CF CO Research Articles

An in-depth in situ IR study of the thermal decomposition of barium trifluoroacetate hydrate

The pyrolysis of Ba(CF 3COO) 2· nH 2O at temperatures up to 1000 °C, under flowing pure Ar, O 2 and O 2 saturated with water vapour, was extensively analysed. The existence of a :CF 2 diradical is inferred and the formation of HF is observed directly for the first time during a trifluoroacetic acid salt decomposition. High resolution thermogravimetry, differential scanning calorimetry, X-ray diffractometry and scanning electron microscopy indicated that the exothermic two-stage decomposition of the anhydrate salt occurs between 282 and 325 °C, forming BaF 2 via an unstable CF 3COOBaF intermediate. Fourier transform infrared spectroscopy revealed the influence of water on the reactions of the liberated gaseous products, identifying CF 3COOH, HF, CHF 3 and CO 2 as the principal volatile species, with C 2F 4, C 2F 6, CO and SiF 4 also detected. The decomposition temperature is significantly lower than previously reported, which has implications for sol–gel processing.

Formation of Unusual Seven-Membered Heterocycles Incorporating Nitrogen and Sulfur by Intramolecular Conjugate Displacement

Baylis-Hillman alcohols derived from methyl acrylate or acrylonitrile and carrying an N-Boc group β to the hydroxyl (CH(OH)CHNBoc) can be converted into unusual seven-membered heterocycles containing both nitrogen and sulfur by O-acylation (AcCl or EtOCOCl), N-deprotection (CF(3)CO(2)H), and reaction with CS(2). In a modification of this process, when the original nitrogen is substituted in the form PhSCH(2)CON(Me), an azepine derivative is then generated. The ring closures occur by intramolecular conjugate displacement.

Functionalization of Metallabenzenes through Nucleophilic Aromatic Substitution of Hydrogen

The cationic metallabenzenes [Ir(C(5)H(4){SMe-1})(κ(2)-S(2)CNEt(2))(PPh(3))(2)]PF(6) (1) and [Os(C(5)H(4){SMe-1})(CO)(2)(PPh(3))(2)][CF(3)SO(3)] (2) undergo regioselective nucleophilic aromatic substitution of hydrogen at the metallabenzene ring position γ to the metal in a two-step process that first involves treatment with appropriate nucleophiles and then oxidation. Thus, reaction between compound 1 and NaBH(4), MeLi, or NaOEt gives the corresponding neutral iridacyclohexa-1,4-diene complexes Ir(C(5)H(3){SMe-1}{H-3}{Nu-3})(κ(2)-S(2)CNEt(2))(PPh(3))(2) (Nu = H (3), Me (4), OEt (5)). Similarly, reaction between 2 and NaBH(4) or MeLi gives the corresponding osmacyclohexa-1,4-diene complexes Os(C(5)H(3){SMe-1}{H-3}{Nu-3})(CO)(2)(PPh(3))(2) (Nu = H (8), Me (9)). The metallacyclohexa-1,4-diene rings in all these compounds are rearomatized on treatment with the oxidizing agent O(2), CuCl(2), or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Accordingly, the cationic metallabenzene 1 or 2 is returned after reaction between 3 and DDQ/NEt(4)PF(6) or between 8 and DDQ/NaO(3)SCF(3), respectively. The substituted cationic iridabenzene [Ir(C(5)H(3){SMe-1}{Me-3})(κ(2)-S(2)CNEt(2))(PPh(3))(2)]PF(6) (6) or [Ir(C(5)H(4){SMe-1}{OEt-3})(κ(2)-S(2)CNEt(2))(PPh(3))(2)]PF(6) (7) is produced in a similar manner through reaction between 4 or 5, respectively, and DDQ/NEt(4)PF(6), and the substituted cationic osmabenzene [Os(C(5)H(3){SMe-1}{Me-3})(CO)(2)(PPh(3))(2)]Cl (10) is formed in good yield on treatment of 9 with CuCl(2). The starting cationic iridabenzene 1 is conveniently prepared by treatment of the neutral iridabenzene Ir(C(5)H(4){SMe-1})Cl(2)(PPh(3))(2) with NaS(2)CNEt(2) and NEt(4)PF(6), and the related starting cationic osmabenzene 2 is obtained by treatment of Os(C(5)H(4){S-1})(CO)(PPh(3))(2) with CF(3)SO(3)CH(3) and CO. The stepwise transformations of 1 into 6 or 7 as well as 2 into 10 provide the first examples in metallabenzene chemistry of regioselective nucleophilic aromatic substitutions of hydrogen by external nucleophiles. DFT calculations have been used to rationalize the preferred sites for nucleophilic attack at the metallabenzene rings of 1 and 2. The crystal structures of 1, 3, 6, and 7 have been obtained.

