Athanasios Zavras

Synthesis, Structure and Gas-Phase Reactivity of a Silver Hydride Complex [Ag3{(PPh2)2CH2}3(μ3-H)(μ3-Cl)]BF4†

Coinage metal hydrides continue to attract attention because of their interesting structural and physical properties, as well as for their role as reagents or intermediates in the transformation of organic substrates. For example, several copper hydride compounds have been structurally characterized and developed as catalysts for 1,4 reduction reactions of enones and for hydrocupration of alkynes. In contrast, whereas their heavier congeners have been implicated as reactive intermediates in oxidation and other reactions, and have been characterized in the gas phase, as well as by matrix isolation experiments, few silver and gold hydride compounds have been synthesized and structurally characterized by X-ray crystallography. We have been examining the role of coinage-metal cluster compounds in C C bond coupling reactions, click chemistry, and C X bond activation 8] of organic substrates. In our work, methods based on mass spectrometry (MS) are employed to explore cluster formation and reactivity, and to direct condensed phase synthesis and characterization of novel clusters. As part of this cluster chemistry program, we became interested in extending the method of generating bis(phosphino)-protected gold nanoclusters by sodium borohydride reduction of gold salts to generate related silver nanoclusters. Herein, we report on the serendipitous MSbased discovery of a novel silver hydride cluster, [Ag3HClL3] + (L = bis(phosphino) ligand), which has prompted its massspectrometry-directed synthesis and X-ray and neutron crystallographic structural characterization, which reveal a {Ag3(m3-H)(m3-Cl)} + core structure. 14] The gas-phase reactivity of this cluster is also explored. Electrospray ionization mass spectrometry (ESI-MS) analysis of methanol/chloroform solutions of silver(I) trifluoroacetate [Ag(tfa)] that had been treated with sodium borohydride in the presence of 1,1-bis(diphenylphosphino)methane (designated hereafter as L) showed evidence of the formation of silver hydride cluster cations (Figure 1; see also the Supporting Information, Figure S1), which, based on isotope patterns (Figures S2 and S3) and high resolution accurate mass measurements (Table S1), are formulated as: [Ag3HL3] , [Ag3HClL3] , [Ag3Cl2L3] + and [Ag10H8L6] . The species [Ag3H2L3] + was not observed in any of the spectra recorded. Replacing NaBH4 with sodium borodeuteride confirmed that NaBH4 is the source of the hydride in the clusters (for example, formation of [Ag3DL3] 2+ and not [Ag3HL3] ; Figures S4 and S5). The observation of abundant silver hydride cluster cations by ESI-MS encouraged us to refine the condensed-phase synthetic route (Supporting Information, Method A) to allow the isolation of a crystalline salt suitable for characterization by IR and H NMR spectroscopy (Figures S6 and S7, as well as supporting text), as well as structural determination by single-crystal X-ray diffraction and neutron diffraction. The presence of the abundant trinuclear silver hydride cluster ligated by the trifluoroacetate (tfa) anion, [Ag3H(tfa)L3] +

Synthesis, Structural Characterization, and Gas-Phase Unimolecular Reactivity of the Silver Hydride Nanocluster [Ag3((PPh2)2CH2)3(μ3-H)](BF4)2

A bis(diphenylphosphino)methane-ligated trinuclear silver hydride nanocluster, [Ag3((Ph2P)2CH2)3(μ3-H)](BF4)2, featuring three silver(I) ions coordinated to a μ3-hydride, and its deuteride analogue, [Ag3((Ph2P)2CH2)3(μ3-D)](BF4)2, have been isolated and structurally characterized using electrospray ionization mass spectrometry (ESI-MS), X-ray crystallography, NMR and IR spectroscopy. The position of the deuteride in [Ag3((Ph2P)2CH2)3(μ3-D)](BF4)2 was determined by neutron diffraction. ESI-MS of [Ag3L3(μ3-H/D)](BF4)2 [L = ((Ph2P)2CH2)2] produces [Ag3L3(μ3-H/D)](2+) and [Ag3L3(μ3-H/D)(BF4)](+). A rich gas-phase ion chemistry of [Ag3L3(μ3-H/D)](2+) is observed under conditions of collision-induced dissociation (CID) and electron-capture dissociation (ECD). CID gives rise to the following complementary ion pairs: [Ag3L2](+) and [L+(H/D)](+); [Ag2(H/D)L2](+) and [AgL](+); [Ag2(H/D)L](+) and [AgL2](+). ECD gives rise to a number of dissociation channels including loss of the bis(phosphine) ligand, fragmentation of a coordinated bis(phosphine) ligand via C-P bond activation, and loss of a hydrogen (deuterium) atom with concomitant formation of [Ag3L3](+). Under CID conditions, [Ag3L3(μ3-H/D)(BF4)](+) fragments via ligand loss, the combined loss of a ligand and [H,B,F4], and cluster fragmentation to give [Ag2(BF4)L2](+) and [Ag2(L-H)L](+) [where (L-H) = (Ph2P)2CH(-)].

