Advancing Inorganic Coordination Chemistry by Spectroscopy of Isolated Molecules: Methods and Applications

A unique feature of the work carried out in the Collaborative Research Center 3MET continues to be its emphasis on innovative, advanced experimental methods which hyphenate mass-selection with further analytical tools such as laser spectroscopy for the study of isolated molecular ions. This allows to probe the intrinsic properties of the species of interest free of perturbing solvent or matrix effects. This review explains these methods and uses examples from past and ongoing 3MET studies of specific classes of multicenter metal complexes to illustrate how coordination chemistry can be advanced by applying them. As a corollary, we will show how the challenges involved in providing well-defined, for example monoisomeric, samples of the molecular ions have helped to further improve the methods themselves thus also making them applicable to many other areas of chemistry

Novel Cofacial Porphyrin-Based Homo- and Heterotrimetallic Complexes of Transition Metals

We present a straightforward and generally applicable synthesis route for cofacially linked homo- and heterotrimetallic trisporphyin complexes. The protocol encompasses synthesising the first aryl-based, trans-o-phenylene trisporphyrin starting from pyrrole and benzaldehyde with an overall yield of 3.6 %. It also allows investigating the respective cis-isomer as the first conformationally restricted planar-chiral trisporphyrin. The free-base ligand was used in subsequent metalation reactions to afford the corresponding homotrimetallic Mn(III)-, Fe(III)-, Ni(II)-, Cu(II)-, Zn(II)- and Pd(II) complexes – additionally, a small adaptation of the protocol resulted in the defined Ni(II)Fe(III)Ni(II) complex in a total yield of 2.3 %. By monitoring Ni(II) insertion into the empty trimeric ligands, we affirmed that the outer porphyrin rings are filled before the internal ring. The molecular species were characterised by $^{1}$H NMR, UV-Vis, photoluminescence, IR, MS, CID, and high-resolution IMS measurements

Long-term monitoring of the internal energy distribution of isolated cluster systems

A method is presented to monitor the internal energy distribution of cluster anions via delayed electron detachment by pulsed photoexcitation and demonstrated on Co$_4{}^-$ in an electrostatic ion beam trap. In cryogenic operation, we calibrate the detachment delay to internal energy. By laser frequency scans, at room temperature, we reconstruct the time-dependent internal energy distribution of the clusters. The mean energies of ensembles from a cold and a hot ion source both approach thermal equilibrium. Our data yield a radiative emission law and the absorptivity of the cluster for thermal radiation.Comment: Manuscript LaTeX with 6 pages, 4 figures, plus LaTeX supplement with 9 pages, 4 figures and 2 tables. This article has been accepted by Physical Review Letter

Mechanistic and kinetic investigations of on/off (photo)switchable binding of carbon monoxide by chromium(0), molybdenum(0) and tungsten(0) carbonyl complexes with a pyridyl‐mesoionic carbene ligand

This work tackles the photochemistry of a series of mononuclear Cr0, Mo0 and W0 carbonyl complexes containing a bidentate mesoionic carbene ligand of the 1,2,3‐triazol‐5‐ylidene type. FTIR spectroscopy, combined with density functional theory calculations, revealed a clean photo‐induced reaction in organic solvents (acetonitrile, pyridine, valeronitrile) to give mainly one photoproduct with monosubstitution of a carbonyl ligand for a solvent molecule. The highest photodissociation quantum yields were reached for the Cr0 complex under UV irradiation (266 nm). Based on previous investigations, the kinetics of the dark reverse reactions have now been determined, with reaction times of up to several hours in pyridine. Photochemical studies in the solid state (KBr matrix, frozen solution) also showed light‐induced reactivity with stabilization of the metastable intermediate with a free coordination site at very low temperature. The identified reactive species emphasizes a mechanism without ligand–sphere reorganization.Deutsche Forschungsgemeinschaf