Poly[(μ2-2,2′-bipyridine-κ2N:N′)bis(μ3-2,2,2-trifluoroacetato-κ3O:O:O′)disilver(I)

In the title salt, [Ag2(CF3CO2)2(C10H8N2)]n, which may also be regarded as a coordination polymer if long Ag⋯O inter­actions are considered, each of the N atoms of the somewhat twisted 2,2′-bipyridine mol­ecule [N—C—C—N = −27.5 (4)°] binds to an Ag atom, and each of the carboxyl­ate ligands is tridentate, linking to three Ag atoms. The bidentate carboxyl­ate O atoms bridge the same two Ag atoms, resulting in the formation of Ag2O2 rings. These rings are bridged by the 2,2′-bipyridine ligands, forming a chain along the b axis. The chains are linked into double chains via the remaining Ag—O bonds and Ag⋯Ag contacts. As a consequence of the Ag⋯Ag contacts, the NO4 donor set about each Ag atom is heavily distorted. Finally, the chains are linked into a three-dimensional network by a combination of C—H⋯O and C—H⋯F inter­actions.

(Acetato-κ2O,O′)bis(1,10-phenanthroline-κ2N,N′)copper(II) trifluoroacetate tetrahydrate

In the title compound, [Cu(CH3CO2)(C12H8N2)2](CF3CO2)·4H2O, the CuII atom shows a distorted octa­hedral coordination with four N atoms [Cu—N = 2.015 (3)–2.244 (3) Å] from the two phenanthroline ligands and two O atoms from the acetate [Cu—O = 1.953 (3) and 2.764 (3) Å]. Strong inter­molecular O—H⋯O hydrogen-bonding inter­actions consolidate the crystal packing. The F atoms of the anion are disordered over two positions in a 0.5233 (3):0.4767 (3) ratio.

Effects of Counter Anions on Intense Photoluminescence of 1-D Chain Gold(I) Complexes

A series of cationic carbene complexes of Au(I) with different types of counteranions, [Au{C(OMe)NHMe}(2)](+)(X(-)) (X(-) = CF(3)SO(3)(-), PF(6)(-), CF(3)CO(2)(-), ClO(4)(-), and I(-)), was synthesized, and their intense photoluminescence was studied. These complexes crystallize in the same space group, and the X-ray crystallographic data of these samples revealed the short Au(I)-Au(I) aurophilic distances (3.263-3.335 A), where planar carbene Au(I) complexes are organized into linear stacks. The aurophilic Au(I)-Au(I) interactions found in the crystalline state give rise to phosphorescence with relatively high emission quantum efficiencies, whereas [Au{C(OMe)NHMe}(2)](+)(X(-)) complexes show no appreciable emission in solutions. The Au(I)-Au(I) distances in the crystal of [Au{C(OMe)NHMe}(2)](+)(X(-)) vary depending on the type of counteranions because the carbene ligands of Au(I) cations are linked through hydrogen bonds with adjacent counteranions. The effects of counteranions on the Au(I)-Au(I) aurophilic interactions allow one to modulate the intense photoluminescence color from blue to yellow by adjusting the counteranions of [Au{C(OMe)NHMe}(2)](+)(X(-)) complexes.

Structural, Spectroscopic, and Anion-Binding Properties of 5,10-Porphodimethenes, An Unusual Class of Calixphyrins

Complete spectroscopic, structural, and anion-binding properties are reported for a special class of calixphyrins, namely, 5,10-disubstituted porphodimethenes (PDMs). The crystal structure clearly shows that PDMs exhibit nonplanar (distorted) structures with both sp(2)- and sp(3)-hybridized meso carbon centers. We were able to obtain and characterize the diacid form [H(4)(PDM)][X](2) upon addition of several acids to PDMs, where X denotes anions of different acids: HCl, HBr, MeSO(3)H, CF(3)CO(2)H, and HClO(4). We found that the PDM dications generated were more conjugated and thus more stable than their corresponding porphyrins. Their potential to coordinate anions was clearly shown by using (1)H NMR spectroscopy. In addition, we found that when HClO(4) was used to protonate PDMs, the conversion occurs through an intermediate species, which has been assigned to the elusive monoacid derivative on the basis of UV-vis and (1)H NMR experiments.

