexes including 4,5-dichlorophthalimidate as ligand coordinating a metal centre. The reaction of bridged imidato precursors against triphenylphosphine to form the mononuclear N-bonded imidato derivatives of general formula [Pd(CˆN)(N-imidate)(PPh3)] IaP, IbP, IcP and IIcP has been achieved under mild conditions. The new complexes were characterized by partial elemental analyses and spectroscopic methods. Structural characterization by X-ray diffraction of Ib and IIcP, the first crystal structure of a complex containing 4,5-diClphthal that has been deposited to date on the Cambridge Structural Database, have confirmed the proposed formulae.

Anionic and Mononuclear Phosphinidene and Imide Complexes of Niobium

The reactivity of a terminal methylidene complex of niobium, [(ArO)2Nb═CH2(CH3)(CH2PPh3)] (1), with the primary phosphine PhPH2 results in formation of the anionic phosphinidene complex [H3CPPh3][(ArO)2Nb═PPh(CH3)2] (2), where both the methylidene and ylide ligands of the precursor experience protonation. Multinuclear NMR spectroscopy and X-ray diffraction studies indicate formation of a bent phosphinidene ligand. Similar reactivity is also observed with primary amines, specifically AdNH2 (Ad = 1-adamantyl) and MesNH2 (Mes = 2,4,6-trimethylphenyl), resulting in formation of the corresponding imide complexes [H3CPPh3][(ArO)2Nb═NR(CH3)2] (R = Mes, (3), Ad, (4)). Whereas 2 has a bent phosphinidene ligand and pseudo trigonal bipyramidal structure, the solid-state structure determination of complex 4 reveals a linear imide ligand and square-pyramidal geometry, where the imide enjoys significant Nb–NR multiple-bond character.

Pyrazine-imide complexes: reversible redox and MOF building blocks.

The synthesis of the symmetric pyrazine imide ligand, N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide, (Hdpzca) and five new first row transition metal complexes of it are reported: [M(II)(dpzca)(2)], M(II) = Fe, Cu, Zn; [Cu(II)(dpzca)(H(2)O)(2)]BF(4), [Cu(II)(dpzca)(H(2)O)(3)](2)SiF(6). The crystal structures of Hdpzca, [Co(II)(dpzca)(2)], [Cu(II)(dpzca)(2)], {[Co(III)(dpzca)(2)](BF(4))}(2)·5CH(3)CN and [Cu(II)(dpzca)(H(2)O)(3))](2)SiF(6)·2H(2)O were determined and reveal an orthogonal positioning of the 'spare' pyrazine nitrogen atoms and 'spare' pairs of imide oxygen atoms. The [M(II)(dpzca)(2)] complexes are therefore useful six-coordinate building blocks for producing larger supramolecular assemblies. Two examples of secondary assembly of [M(II)(dpzca)(2)] complexes, with M = Co and Ni, with silver nitrate gave single crystals; {[Co(III)(dpzca)(2)Ag](NO(3))(2)·2H(2)O}n and {([Ni(II)(dpzca)(2)Ag(I)(1/2)](1/2NO(3))(xH(2)O}n were structurally characterised. The redox processes of [M(II)(dpzca)(2)], with M(II) = Fe, Ni, Cu and Zn, are reported and, as seen for M(II) = Co, reversible metal- and ligand-based redox processes are observed, with E(m)(M(II)/M(III)) values 0.15-0.24 V higher than for the analogous complexes of Hpypzca (non-symmetric pyridine/pyrazine imide ligand), and 0.35-0.36 V higher than for the complexes of Hbpca (symmetric pyridine imide ligand).

C–H Activation by Multiply Bonded Complexes with Potentially Noninnocent Ligands: A Computational Study

Second- and third-row (typically precious metals) transition metal complexes are known to possess certain electronic features that define their structure and reactivity and are usually not observed in their first-row (base metal) congeners. Can these electronic features be conferred onto first-row transition metals with the aid of noninnocent and/or very high-field ligands? In this research, the impact upon methane C-H bond activation was modeled using the dipyridylazaallyl (smif) supporting ligand for late, first-row transition metal (M) imide, oxo, and carbene complexes (M = Fe, Co, Ni, or Cu; E = O, NMe, or CMe2). Density functional theory calculations suggest that the combination of smif with iron and the oxo activating ligand is the most energetically favorable complex for methane C-H activation. A change in the preferred transition state for methane C-H activation from [2+2] addition to hydrogen atom abstraction was observed upon going from Fe to Cu and for Fe as compared to precious metals. Contrary to expectations, it was the imide ligand rather than the dipyridylazaallyl ligand that was found to possess redox "noninnocent" characteristics.