Cooperativity‐Driven Reactivity of a Dinuclear Copper Dimethylglyoxime Complex

In this report, we present the dinuclear copper(II) dimethylglyoxime (H$_2$dmg) complex [Cu$_2$(H$_2$dmg)(Hdmg)(dmg)]$^+$ (1), which, in contrast to its mononuclear analogue [Cu(Hdmg)$_2$] (2), is subject to a cooperativity-driven hydrolysis. The combined Lewis acidity of both copper centers increases the electrophilicity of the carbon atom in the bridging μ$_2$-O−N=C-group of H$_2$dmg and thus, facilitates the nucleophilic attack of H2O. This hydrolysis yields butane-2,3-dione monoxime (3) and NH$_2$OH that, depending on the solvent, is then either oxidized or reduced. In ethanol, NH$_2$OH is reduced to NH$_4$$^+$, yielding acetaldehyde as the oxidation product. In contrast, in CH$_3$CN, NH$_2$OH is oxidized by Cu$^{II}$ to form N$_2$O and [Cu(CH$_3$CN)4]$^+$. Herein are presented the combined synthetic, theoretical, spectroscopic and spectrometric methods that indicate and establish the reaction pathway of this solvent-dependent reaction

On the Hydrogen Oxalate Binding Motifs onto Dinuclear Cu and Ag Metal Phosphine Complexes

We report the binding geometries of the isomers that are formed when the hydrogen oxalate ((CO$_{2}$)$_{2}$H=HO$_{x}$) anion attaches to dinuclear coinage metal phosphine complexes of the form [M$_{1}$M$_{2}$dcpm$_{2}$(HOx)]$^{+}$ with M=Cu, Ag and dcpm=bis(dicyclohexylphosphino)methane, abbreviated [MM]$^{+}$. These structures are established by comparison of isomer-selective experimental vibrational band patterns displayed by the cryogenically cooled and N$_{2}$-tagged cations with DFT calculations of the predicted spectra for various local minima. Two isomeric classes are identified that feature either attachment of the carboxylate oxygen atoms to the two metal centers (end-on docking) or attachment of oxygen atoms on different carbon atoms asymmetrically to the metal ions (side-on docking). Within each class, there are additional isomeric variations according to the orientation of the OH group. This behavior indicates that HOx undergoes strong and directional coordination to [CuCu]$^{+}$ but adopts a more flexible coordination to [AgAg]$^{+}$. Infrared spectra of the bare ions, fragmentation thresholds and ion mobility measurements are reported to explore the behaviors of the complexes at ambient temperature

Inverse H/D Isotope Effects in Benzene Activation by Cationic and Anionic Cobalt Clusters

Reactions under single collision conditions with benzene C₆H₆ and with benzene-<i>d</i>₆ C₆D₆ of size selected cationic cobalt clusters Co_<i>n</i>⁺ and of anionic cobalt clusters Co_<i>n</i>^– in the cluster size range <i>n</i> = 3–28 revealed that dehydrogenation by cationic clusters is sparse, whereas it is ubiquitous in reactions by anionic clusters. Kinetic isotope effects (KIE) in total reaction rates are inverse and, in part, large. Dehydrogenation isotope effects (DIE) are normal. A multistep model of adsorption and stepwise dehydrogenation from the precursor adsorbate unravels a possible origin of the inverse KIE: Single step C–H bond activation is swift (no KIE in forward direction) and largely reversible (normal KIE backward) whereas H/D tunneling is likely to contribute (backward). DFT calculations of the structures and energetics along the reaction path in [Co₁₃C₆H₆]⁺ lend support to the proposed multistep model. The observed effects on rates and KIEs of cluster charges and of cluster sizes are noted to elucidate further

Cryo Kinetics and Spectroscopy of Cationic Nickel Clusters: Rough and Smooth Surfaces

The stepwise N₂ adsorption on size selected Ni₉⁺ and Ni₁₃⁺ clusters at 26 K is studied in a hybrid tandem ion trap instrument. Adsorption kinetics of these clusters in conjunction with infrared photon dissociation (IR-PD) spectroscopy of their cluster adsorbate complexes allows for the elucidation of various N₂ coverage and cluster size dependent effects, which are related to the rough Ni₉⁺ and smooth Ni₁₃⁺ cluster surface morphologies. Pseudo-first-order kinetic fits confirm consecutive adsorption steps by single exponential decays exclusively. The recorded IR-PD spectra of all observed cluster adsorbate complexes reveal IR active vibrational bands at frequencies of 2170–2260 cm^–1, which coincides with the range of metal head-on coordinated N–N stretching modes. Density functional theory (DFT) calculations confirm the experiments and reinforce a possible isomerization with low N₂ coverage in the case of Ni₉⁺