Dynamic ring-opening polymerization of silver(i) complexes with bis(amidopyridine) ligands

The factors which influence the formation of chelate, macrocycle or polymer in the reaction of silver(i) salts with bis(pyridine) ligands have been probed by studying structures in the solid state and cold spray ionization mass spectra in solution, with the ligands C(6)H(4)-1,3-[CONR(CH(2))(n)-3-C(5)H(4)N](2), 1 (R = Me, n = 0) or (R = H, n = 1) or 5-t-Bu-C(6)H(3)-1,3-[CONR(CH(2))(n)-4-C(5)H(4)N](2), 2 (R = Me, n = 0) or 4 (R = H, n = 1). In both the solid state and solution, the complex [Ag12)]BF(4) exists as a chelate complex 5. The ligands NN = 2-4 form complexes in the solid state with either macrocyclic structures [Ag(2)(mu-NN)(2)]X(2) [6, NN =2, X = BF(4); 9, NN = 3, X = NO(3)] or polymeric structures [7, NN = 2, X = NO(3); 8, NN = 3, X = CF(3)CO(2); 10, NN = 4, X = CF(3)CO(2)]. The ligands 2 and 3 gave both macrocyclic and polymeric complexes, depending on the anion. In solution, these complexes existed as mixtures of macrocycles and ring-opened oligomers. In the crystalline state, the complexes 6-10 underwent supramolecular association through combinations of hydrogen bonding, secondary bonding of the type Ag...X to anions, or argentophilic bonding of the type Ag...Ag.

The first unpaired electron placed inside a C3-symmetry P-chirogenic cluster

The Pd(3)(dppm*)(3)(CO)(n+) enantiomers (n = 2 (2), 1 (3)) were prepared either from (R,R)- or (S,S)-P-chirogenic bis(phenyl-m-xylylphosphino)methane (dppm*; 1) and Pd(OAc)(2) in the presence of CF(3)CO(2)H, CO and water (n = 2), and then by reductive electrolysis (n = 1). The stable enantiomeric [Pd(3)((S,S)-dppm*)(3)(CO)](+)˙ (3), is the first C(3)-symmetry radical-cation M-M bonded cluster, therefore the odd electron is delocalized onto the Pd(3) frame within this symmetry. The novel chiral species have been characterized by circular dichroism (CD) of both enantiomers of the Pd(3)(dppm*)(3)(CO)(2+) clusters (2) and by EPR spectroscopy for the Pd(3)((S,S)-dppm*)(3)(CO)(+)˙ paramagnetic compounds (3, g = 2.041). Evidence for reduced symmetry with respect to the achiral cluster was also obvious from the hyperfine splittings of the EPR signal which display three different hyperfine coupling values: 3 ×A((31)P) = 83.9 × 10(-4) cm(-1), 3 ×A((31)P) = 69.7 × 10(-4) cm(-1), 3 ×A((105)Pd) = 12.5 × 10(-4) cm(-1). In the absence of an X-ray structure for the paramagnetic clusters, DFT computations were performed to address the geometry. The optimized geometry of the Pd(3)((S,S)-dppm*)(3)(CO)(+)˙ radicals (3) exhibits three phosphorus atoms placed well above the Pd(3) plane, while the three others are located below the trimetallic frame within C(3)-symmetry due to intramolecular steric hindrance. This makes them chemically different with respect to the carbonyl group and explains the experimental EPR spectrum well. Consequently this C(3)-symmetry deformation also induces a change in the shape of the SOMO (semi-occupied molecular orbital) towards this same symmetry compared to the corresponding achiral C(3v) species.