Synthesis and Reactivity of N-Heterocyclic Carbene Gold(I) and Gold(III) Imidate Complexes and Their Catalytic Activity in 1,5-Enyne Cycloisomerization

The effects of substituting (pseudo)halide for anionic imidate ligands in Au(I) and Au(III) (i.e. [AuBr(NHC)] and [AuBr3(NHC)]) complexes have been investigated. [Au(N-imidate)(NHC)] and [AuBr2(N-imidate)(NHC)] complexes were prepared and the structure and bonding of the complexes examined spectroscopically and crystallographically. The [AuBr2(N-imidate)(NHC)] complexes, in combination with Ag salts, were tested for catalytic activity in the cycloisomerization of 1,5-enynes and found to be more effective than the tribromide analogues (e.g. [AuBr3(NHC)]). Subtle changes to the anionic imidate ligand structure had a pronounced effect on the catalytic activity of the Au(III) complexes.

Synthesis and reactivity of ruthenium(II) complex with an ortho-metalated bis(diphenylthiophosphoryl)imide

Reaction of RuCl(CHCHPh)(CO)(PPh3)2 with K[N(Ph2PS)2] afforded a σ-aryl complex, Ru(CO)[η1(C),η2(S,S′)-N{(C6H4)PhPS}(Ph2PS)](PPh3)2 (1), with an ortho-metalated bis(diphenyl-thiophosphoryl)imide ligand in a quantitative yield. Treatment of 1 with an excess hydrogen chloride in diethyl ether solution led to isolation of a binuclear complex {RuCl(CO)(PPh3)}2(μ-Cl)(μ-η2(S),η2(S′)-N(Ph2PS)2) (2) which was also obtained from the direct reaction of RuCl(CHCHPh)(CO)(PPh3)2 with HN(Ph2PS)2 in dichloromethane. The structures of complexes 1 and 2 have been established by X-ray crystallography.

Platinum(II) complexes containing the 3,3-dimethylglutarimidate ligand

Reaction of cis-[PtCl2(PPh3)2] with excess 3,3-dimethylglutarimide (dmgH) and sodium chloride in refluxing methanol gives the mono-imidate complex cis-[PtCl(dmg)(PPh3)2], which was structurally characterized. The plane of the imidate ligand is approximately perpendicular to the platinum coordination plane which, coupled with restricted rotation about the Pt–N bond, results in inequivalent methyl groups and CH2 protons of the dmg ligand in the room temperature 1H NMR spectrum. These observations were corroborated by a theoretical study using density functional theory methods. The analogous bromide complex cis-[PtBr(dmg)(PPh3)2] can be prepared by replacing NaCl with NaBr in the reaction mixture.

(μ-3,5,9,11-Tetraoxo-4,10-diazatetracyclo[5.5.2.02,6.08,12]tetradec-13-ene-4,10-diido-κ2N:N′)bis[(2,2′-bipyridine-κ2N,N′)silver(I)] dihydrate

In the title complex, [Ag2(C12H8N2O4)(C10H8N2)2]·2H2O, the AgI ion is three-coordinated by two N atoms from a chelating 2,2′-bipyridine ligand and one N atom from an imide ligand in a Y-shaped fashion. The imide ligand and the complex lie on a twofold rotation axis. The ligand bridges two AgI ions, forming a dinuclear complex. In the crystal, O—H⋯O hydrogen bonds link the lattice water mol­ecules and the complex mol­ecules into a ribbon-like structure along [001]. π–π inter­actions are observed between the pyridine rings [centroid–centroid distance = 3.8289 (14) Å].