Ligand-induced substrate steering and reshaping of [Ag2(H)]+ scaffold for selective CO2 extrusion from formic acid

Metalloenzymes preorganize the reaction environment to steer substrate(s) along the required reaction coordinate. Here, we show that phosphine ligands selectively facilitate protonation of binuclear silver hydride cations, [LAg2(H)]+ by optimizing the geometry of the active site. This is a key step in the selective, catalysed extrusion of carbon dioxide from formic acid, HO2CH, with important applications (for example, hydrogen storage). Gas-phase ion-molecule reactions, collision-induced dissociation (CID), infrared and ultraviolet action spectroscopy and computational chemistry link structure to reactivity and mechanism. [Ag2(H)]+ and [Ph3PAg2(H)]+ react with formic acid yielding Lewis adducts, while [(Ph3P)2Ag2(H)]+ is unreactive. Using bis(diphenylphosphino)methane (dppm) reshapes the geometry of the binuclear Ag2(H)+ scaffold, triggering reactivity towards formic acid, to produce [dppmAg2(O2CH)]+ and H2. Decarboxylation of [dppmAg2(O2CH)]+ via CID regenerates [dppmAg2(H)]+. These gas-phase insights inspired variable temperature NMR studies that show CO2 and H2 production at 70 °C from solutions containing dppm, AgBF4, NaO2CH and HO2CH.

Modular Molecules: Site‐Selective Metal Substitution, Photoreduction, and Chirality in Polyoxometalate Hybrids

The first members of a promising new family of hybrid amino acid-polyoxometalates have emerged from a search for modular functional molecules. Incorporation of glycine (Gly) or norleucine (Nle) ligands into an yttrium-tungstoarsenate structural backbone, followed by crystallization with p-methylbenzylammonium (p-MeBzNH3(+)) cations, affords (p-MeBzNH3)6K2(GlyH)[As(III)4(Y(III)W(VI)3)W(VI)44Y(III)4O159(Gly)8(H2O)14]⋅47 H2O (1) and enantiomorphs (p-MeBzNH3)15(NleH)3[As(III)4(Mo(V)2Mo(VI)2)W(VI)44Y(III)4O160(Nle)9(H2O)11][As(III)4(Mo(VI)2W(VI)2)W(VI)44Y(III)4O160(Nle)9(H2O)11] (generically designated 2: L-Nle, 2 a; D-Nle, 2 b). An intensive structural, spectroscopic, electrochemical, magnetochemical and theoretical investigation has allowed the elucidation of site-selective metal substitution and photoreduction of the tetranuclear core of the hybrid polyanions. In the solid state, markedly different crystal packing is evident for the compounds, which indicates the role of noncovalent interactions involving the amino acid ligands. In solution, mass spectrometric and small-angle X-ray scattering studies confirm maintenance of the structure of the polyanions of 2, while circular dichroism demonstrates that the chirality is also maintained. The combination of all of these features in a single modular family emphasizes the potential of such hybrid polyoxometalates to provide nanoscale molecular materials with tunable properties.

Selectivity Effects in Bimetallic Catalysis: Role of the Metal Sites in the Decomposition of Formic Acid into H2 and CO2 by the Coinage Metal Binuclear Complexes [dppmMM′(H)]+

Design of new bimetallic catalysts requires an understanding of how cooperative effects of the metal sites influences reactivity. Here we show how switching one or both of the silver atoms in binuclear silver hydride cations, [dppmAg2(H)]+ (dppm=1,1‐Bis(diphenylphosphino)‐methane), with all combinations of copper and/or gold maintains selective dehydrogenation of formic acid, enhancing reactivity by up to 2 orders of magnitude. This is a key step in the selective, catalyzed extrusion of carbon dioxide from formic acid, HO2CH, with important applications in hydrogen storage and in situ generation of H2. Decarboxylation of [dppmMM′(O2CH)]+ through collision induced dissociation regenerates [dppmMM′(H)]+. DFT calculations provide insights into these cooperative effects. The copper homobinuclear catalyst performs best overall.