Dipyrazinyl Sulfoxide Complexes of Silver(I), Zinc(II), and Cadmium(II): Ligation Modes and Anion Tuning

The new ligand dipyrazinyl sulfoxide (also named sulfinyldipyrazine and abbreviated as pyz(2)SO) and a series of its metal complexes including {[Ag(pyz(2)SO)](NO(3)).CH(3)CN}(infinity) (1), {[Ag(pyz(2)SO)](PF(6))}(infinity) (2), [Ag(3)(pyz(2)SO)(2)(ClO(4))(3)](infinity) (3), [Ag(pyz(2)SO)(CF(3)CO(2))](infinity) (4), {[Zn(pyz(2)SO)(H(2)O)(4)](NO(3))(2).H(2)O}(infinity) (5), {[Zn(pyz(2)SO)(H(2)O)(2)](ClO(4))(2)}(infinity) (6), and {[Cd(pyz(2)SO)(2)(H(2)O)](ClO(4))(2).H(2)O}(infinity) (7) have been synthesized and characterized by single-crystal X-ray analysis. The counteranions in these complexes prefer to be embraced by a pair of pi-acidic heterocyclic rings via anion-pi interactions, which consequently affect the process of supramolecular assembly. Seven distinct ligation modes of pyz(2)SO involving various bonding combinations of the sulfoxide oxygen and/or pyrazinyl nitrogen atoms (labeled A-G) are observed. Diverse coordination motifs such as (4,4) network, ladder-type, necklace-like, linear, and zigzag-chain structures are found in 1-7. Interestingly, the sulfoxide group of the pyz(2)SO ligand exhibits unusual dipolar sulfinyl...sulfinyl and S=O...pi(pyrazinyl) intermolecular interactions in the supramolecular assemblies of neat pyz(2)SO, 1, and 3-5.

Sc3N@(C80-Ih(7))(CF3)14 and Sc3N@(C80-Ih(7))(CF3)16. Endohedral Metallofullerene Derivatives with Exohedral Addends on Four and Eight Triple-Hexagon Junctions. Does the Sc3N Cluster Control the Addition Pattern or Vice Versa?

The compounds Sc(3)N@(C(80)-I(h)(7))(CF(3))(14) (1) and Sc(3)N@(C(80)-I(h)(7))(CF(3))(16) (2) were prepared by heating Sc(3)N@C(80)-I(h)(7) and Ag(CF(3)CO(2)) to 350 degrees C in a sealed tube. The structures of 1 and 2 were determined by single-crystal X-ray diffraction. They are the first X-ray structures of any endohedral metallofullerene with more than four cage C(sp(3)) atoms. The structures exhibit several unprecedented features for metallic nitride fullerenes, including multiple cage sp(3) triple-hexagon junctions (four on 1 and eight on 2), no cage disorder and little (2) or no (1) endohedral atom disorder, high-precision (C-C esd's are 0.005 A for 1 and 0.002 A for 2), an isolated aromatic C(sp(2))(6) hexagon on 2, and two negatively charged isolated aromatic C(sp(2))(5)(-) pentagons on 2 that are bonded to one of the Sc atoms. DFT calculations are in excellent agreement with the two Sc(3)N conformations observed for 2 (DeltaE(calc) = 0.36 kJ mol(-1); DeltaE(exp) = 0.26(2) kJ mol(-1)).

Functionalization and Rearrangement of Spirocyclohexadienyl Oxindoles: Experimental and Theoretical Investigations

The preparation and functionalization of spirocyclohexa-2,5-diene oxindoles is described. The spirocyclic core of the title compounds was installed by using a SmI(2)-mediated cyclization of aryl iodobenzamides. Epoxidation with CF(3)CO(3)H was then carried out and was shown to occur with a high level of diastereocontrol: the reagent approaches the diene moiety syn to the amide group, which is likely to be as a consequence of hydrogen bonding between the amide C=O bond and the peracid hydrogen. Carbanionic functionalization of the spirocyclohexa-2,5-diene oxindoles was then examined, leading to an unprecedented rearrangement of the strained spiro system into dearomatized phenanthridinones. Upon treatment with lithium diisopropylamide (LDA) at -40 degrees C, the dienes rearranged to provide a phenanthridinone lithium enolate intermediate that was trapped by electrophiles including alkyl halides and aldehydes. Interestingly, alkylation and hydroxyalkylation occurred with different regiocontrol. DFT calculations were performed that rationalize the observed skeleton rearrangement, emphasizing the role of LDA/diisopropylamine in this rearrangement. The proposed mechanism thus relies on a thermodynamically driven diisopropylamine-mediated proton transfer with the cleavage of the diene-amide C=O bond as the key step.