Nine non-symmetric pyrazine-pyridine imide-based complexes: reversible redox and isolation of [MII/III(pypzca)2]0/+when M = Co, Fe

The non-symmetric imide ligand Hpypzca (N-(2-pyrazylcarbonyl)-2-pyridinecarboxamide) has been deliberately synthesised and used to produce nine first row transition metal complexes: [M(II)(pypzca)(2)], M = Zn, Cu, Ni, Co, Fe; [M(III)(pypzca)(2)]Y, M = Co and Y = BF(4), M = Fe and Y = ClO(4); [Cu(II)(pypzca)(H(2)O)(2)]BF(4), [Mn(II)(pypzca)(Cl)(2)]HNEt(3). These are the first deliberately prepared complexes of a non-symmetric imide ligand. X-ray crystal structures of [Cu(II)(pypzca)(2)]·H(2)O, [Co(II)(pypzca)(2)], [Co(III)(pypzca)(2)]BF(4), [Cu(II)(pypzca)(H(2)O)(2)]BF(4)·H(2)O and [Mn(II)(pypzca)Cl(2)]HNEt(3) show that each of the (pypzca)(-) ligands binds in a meridional fashion via the N(3) donors. In the first three complexes, two such ligands are bound such that the 'spare' pyrazine nitrogen atoms are positioned approximately orthogonally to one another and also to the imide oxygen atoms. In MeCN the [M(II/III)(pypzca)(2)](0/+) complexes, where M = Ni, Co or Fe, exhibit one reversible metal based M(II/III) process and two distinct, quasi-reversible ligand based reduction processes, the latter also observed for M(II) = Zn. [Mn(II)(pypzca)Cl(2)]HNEt(3) displays a quasi-reversible oxidation process in MeCN, along with several irreversible processes. Both copper(II) complexes show only irreversible processes. Variable temperature magnetic measurements show that [Fe(III)(pypzca)(2)]ClO(4) undergoes a gradual spin crossover from partially high spin at 298 K (3.00 BM) to fully low spin at 2 K (1.96 BM), and that [Co(II)(pypzca)(2)] remains high spin from 298 to 4 K. All of the complexes are weakly coloured, other than [Fe(II)(pypzca)(2)] which is dark purple and absorbs strongly in the visible region.

Diironhexacarbonyl clusters with imide and amine ligands: hydrogen evolution catalysts

The reaction of Fe3(CO)12 and N-(4-thiolphenyl)-1,8-naphthalimide afforded a new diironhexacarbonyl complex (3). The integrity and electronic structure of 3 has been determined by elemental analysis and spectroscopy (NMR and infrared). Infrared spectrum of 3 shows peaks at 2000, 2040, and 2075 cm−1 ascribed to stretching frequencies of the terminal metal carbonyls. Compound 4 was obtained from the reaction of Fe3(CO)12 and 4-aminothiolphenol. A comparison of the electronic, electrochemical, and electrocatalytic properties of 3 and 4 are discussed. Cyclic voltammetric studies show that 3 and 4 catalyze the reduction of acetic acid to produce hydrogen at −2.19 V and −1.88 V versus Fc/Fc+, respectively.

Oxidative Group Transfer to a Triiron Complex to Form a Nucleophilic μ3-Nitride, [Fe3(μ3-N)]−

Utilizing a hexadentate ligand platform, a high-spin trinuclear iron complex of the type ((tbs)L)Fe(3)(thf) was synthesized and characterized ([(tbs)L](6-) = [1,3,5-C(6)H(9)(NPh-o-NSi(t)BuMe(2))(3)](6-)). The silyl-amide groups only permit ligation of one solvent molecule to the tri-iron core, resulting in an asymmetric core wherein each iron ion exhibits a distinct local coordination environment. The triiron complex ((tbs)L)Fe(3)(thf) rapidly consumes inorganic azide ([N(3)]NBu(4)) to afford an anionic, trinuclear nitride complex [((tbs)L)Fe(3)(μ(3)-N)]NBu(4). The nearly C(3)-symmetric complex exhibits a highly pyramidalized nitride ligand that resides 1.205(3) Å above the mean triiron plane with short Fe-N (1.871(3) Å) distances and Fe-Fe separation (2.480(1) Å). The nucleophilic nitride can be readily alkylated via reaction with methyl iodide to afford the neutral, trinuclear methylimide complex ((tbs)L)Fe(3)(μ(3)-NCH(3)). Alkylation of the nitride maintains the approximate C(3)-symmetry in the imide complex, where the imide ligand resides 1.265(9) Å above the mean triiron plane featuring lengthened Fe-N(imide) bond distances (1.892(3) Å) with nearly equal Fe-Fe separation (2.483(1) Å).