An unusual co-crystal [(μ2-dcpm)Ag2(μ2-O2CH)(η2-NO3)]2·[(μ2-dcpm)2Ag4(μ2-NO3)4] and its connection to the selective decarboxylation of formic acid in the gas phase

ESI/MS of an acetonitrile solution containing a mixture of AgNO3 :  bis(dicyclohexylphosphino)methane (dcpm, L) : NaO2CH in a molar ratio of 2 : 1 : 1 gave an abundant peak due to [LAg2(O2CH)]+ and a minor peak assigned as [L2Ag4(O2CH)3]+. When this acetonitrile solution was frozen and layered with diethyl ether and left undisturbed for six days, crystalline material suitable for X-ray crystallography was identified and separated from amorphous solids. Single crystal X-ray diffraction revealed an unusual co-crystal consisting of two discrete tetranuclear silver clusters [(μ2-dcpm)Ag2(μ2-O2CH)(η2-NO3)]2·[(μ2-dcpm)2Ag4(μ2-NO3)4]. While all of the coordinated formates in [LAg2(O2CH)]+ and [L2Ag4(O2CH)3]+ can be decarboxylated in the gas-phase under conditions of collision induced dissociation, only the hydride [LAg2(H)]+ thus formed reacts with formic acid via protonation and liberation of H2 to regenerate to formate, thereby closing a catalytic cycle for the selective decomposition of formic acid.

Two Spin-State Reactivity in the Activation and Cleavage of CO2 by [ReO2]−

The rhenium dioxide anion [ReO2](-) reacts with carbon dioxide in a linear ion trap mass spectrometer to produce [ReO3](-) corresponding to activation and cleavage of a C-O bond. Isotope labeling experiments using [Re(18)O2](-) reveal that (18)O/(16)O scrambling does not occur prior to cleavage of the C-O bond. Density functional theory calculations were performed to examine the mechanism for this oxygen atom abstraction reaction. Because the spins of the ground states are different for the reactant and product ions ((3)[ReO2](-) versus (1)[ReO3](-)), both reaction surfaces were examined in detail and multiple [O2Re-CO2](-) intermediates and transition structures were located and minimum energy crossing points were calculated. The computational results show that the intermediate [O2Re(η(2)-C,O-CO2)](-) species most likely initiates C-O bond activation and cleavage. The stronger binding affinity of CO2 within this species and the greater instabilities of other [O2Re-CO2)](-) intermediates are significant enough that oxygen atom exchange is avoided.

Gas-Phase Ion–Molecule Reactions of Copper Hydride Anions [CuH2]− and [Cu2H3]−

Gas-phase reactivity of the copper hydride anions [CuH2]- and [Cu2H3]- toward a range of neutral reagents has been examined via multistage mass spectrometry experiments in a linear ion trap mass spectrometer in conjunction with isotope labeling studies and Density Functional Theory (DFT) calculations. [CuH2]- is more reactive than [Cu2H3]-, consistent with DFT calculations, which show it has a higher energy HOMO. Experimentally, [CuH2]- was found to react with CS2 via hydride transfer to give thioformate (HCS2-) in competition with the formation of the organometallic [CuCS2]- ion via liberation of hydrogen; CO2 via insertion to produce [HCuO2CH]-; methyl iodide and allyl iodide to give I- and [CuHI]-; and 2,2,2-trifluoroethanol and 1-butanethiol via protonation to give hydrogen and the product anions [CuH(OCH2CF3)]- and [CuH(SBu)]-. In contrast, the weaker acid methanol was found to be unreactive. DFT calculations reveal that the differences in reactivity between CS2 and CO2 are due to the lower lying π* orbital of the former, which allows it to accept electron density from the Cu center to form the initial three-membered ring complex intermediate, [H2Cu(η2-CS2)]-. In contrast, CO2 undergoes the barrierless side-on hydride transfer promoted by the high electronegativity of the oxygen atoms. Side-on SN2 mechanisms for reactions of [CuH2]- with methyl iodide and allyl iodide are favored on the basis of DFT calculations. Finally, the DFT calculated barriers for protonation of [CuH2]- by methanol, 2,2,2-trifluoroethanol, and 1-butanethiol correlate with their gas-phase acidities, suggesting that reactivity is mainly controlled by the acidity of the substrate.

Gas Phase Formation, Structure and Reactivity of Gold Cluster Ions

With the advent of electrospray ionisation (ESI) and matrix-assisted laser desorption ionisation (MALDI), mass spectrometry (MS) is now routinely used to establish the molecular formulae of gold nanoclusters (AuNCs). ESI-MS has been used to monitor the solution phase growth of AuNCs when gold salts are reduced in the presence of phosphine or thiolate ligands. Beyond this analytical role, over the past 2 decades MS-based methods have been employed to examine the fundamental properties and reactivities of AuNC ions. For example, ion mobility and spectroscopic measurements may be used to assign structures; thermochemical data provides important information on ligand binding energies; unimolecular chemistry can be explored; and ion–molecule reactions with various substrates can be used to probe catalysis by AuNC ions. MS can also be used to monitor and direct the synthesis of AuNC bulk material either by guiding solution phase synthesis conditions or by soft landing a beam of mass-selected (i.e. monodisperse) AuNC ions onto a surface. This review showcases all areas in which mass spectrometry has played a role in AuNC science.