Bis[N′-(3-cyanobenzylidene)isonicotinohydrazide]silver(I) trifluoroacetate

In the title compound, [Ag(C14H10N4O)2]CF3CO2, the AgI ion is coordinated by two N atoms of the pyridine rings of two N′-(3-cyano­benzyl­idene)isonicotinohydrazide ligands in a nearly linear geometry. In the crystal structure, a combination of close contacts formed via Ag⋯N inter­actions [Ag⋯N = 3.098 (2) and 3.261 (2) Å] from symmetry-related mol­ecules and inter­molecular N—H⋯O hydrogen bonds between CF3CO2 − anions and the hydrazone groups of two ligands give rise to chains. Furthermore, there are Ag⋯O inter­actions with a separation of 2.765 (2) Å between chains. The F atoms of the CF3CO2 − anion are disordered over two sites with refined occupancies of 0.593 (5) and 0.407 (5).

Electron Transfer Collisions with Oriented Trifluoroacetic Acid (CF3CO2H)

Electron transfer collisions between neutral K atoms and neutral, oriented trifluoroacetic acid molecules, CF(3)CO(2)H, are studied in crossed molecular beams at center of mass energies from 6 to 18 eV. An electron transfer produces a pair of ions with enough energy to escape the Coulomb attraction, and the ions are detected in separate time-of-flight mass spectrometers. The principle ions formed are K(+) and the trifluoroacetate ion, CF(3)CO(2)(-) ion, and this channel is favored for attack at the positive (-CO(2)H) end of the molecule. The steric asymmetry suggests that the electron is transferred into the pi*(CO) orbital. The nascent K(+) perturbs the molecular symmetry, allowing electron migration to the sigma*(OH) orbital to break the O-H bond and form CF(3)CO(2)(-).

Synthesis of trifluoromethyl fluoroformate from trifluoromethyl hypofluorite and carbon monoxide: Thermal and catalyzed reaction

New and improved routes to trifluoromethyl fluoroformate were developed. Sterically hindered halogenated olefins initiated the reaction of CF 3OF and CO under mild conditions, giving yields of up to 80%. The thermal reaction of CF 3OF and CO in a flow system was highly dependent on temperature and the type of tubular reactor material. A PTFE reactor gave moderate conversion and high selectivity for the formate at 120 °C.

Revision of the Gas-Phase Acidity Scale below 300 kcal mol−1

The gas-phase acidity (GA) scale from (CF(3)CO)(2)NH to (C(2)F(5)SO(2))(2)NH--about a 24 kcal mol(-1) range of gas-phase acidities--was reexamined using the Fourier transform ion cyclotron resonance equilibrium measurement approach. Some additions and modifications to the standard methodology of GA measurements were introduced (estimation of partial pressures from mass spectra of the compounds, instead of the pressure gauge readings and use of long reaction times) to achieve higher reliability. Gas-phase acidities of 18 compounds were determined for the first time. The results reveal a contraction of the previously published values in this part of the scale. In particular, the GA values of (CF(3)SO(2))(2)NH and (C(2)F(5)SO(2))(2)NH (important components of lithium ion battery electrolytes and ionic liquids) were revised toward stronger acidities from 291.8 kcal mol(-1) to 286.5 kcal mol(-1) and from 289.4 kcal mol(-1) to 283.7 kcal mol(-1) (i.e., by 5.3 and 5.7 kcal mol(-1)), respectively. Experimental and computational evidence is presented in support of the current results.

Control of Channel Size for Selective Guest Inclusion with Inlaid Anionic Building Blocks in a Porous Cationic Metal–Organic Host Framework

Step by step: By attaching anionic building blocks of variable bulk to a cationic metal-organic framework, stepwise channel-size adjustment of the resulting porous three-dimensional host framework is achieved (see picture). This method is a new and viable approach for materials with predesigned nanopores for application in molecular recognition and selective guest inclusion.Through the introduction of perfluorocarboxylates as counteranions that line the inner surface of each channel in a host cationic metal-organic open framework, stepwise channel-size control has been realized, resulting in wide guest compatibility for [{Ag(L)(CF(3)CO(2))}(6)6 G](infinity) (1 supersetG; G=guest, L=ligand), selective guest recognition for [{Ag(L)(C(2)F(5)CO(2))}(6)4 G'](infinity) (2 supersetG'), and a lack of inclusion behavior for [{Ag(L)(C(3)F(7)CO(2))}(6)](infinity) (3; G and G' represent the same or different guest molecules). The cationic frameworks in 1-3 are constructed from the linkage of hexameric inorganic-organic hybrid macrocycles through multiple argentophilic interaction plus pi-pi interactions between pyridyl rings and carbonyl-carbonyl interactions, to which corresponding counteranions are attached. With different anions as intrachannel arms, similar frameworks in complexes 1 supersetG, 2 supersetG', and 3 exhibit percentages of guest-accessible voids of approximately 30-35, 25, and 18 % for 1-3, respectively. The highly flexible framework 1 in 1 supersetG contains stretchable channels with up to 21.7 % effective-volume change of the solvent-accessible void for inclusion of various guest species in the series of solvates 1 a-m. The pair of complexes 1 supersetG and [Ag(L)(CF(3)CO(2))](infinity) (4), and likewise the pair 2 supersetG' and [Ag(L)(C(2)F(5)CO(2))](infinity) (5), are interconvertible through distinct controllable processes.