Bis(imidate)palladium(ii) complexes with labile ligands. Mimics of classical precursors?

A novel synthetic route to prepare palladium(II) precursor analogous of classical [Pd(Cl)(2)(solvent)(2)] has been developed. Just stirring Pd(3)(AcO)(6) in dimethyl sulfide at room temperature, in the stoichiometric presence of protic imidate ligands, resulted in the precipitation of the desired complexes [Pd(imidate)(2)(SMe(2))(2)] (imidate = succinimidate (succ) 1, phthalimidate (phthal) 2, maleimidate (mal) 3, saccharinate (sac) 4 or glutarimidate (glut) 5). The new complexes are very soluble in common solvents and have been fully characterized, including an X-ray diffraction analysis of 2. Analogous reactions with succinimide in acetonitrile or dimethylsulfoxide produced [Pd(succinimidate)(2)(solvent)(2)] (6 and 7, respectively) as off-white powders. Thermal decomposition of 6 produces a new species 6* with bridging imidate ligands that can be formulated as a trimer similar to Pd(3)(AcO)(6). The usefulness of 1-5 as precursors has been tested by reactions against monodentated neutral donor ligands, PPh(3) (a compounds), or pyridine (py, b compounds), to produce ten new derivatives of the general formula trans-[Pd(imidate)(2)(L)(2)]. The single-crystal structures of compounds 2a, 3a, 4a, 4a', 5a and 4b have also been established, allowing an interesting molecular and supramolecular structural discussion. A cis-conformation was induced when the bidentate chelate ligand 1,2-bis(diphenylphosphino)benzene (dppb, c compounds) was made to react with 1-5. Structural characterization by X-ray diffraction of complex 2c confirmed the proposed formula. Catalytic activity in Suzuki-Miyaura cross-coupling of aryl bromides and benzyl bromides with aryl boronic acids has been tested.

(2,2′-Bipyridine-κ2N,N′)[2-tert-butylanilinato(2−)]dichloridooxidomolybdenum(VI) dichloromethane hemisolvate

The MoVI atom in the title structure, [Mo(C10H13N)Cl2O(C10H8N2)]·0.5CH2Cl2, has a distorted octa­hedral coord­ination sphere with cis-orientated oxide and imide ligands, trans-chloride ligands and the 2,2′-bipyridine (bipy) ligand N atoms lying trans to the oxide and imide ligands. An imide-ligand tert-butyl-methyl-group H atom makes a close approach with the oxide ligand (distance = 2.53 Å) and the imide-ligand N atom (distance = 2.41 Å). Another imide-ligand tert-butyl-methyl-group H atom makes a close approach to a chloride ligand (distance = 2.82 Å). One bipy-ligand α-H atom makes a close approach to the oxide ligand (distance = 2.4 Å) and the other α-H atom makes a close approach to the imide-ligand phenyl-ring ortho-H atom (distance = 2.52 Å). These close approaches suggest the presence of weak intra­molecular hydrogen bonds. The solvent molecule has been modelled under consideration of half-occupancy.

Steric Control of Coordination Geometry in Titanium-Imido Complexes of N,N′-bis(arylimino)acenaphthylene Ligands

Titanium complexes of N,N'-bis(arylimino)acenaphthylene (BIAN) alpha-diimine ligands with varied steric profiles have been prepared. Coordination of the BIAN ligand derivatives to TiCl(4) afforded the adducts (dpp-BIAN)TiCl(4) (1a), (tmp-BIAN)TiCl(4) (1b), and (dmp-BIAN)TiCl(4) (1c) (dpp = 2,6-diisopropylphenyl; tmp = 2,4,6-trimethylphenyl; dmp = 3,5-dimethylphenyl). While the least sterically crowded complex 1c is robust toward loss of the diimine ligand, the dpp-BIAN and tmp-BIAN ligands are readily displaced by pyridine from the more crowded derivatives 1a and 1b, respectively. The crowded profiles engendered by the tmp-BIAN and dpp-BIAN ligands result in the formation of five-coordinate titanium-imide complexes, (dpp-BIAN)TiCl(2)(=N(t)Bu) (2a) and (tmp-BIAN)TiCl(2)(=N(t)Bu) (2b), upon addition of (t)BuNH(2) to solutions of 1a or 1b, respectively. Single-crystal X-ray diffraction studies reveal a square pyramidal coordination environment with an apical imide ligand and a short Ti-N distance, consistent with a Ti-N triple bond. Conversely, the less crowded dmp-BIAN ligand affords a six-coordinate titanium imido complex, (dmp-BIAN)TiCl(2)(=N(t)Bu)(NH(2)(t)Bu) (4), upon treatment of 1c with (t)BuNH(2). Surprisingly the imido ligand is coordinated trans to one arm of the diimine. This six coordinate species is fluxional in solution, and exchange and variable temperature (1)H NMR experiments suggest dissociation of the coordinated (t)BuNH(2) ligand to generate a five-coordinate imido intermediate analogous to 2a and 2b.

In Situ Synthesis of an Imidazolate‐4‐amide‐5‐imidate Ligand and Formation of a Microporous Zinc–Organic Framework with H2‐and CO2‐Storage Ability

Narrow channels with polar walls are the structural and functional features responsible for the high capacity of a zinc–organic framework based on an imidazolate–amide–imidate ligand for the uptake of H2 and CO2 (see structure: orange Zn, blue N, red O, dark gray C, light gray H). The rigid and stable chelating ligand was synthesized in situ by partial hydrolysis of a dicyanoimidazole compound.

Remarkable anion effects uncovered in the development of a Au(iii)-catalyzed tandem nucleophilic substitution–1,5-enyne cycloisomerization process

(I(t)Pe)AuBr(2)(N-imidate) complexes, prepared in high yield by oxidative bromination, are active catalysts for 1,5-enyne cycloisomerization. An efficient tandem nucleophilic substitution-1,5-enyne cycloisomerization is promoted by these novel Au(III) precatalysts. Catalyst efficacy is affected by the imidate ligand and the silver salt used (e.g. Ag[Al(OC(CF(3))(3))(4)]).

Reusable Gold(I) Catalysts with Unique Regioselectivity for Intermolecular Hydroamination of Alkynes

AbstractTwo gold(I) phosphine complexes bearing the low‐coordinating bis(trifluoromethanesulfonyl)imidate ligand, namely AuSPhosNTf2 and AuPPh3NTf2, are active catalysts for the regioselective intermolecular hydroamination of both internal and terminal alkynes under mild reaction conditions. The catalysts show a regioselectivity based on electronic rather than steric factors, which allow the preferential synthesis of regioisomers opposite to those described previously. This subtle chemo‐ and regioselectivity depends on the catalyst, substrates and reaction conditions employed, and allows one to perform new tandem reactions. These gold(I) complexes operate under free‐solvent conditions, without exclusion of air, without addition of acidic promoters and can be quantitatively recovered and reused by simple precipitation in hexane.

Palladium complexes containing novel cyclic selenium imides

The first metal complexes of cyclic selenium(II) imide ligands, [PdCl2{Se,Se'-Se4(NtBu)3}] and [PdCl2{Se,Se'-Se4(NtBu)4}], which are obtained from the reaction of Se(NtBu)2 with [PdCl2(NCPh)2], contain the novel Se-N heterocycles Se4(NtBu)3 and Se4(NtBu)4.

Probing the Chemistry, Electronic Structure and Redox Energetics in Organometallic Pentavalent Uranium Complexes