Highly Enantioselective Synthesis of Linear β‐Amino Alcohols

Beta-amino alcohols derived from alpha-amino acids have been extensively used as a powerful source of chirality. Transforming the alcohol moiety into a good leaving group has allowed the rearrangement of these beta-amino alcohols and the introduction of a large number of nucleophiles through the anchimeric participation of the nitrogen atom. An overview on the recent progress realized on the rearrangement of these beta-amino alcohols in the presence of (CF(3)CO)(2)O and H(2)SO(4) is reported.

Ionothermal synthesis of inorganic–organic hybrid materials containing perfluorinated aliphatic dicarboxylate ligands

Two new hybrid inorganic-organic frameworks containing perfluorinated dicarboxylate ligands have been synthesized ionothermally from a mixture of 1-ethyl-3-methylimidazolium bromide (emim-Br), and triflimide (emim-Tf(2)N). The cobalt(ii) tetrafluorosuccinate, [emim](2)[Co(H(2)O)(2)(O(2)CCF(2)CF(2)CO(2))(2)] (), is a two-dimensional coordination polymer containing anionic framework layers separated by emim cations. When hexafluoroglutaric acid is used in similar reactions, [emim](2)[Co(3)(O(2)CCF(2)CF(2)CF(2)CO(2))(4)(H(2)O)(4)] () forms. Like , this phase contains anionic layers of cobalt and the fluorinated carboxylate separated by emim cations. These new phases represent the first examples of ionothermally synthesized materials using perfluorinated aliphatic carboxylates.

Ancillary Ligands and Spectator Cations as Controlling Factors in the Construction of Coordination and Hydrogen‐Bonded Networks with the tert‐Bu‐CC⊃Agn (n=4, 5) Supramolecular Synthon

Supramolecular networks constructed with the tBu--C[triple bond]C superset Ag(n) (n=4 or 5) metal-ligand synthon and trifluoroacetate have been transformed through the introduction of ancillary terminal nitrile ligands, from acetonitrile through propionitrile to tert-butyronitrile, giving rise to a 2D coordination network in AgC[triple chemical bond]CtBu3 AgCF(3)CO(2)H(2)O (1), a 2D hydrogen-bonded network in AgC[triple chemical bond]CtBu5 AgCF(3)CO(2)4 CH(3)CNH(2)O (2), a 2D hybrid coordination/hydrogen-bonded network in AgC[triple chemical bond]CtBu3 AgCF(3)CO(2)CH(3)CH(2)CN2 H(2)O (3), and another 2D coordination network in AgC[triple chemical bond]CtBu4 AgCF(3)CO(2) (CH(3))(3)CCN2 H(2)O (4). Concomitantly, the linkage modes between adjacent ethynide-bound Ag(n) aggregates in these compounds are also changed. A layer-type hydrogen-bonded host lattice in isostructural AgC[triple chemical bond]CtBu4 AgCF(3)CO(2)(R(4)N)(CF(3)CO(2)) 2 H(2)O (R(4)=BnMe(3), 5; R(4)=Et(4), 6; R(4)=nPr(4), 7) is obtained by introducing quaternary ammonium cations as guest templates, which occupy the interstices and thereby mediate the interlayer separation. Use of the bulky nBu(4)N(+) cation leads to disruption of the host network in AgC[triple bond]CtBu4 AgCF(3)CO(2)3[(nBu(4)N)(CF(3)CO(2))]H(2)O (8) with generation of a discrete dense nido-Ag(5) cluster.