A series of organometallic pentavalent uranium complexes of the general formula (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(Y) (Y = monoanionic, non-halide ligand) have been prepared using a variety of routes. Utilizing the direct oxidation of (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(THF) (2) with the appropriate copper(I) salt yielded the triflate (Y = OTf (OSO(2)CF(3)), 11), thiolate (Y = SPh, 12), and acetylide (Y = C[triple bond]CPh, 13) complexes, while a salt metathesis route between the U(V)-imido (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(I) (10) and various alkali salts gave the diphenylamide (Y = NPh(2), 14), aryloxide (Y = OPh, 15), alkyl (Y = Me, 16), and aryl (Y = Ph, 17) complexes. Paired with 13, the isolation of 16 and 17 shows that U(V) can support the full range of carbon anions (sp, sp(2), and sp(3)), and these are, to the best of our knowledge, the first examples of pentavalent uranium complexes with anionic carbon moieties other than carbocyclic (C(5)R(5), C(7)H(7), C(8)H(8)) ligands. Finally, both protonolysis and insertion pathways afforded the U(V)-imido ketimide complex (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(N=CPh(2)) (18). The complexes have been isolated in good yield and characterized using various combinations of (1)H NMR spectroscopy, elemental analysis, mass spectrometry, single crystal X-ray diffraction, cyclic voltammetry, UV-visible-NIR absorption spectroscopy, and magnetic susceptibility measurements. All (C(5)Me(5))(2)U(=N-Ar)(X) (X = F, Cl, Br, I) and (C(5)Me(5))(2)U(=N-Ar)(Y) complexes exhibit U(VI)/U(V) and U(V)/U(IV) redox couples by voltammetry. The potential separation between these couples remains essentially constant at approximately 1.50 V, but both processes shift in tandem in potential by approximately 700 mV across the series of X/Y ligands. No significant differences between mu(eff) values or temperature dependencies in the magnetic susceptibility were observed for these complexes regardless of the identity of the ancillary X/Y ligand. However, an excellent linear correlation was observed between the chemical shift values of C(5)Me(5) ligand protons in the (1)H NMR spectra and the oxidation potentials of (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(X/Y), suggesting that there is a common origin, overall sigma-/pi-donation from the ancillary X/Y ligand to the metal, contributing to both observables. Combined, these data confer the following trend in increasing sigma/pi-donating ability of the X/Y ligand to the U(V) metal center: OTf < I < Br < Cl < SPh < C[triple bond]CPh < F < [OPh approximately Me approximately Ph] << NPh(2) < N=CPh(2). These (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(X/Y) complexes also show distinct hallmarks of a covalent bonding interaction between the metal and the imide ligand that is modulated to varying degrees by the interaction between the X/Y ancillary ligand and the U(V) metal center. These signatures of covalency include stabilization of multiple metal oxidations states [U(VI), U(V), and U(IV)] and enhanced intensities in the intraconfiguration (f-f) transitions. Of particular note in this regard is the more than 20-fold enhancement in the f-f intensities observed for Y = C[triple bond]CPh and N=CPh(2), which is a clear reflection of the covalent metal-ligand bonding interactions sustained by the acetylide and ketimide ligands in these pentavalent systems.

The Use of Halide‐Substituted Anilines for the Formation of Magnesium Imides

AbstractThe equimolar reactions of the halide‐substituted anilines 2,4,6‐trichloroaniline (ArClNH2) and 2,3,4,5,6‐pentafluoroaniline (ArFNH2) with Bu2Mg in the appropriate solvent system results in the formation of the magnesium imide compounds [(ArClNMg·thf)4·tol] (4), [(ArClNMg·diox)4·3diox] (5), [(ArFNMg·thf)6·3C6H6] (6) and [(ArFNMg·diox)6] (7). Single‐crystal X‐ray diffraction analyses show that 4 and 5 adopt tetrameric cubane arrangements in the solid state, whereas 6 and 7 form prismatic hexameric aggregates. In comparison, reaction of 2 mol‐equiv. of ArFNH2 with Bu2Mg produces the trimeric primary amide species [{(ArFNH)6Mg3·(thf)6}·2tol·thf] (9). In addition, the serendipitous synthesis of the decametallic imide [(ArFN)9(F)2Mg10(thf)6·1.25tol] (8a) and the structural isomer [(ArFN)9(F)2Mg10(thf)6·4.5tol] (8b) were discovered during the attempted synthesis of 6. It is presumed that the formation of these unusually large cage compounds results from the partial decomposition of the imide ligand by C–F bond cleavage. The compounds 8a and 8b have similar core‐cage structures, but the orientation of their aryl groups and coordinated solvent molecules vary. The 20‐vertex Mg10N9F aggregates utilize one fluoride ion as a vertex, with a second fluoride ion encapsulated within the cage. (© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2008)